JPH04206165A - Negative electrode gas absorbing type sealed type lead acid battery - Google Patents
Negative electrode gas absorbing type sealed type lead acid batteryInfo
- Publication number
- JPH04206165A JPH04206165A JP2332500A JP33250090A JPH04206165A JP H04206165 A JPH04206165 A JP H04206165A JP 2332500 A JP2332500 A JP 2332500A JP 33250090 A JP33250090 A JP 33250090A JP H04206165 A JPH04206165 A JP H04206165A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- negative electrode
- acid battery
- active material
- tin
- 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
- 239000002253 acid Substances 0.000 title claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 5
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 12
- 239000003365 glass fiber Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 239000011149 active material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910014474 Ca-Sn Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002637 fluid replacement therapy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は負極ガス吸収式密閉型鉛蓄電池、とくにその放
電容量の向上に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a negative electrode gas absorption type sealed lead acid battery, and particularly to improvement of its discharge capacity.
従来の技術
鉛蓄電池は二次電池として性能とコストのバランスがよ
くとれた電池であり、自動車用のＳＬＩ用電源、小型電
子機器や電動車に用いられる移動用電源、あるいはコン
ピューターなどの電源の停電時に作動するバックアップ
用据置き用電源と広く普及している。Conventional technology Lead-acid batteries are secondary batteries with a good balance of performance and cost, and can be used as power sources for SLI in automobiles, mobile power sources for small electronic devices and electric vehicles, or power outages for computers, etc. It is widely used as a backup stationary power supply that operates occasionally.
鉛蓄電池の特長の一つとして補液などのメンテナンスを
不要とする密閉化が可能であることかあげられる。この
密閉化の反応は正極表面上で発生した酸素がリテーナ中
を拡散し負極に達し、下式に示すような反応によって水
に還元されると同時に負極からの水素発生も制御される
ため、水の電気分解による電解液減少が低減される。One of the features of lead-acid batteries is that they can be sealed, eliminating the need for maintenance such as fluid replacement. In this sealing reaction, oxygen generated on the surface of the positive electrode diffuses through the retainer and reaches the negative electrode, and is reduced to water by the reaction shown in the equation below.At the same time, hydrogen generation from the negative electrode is also controlled. The decrease in electrolyte due to electrolysis is reduced.
正極：Ｈ２Ｃ１，／２０２÷２ ）（＋ ＋ ２ｅ負極
・Ｐｂ＋１／２０２− Ｐｂ○
ＰｂＯ＋Ｈ２ＳＯ４→ Ｐ ｂ Ｓ ０４ＰｂＳＯ４＋
２８＋＋２ｅ −
Ｐｂ＋Ｈ２ＳＯ＋
正極で発生した酸素ガスがいかに効率よく水に還元され
るかは、リテーナ中の酸素ガスの透過のしやすさに左右
される。そこで負極ガス吸収式密閉型鉛蓄電池では電解
液量を少なくし酸素ガスがすテーナ中を透過しやすいよ
うに設計しである。しかし、リテーナ中の電解液が歩な
（なると極板中に含まれる電解液も少なくなるっ
一方、正極の放電反応は下式に示すようにｐｂｏ、とＨ
こＳＯ４の反応であり、
ＰｂＯ２＋４Ｈ”−，２ｅ十Ｓ○４２−−Ｐ ｂ Ｓ
０４＋ ２ Ｈ：Ｏ
３○４２−イオンの移動のしやすさが正極の利用率を向
上させるのに重要となり、多くの研究がなされてきた。Positive electrode: H2C1, /202÷2 ) (+ + 2e negative electrode・Pb+1/202− Pb○ PbO+H2SO4→ P b S 04PbSO4+
28++2e − Pb+H2SO+ How efficiently the oxygen gas generated at the positive electrode is reduced to water depends on how easily the oxygen gas permeates through the retainer. Therefore, the negative electrode gas absorption type sealed lead-acid battery is designed to reduce the amount of electrolyte so that oxygen gas can easily permeate through the container. However, as the electrolyte in the retainer decreases (as the electrolyte contained in the electrode plate decreases), the discharge reaction of the positive electrode becomes pbo and H as shown in the equation below.
This is the reaction of SO4, PbO2+4H"-,2e10S○42--PbS
The ease of movement of 04+ 2 H:O 3○42- ions is important for improving the utilization rate of the positive electrode, and many studies have been conducted on this.
また、負極ガス吸収式密閉型鉛蓄電池では、前述のガス
吸収反応が負極上で起こるために負極容量のほうが正極
容量よりも大きくなるように正極容量規制の電池設計が
なされている。従って、負極ガス吸収式密閉型鉛蓄電池
の放電容量を増大させるためには、正極の利用率を向上
させることが最も重要である。Furthermore, in a sealed lead-acid battery with negative electrode gas absorption, the battery design is such that the negative electrode capacity is larger than the positive electrode capacity because the gas absorption reaction described above occurs on the negative electrode. Therefore, in order to increase the discharge capacity of a negative electrode gas absorption type sealed lead acid battery, it is most important to improve the utilization rate of the positive electrode.
発明が解決しようとする課題
負極ガス吸収式密閉型鉛蓄電池の正極活物質の１時間率
放電による放電前と後の孔径分布を水銀ポロシメーター
を用いて測定を行うと第１図にイミすような孔径分布の
差か見られた。すなわち、放電によって、おもに０．１
〜１μｍの孔径を有する正極活物質が反応することかわ
かる。このことから負極ガス吸収式密閉型鉛蓄電池の正
極利用率を向上させるためには、０．１〜１μｍの孔径
を有する正極活物質を増やせばよいことかわかる本発明
は、この０．１〜１μｍの孔径を有する正極活物質を選
択的に増加させ、負極カス吸収式密閉型鉛蓄電池の容量
を向上させるものである。Problem to be Solved by the Invention When the pore size distribution of the positive electrode active material of a negative electrode gas absorption type sealed lead-acid battery is measured before and after discharge by 1-hour rate discharge using a mercury porosimeter, the result is as shown in Figure 1. Differences in pore size distribution were observed. That is, due to the discharge, mainly 0.1
It can be seen that the positive electrode active material having a pore diameter of ~1 μm reacts. From this, it can be seen that in order to improve the positive electrode utilization rate of a negative electrode gas absorption type sealed lead-acid battery, it is sufficient to increase the positive electrode active material having a pore diameter of 0.1 to 1 μm. The capacity of a sealed lead-acid battery with negative electrode sludge absorption is improved by selectively increasing the amount of positive electrode active material having a pore diameter of 1 μm.
課題を解決するための手段
上記の課題を解決するために正極活物質中に金属錫、錫
酸化物、あるいは錫化合物を錫元素のモル数を正極活物
質中の鉛のモル数に対して０．０１〜５％添加すること
により０．１〜１μｍの細孔体積を増加させた活物質を
負極ガス吸収式密閉型鉛蓄電池に用いるものである。ま
た、正極活物質中の０．１〜１μｍの細孔体積が全細孔
体積の４０％以上にすることにより最も効果的な利用率
を得るものである。Means for Solving the Problems In order to solve the above problems, metallic tin, tin oxide, or a tin compound is added to the positive electrode active material so that the number of moles of the tin element is 0 to the number of moles of lead in the positive electrode active material. An active material whose pore volume has been increased by 0.1 to 1 μm by adding .01 to 5% is used in a negative electrode gas absorption type sealed lead acid battery. Further, the most effective utilization rate is obtained by making the volume of 0.1 to 1 μm pores in the positive electrode active material 40% or more of the total pore volume.
作用
表１に正極中に添加したＳ ｎ Ｓ ０４の添加量と平
均細孔径の関係を示した。表１によると、Ｓ ｎ Ｓ
０４の添加量が多いぼと平均細孔径が小さくなり孔径分
布か変化していることがわかる。この効果を鉛蓄電池に
適用すれば正極の利用率の向上に最も効果的な０．１〜
１μｍの細孔体積を選択的に増加させることが可能とな
る。さらに、Ｓ ｎ Ｓ Ｏ４の添加量と正極活物質の
全細孔体積および０．１〜１μｍの細孔体積を表２に示
した。Table 1 shows the relationship between the amount of S n S 04 added to the positive electrode and the average pore diameter. According to Table 1, S n S
It can be seen that as the amount of 04 added is large, the average pore diameter becomes smaller and the pore diameter distribution changes. If this effect is applied to lead-acid batteries, 0.1~
It becomes possible to selectively increase the pore volume of 1 μm. Furthermore, Table 2 shows the amount of S n S O 4 added, the total pore volume of the positive electrode active material, and the pore volume of 0.1 to 1 μm.
表２かられかるように、Ｓ ｎ Ｓ ０４の添加量を変
化させることによって０．１〜１μｍの細孔体積を選択
的に増加させることができるので、Ｓ ０４２−イオン
の正極活物質中への拡散性が向上し、電解液が少ない状
態での容量がアップすると考えられる。As shown in Table 2, by changing the amount of S n S 04 added, the pore volume of 0.1 to 1 μm can be selectively increased. It is thought that this improves the diffusivity of the electrolyte and increases the capacity when the amount of electrolyte is small.
（以 下 余 白） 実施例 本発明の実施例について以下゛説明する。(Hereafter, remaining white) Example Examples of the present invention will be described below.
鉛蓄電池製造用の鉛粉に、鉛粉中の鉛のモル数に対して
錫元素のモル数かＯ〜７％七なるように硫酸第１錫を添
加後、混合した。これに、常法にしたがって水と希硫酸
を滴下しなから練合し、正極用ペーストを作製した。Ｐ
ｂ−Ｃａ−Ｓｎ合金正極格子にこのペーストを充填した
後、熟成、乾燥の工程を経て未化成正極を得た。この未
化成正極と従来の未化成負極とをガラス繊維を主成分と
する不織布（リテーナ）を介して対向させた極板群を電
槽内に納め、所定量の電解液を注入した後、化成を行い
、容量２Ａｈ（１０時間率）の負極ガス吸収式の密閉型
鉛蓄電池を作製した。Stannous sulfate was added to lead powder for manufacturing lead-acid batteries so that the number of moles of tin element was 0 to 7% with respect to the number of moles of lead in the lead powder, and then mixed. To this, water and dilute sulfuric acid were added dropwise and kneaded according to a conventional method to prepare a positive electrode paste. P
After filling the b-Ca-Sn alloy positive electrode grid with this paste, an unformed positive electrode was obtained through aging and drying steps. A group of electrode plates in which this unformed positive electrode and a conventional unformed negative electrode are placed facing each other via a nonwoven fabric (retainer) mainly composed of glass fibers is placed in a battery container, and after injecting a predetermined amount of electrolyte, the chemical A negative electrode gas absorption type sealed lead-acid battery with a capacity of 2 Ah (10 hour rate) was prepared.
これらの電池を充電○、ＩＣ（放電容量の１２０％まで
充電）、放電ＩＣ（放電終止電池圧１．６０Ｖ）の条件
でサイクル試験を行い、各電池の容量とサイクル寿命（
初期容量の１／２容量に達したサイクル数）を測定した
。サイクル試験中の容量の比較とサイクル寿命を表３に
示す。These batteries were subjected to cycle tests under the conditions of charge ○, IC (charged to 120% of discharge capacity), and discharge IC (cell pressure at end of discharge 1.60V), and the capacity and cycle life of each battery (
The number of cycles at which the capacity reached 1/2 of the initial capacity was measured. Table 3 shows a comparison of capacities during cycle tests and cycle life.
ニド “１ｃｃ：
・ ・−： （Ｎ ：
・ ｉ：１
１ へ １− 〇 □
１− ｉ ” ｌ ： １
１ ′−１″′）１
ヒー千−冊−Ｈ
この表３かられかるように、ＳｎＳＯ４を添加 ４す
ると０．０１％以上の添加率の場合に、放電容量かアッ
プすることかわかった。しかし、７％まで添加量を増や
すと放電容量の増加傾向が認められなくなり、さらにサ
イクル寿命も無添加の場合よりも短（なった。また、０
．１〜１μｍの細孔体積の占有率と放電容量、サイクル
寿命の関係を見ると占有率が４０％を越えた場合に、著
しく放電容量の増加が認められた。Nido "1cc: ・ ・-: (N: ・i: 1 1 to 1- 〇 □ 1- i ” l: 1 1 '-1''') 1 He 1000 volumes-H As can be seen from this table 3 , it was found that the discharge capacity increased when the addition rate of SnSO4 was 0.01% or more.However, when the addition amount was increased to 7%, the tendency for the discharge capacity to increase was no longer observed, and further cycles The lifespan was also shorter than that without additives.
．． Looking at the relationship between the occupancy of pore volume of 1 to 1 μm, discharge capacity, and cycle life, when the occupancy exceeded 40%, a significant increase in discharge capacity was observed.
なお、上記実施例には、添加物として硫酸第１錫を用い
たが、金属錫、錫酸化物を用いても同様の効果が得られ
ることがわかった。Although stannous sulfate was used as an additive in the above embodiments, it was found that similar effects could be obtained by using metallic tin or tin oxide.
発明の効果
以上のように、本発明によれば金属錫、錫酸化物、ある
いは錫化合物を正極活物質中に添加することにより、０
．１〜１μｍの細孔を有する活物質の占有率を増加させ
、放電容量を増加させることが可能となった。Effects of the Invention As described above, according to the present invention, by adding metal tin, tin oxide, or a tin compound to the positive electrode active material,
．． It became possible to increase the occupancy of the active material having pores of 1 to 1 μm, thereby increasing the discharge capacity.
第１図は正極活物質の放電前と後の孔径分布をしした図
である。FIG. 1 is a diagram showing the pore size distribution of the positive electrode active material before and after discharge.
Claims (2)
る錫元素のモル数が、鉛蓄電池の正極活物質中の鉛元素
のモル数の０．０１〜５％の割合で添加された正極と、
ガラス繊維を主成分とした不織布に電解液を保持させた
リテーナと、負極とよりなる負極ガス吸収式密閉型鉛蓄
電池。(1) The number of moles of tin element contained in metallic tin, tin oxide, or tin compound is 0.01 to 5% of the number of moles of lead element in the positive electrode active material of the lead-acid battery. a positive electrode;
A negative electrode gas absorption type sealed lead-acid battery consisting of a negative electrode and a retainer that holds an electrolyte in a nonwoven fabric mainly made of glass fiber.
孔径を有する細孔の体積が全細孔体積の４０％以上であ
る負極ガス吸収式密閉型鉛蓄電池。(2) A negative electrode gas absorption type sealed lead-acid battery, in which the volume of pores having a pore diameter of 0.1 to 1 μm in the positive electrode active material according to claim 1 is 40% or more of the total pore volume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2332500A JP2949839B2 (en) | 1990-11-28 | 1990-11-28 | Negative gas absorption sealed lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2332500A JP2949839B2 (en) | 1990-11-28 | 1990-11-28 | Negative gas absorption sealed lead-acid battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04206165A true JPH04206165A (en) | 1992-07-28 |
| JP2949839B2 JP2949839B2 (en) | 1999-09-20 |
Family
ID=18255631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2332500A Expired - Lifetime JP2949839B2 (en) | 1990-11-28 | 1990-11-28 | Negative gas absorption sealed lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2949839B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009158286A (en) * | 2007-12-26 | 2009-07-16 | Gs Yuasa Corporation | Lead-acid battery and method of manufacturing the same |
| JP2021057108A (en) * | 2019-09-26 | 2021-04-08 | 古河電池株式会社 | Lead-acid battery |
| JP2021086732A (en) * | 2019-11-27 | 2021-06-03 | 古河電池株式会社 | Positive electrode plate for lead acid battery, and lead acid battery |
-
1990
- 1990-11-28 JP JP2332500A patent/JP2949839B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009158286A (en) * | 2007-12-26 | 2009-07-16 | Gs Yuasa Corporation | Lead-acid battery and method of manufacturing the same |
| JP2021057108A (en) * | 2019-09-26 | 2021-04-08 | 古河電池株式会社 | Lead-acid battery |
| JP2021086732A (en) * | 2019-11-27 | 2021-06-03 | 古河電池株式会社 | Positive electrode plate for lead acid battery, and lead acid battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2949839B2 (en) | 1999-09-20 |
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