JPH02160369A - Grating for lead-acid battery - Google Patents
Grating for lead-acid batteryInfo
- Publication number
- JPH02160369A JPH02160369A JP63314634A JP31463488A JPH02160369A JP H02160369 A JPH02160369 A JP H02160369A JP 63314634 A JP63314634 A JP 63314634A JP 31463488 A JP31463488 A JP 31463488A JP H02160369 A JPH02160369 A JP H02160369A
- Authority
- JP
- Japan
- Prior art keywords
- lead
- zinc
- grating
- lattice
- acid battery
- 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
- 239000002253 acid Substances 0.000 title claims description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 239000002344 surface layer Substances 0.000 claims description 15
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 4
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 3
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 229910002058 ternary alloy Inorganic materials 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000000704 physical effect Effects 0.000 abstract description 2
- 230000001815 facial effect Effects 0.000 abstract 5
- 239000013543 active substance Substances 0.000 abstract 3
- 239000011149 active material Substances 0.000 description 13
- 238000012423 maintenance Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002142 lead-calcium alloy Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/68—Selection of materials for use in lead-acid accumulators
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、鉛蓄電池のサイクル寿命性能を向」ニさせる
ための改良を加えた鉛蓄電池用格子体に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a grid for lead-acid batteries that has been improved to improve the cycle life performance of lead-acid batteries.
従来より、鉛蓄電油用ペースト式極板は、活物質および
、この活物質の支持体である格子体により構成されてい
る。Conventionally, paste-type electrode plates for lead-acid electrical oil are composed of an active material and a lattice body that is a support for the active material.
近年、この種の格子体として鉛−カルシウム系合金から
なるものが開発されているが、この格ｒ体は自己放電咀
および電解液の減液量が少なく、メンテナンス性能に優
れている反面、鋳造性が悪く、粒界腐食による格丁内ｆ
ｆｉ糧への侵食が進みやすいなどの問題点があった。In recent years, this type of lattice body made of a lead-calcium alloy has been developed, but this lattice body has low self-discharge and electrolyte loss, and has excellent maintenance performance. The internal corrosion is poor due to intergranular corrosion.
There were problems such as easy erosion of fi food.
そこで、従来から広〈実施されている鋳造による格子体
の製法に代わるものとして、圧延シート祠料をエキスパ
ンド加工して成形されるエキスパンド格Ｙが開発された
。このエキスパンド格子の開発により、前記鉛−カルシ
ウム系合金からなる格子体の生産性を著しく向１−させ
ることができる七、圧延シートを使用することで、微細
な繊維状結晶組織が形成されるので、均一な表面腐食が
生じ、粒界腐食による格ｒの骨切れを防１ヒできるなど
の優れた特性を付加できて、メンテナンス性能を史に向
上させることができるに至った。Therefore, as an alternative to the conventional method of manufacturing lattice bodies by casting, expanded grade Y, which is formed by expanding a rolled sheet abrasive material, was developed. With the development of this expanded lattice, the productivity of the lattice made of the lead-calcium alloy can be significantly improved. 7. By using a rolled sheet, a fine fibrous crystal structure is formed. This has resulted in the addition of excellent properties such as uniform surface corrosion and the ability to prevent cracking of bones due to intergranular corrosion, resulting in an unprecedented improvement in maintenance performance.
しかしながら、この鉛−カルシウム系合金からなるエキ
スパンド格子の場合、充放電サイクルが繰り返されると
、活物質が軟化して格ｒ表面から脱落しやすくなる傾向
にあり、充放電サイクル寿命が必然的に短くなるという
問題点があった。However, in the case of an expanded lattice made of this lead-calcium alloy, when charge/discharge cycles are repeated, the active material tends to soften and easily fall off the surface, resulting in a short charge/discharge cycle life. There was a problem with that.
そこで、格子表面の活物質の脱落を防止するために、極
板間に介装するセパレータとして、ガラス繊維をＬ体と
する弾力性に富むマット状セパレータを使用して高群圧
構成にすることで、活物質と格子との密着性を強化して
充放電サイクルの性能向１−を図ることが考えられるが
、この場合、組立時において、１１う群圧構成とするに
は、多大な困難を伴い、１−業的１４産［二程において
は更に改良が必要となるものであった。Therefore, in order to prevent the active material on the lattice surface from falling off, a highly elastic mat-like separator made of L-shaped glass fibers is used as the separator interposed between the electrode plates to create a high group pressure configuration. In this case, it is possible to improve the performance of charge/discharge cycles by strengthening the adhesion between the active material and the lattice, but in this case, it would be extremely difficult to achieve a group pressure configuration of 11 during assembly. With this, 1-14 industrial products were produced [further improvement was required in step 2].
本発明は、メンテナンス性能に優れた上記のような鉛蓄
電池において、格子体を構成する合金の成分構成を改良
することにより、充放電サイクル寿命の向」二を図るこ
とを目的とするものである。The present invention aims to improve the charge/discharge cycle life of the above-mentioned lead-acid battery, which has excellent maintenance performance, by improving the composition of the alloy constituting the lattice body. .
このような目的を達成するために本発明は、格子体本体
の表面に多量の亜鉛を含有する表面層が形成されている
ことを特徴とする。鉛蓄電池用格子体を提供するもので
ある。In order to achieve this object, the present invention is characterized in that a surface layer containing a large amount of zinc is formed on the surface of the lattice body. The present invention provides a grid body for lead-acid batteries.
より具体的には、アンチモンレス鉛合金、中でも鉛−カ
ルシウム−錫系合金からなるシートを格子体本体の構成
材料とし、また、鉛−亜鉛系合金箔または鉛−亜鉛一錫
の二円元合金箔を表面層の構成材料として、前記合金シ
ートの表面に合金箔を圧７ｔシた１ユでエキスパンド加
Ｅを施して成形されるものであり、前記表面層の亜鉛３
打比率は０．旧ｉＴ（ｆｆｉ％以」−とすることが望ま
しい。More specifically, a sheet made of an antimony-free lead alloy, especially a lead-calcium-tin alloy, is used as the constituent material of the grid body, and a lead-zinc alloy foil or a lead-zinc one-tin alloy is used. The foil is used as a constituent material of the surface layer, and the alloy sheet is formed by applying an expanding process E at a pressure of 7 tons and 1 unit to form the alloy sheet, and the zinc 3 of the surface layer is
The batting ratio is 0. It is desirable to set it to the old iT (ffi% or more).
鉛蓄電池は充放電サイクルを繰り返して行うと、ｉＥ極
活物質が軟化脱落する傾向にあることは前述した。中で
もアンチモンレスの鉛合金、例えば鉛−カルシウム−錫
系合金を格子体に用いた場合、格子体と活物質との密着
性が低ドし、界面に剥離、亀裂現象などを生起して電池
容量が劣化するが、上記構成の本発明によると、格子体
の表面層が亜鉛を多量に含有しているので、表面層に生
じる酸化腐食層の特性が改善され、この腐食層の格子体
本体への密着性が増大して、活物質との界面における剥
離現象を抑制すると考えられ、また、亜鉛を多量に含ん
だ表面層では過充電電位が低下し、格子に近い部分に存
在する活物質の物性に影響を５えることも推察される。As mentioned above, when a lead-acid battery is repeatedly charged and discharged, the iE electrode active material tends to soften and fall off. Among these, when an antimony-free lead alloy, such as a lead-calcium-tin alloy, is used for the lattice, the adhesion between the lattice and the active material is low, causing peeling and cracking at the interface, which reduces battery capacity. However, according to the present invention having the above structure, since the surface layer of the lattice body contains a large amount of zinc, the characteristics of the oxidized corrosion layer formed on the surface layer are improved, and this corrosion layer is transferred to the lattice body body. It is thought that this increases the adhesion of the active material and suppresses the peeling phenomenon at the interface with the active material.Also, in the surface layer containing a large amount of zinc, the overcharge potential decreases, and the active material present near the lattice It is also inferred that it has a significant influence on physical properties.
以Ｆ１本発明の実施例を図面を参照しながら説明する。 Embodiments of the F1 invention will now be described with reference to the drawings.
この実施例に係る鉛蓄電池用格子体は、格子体本体の表
面に多量の亜鉛を含有する表面層を形成してなるもので
あり、具体的には以下の−Ｌ稈を経て作成した。The lattice body for a lead-acid battery according to this example was formed by forming a surface layer containing a large amount of zinc on the surface of the lattice body body, and was specifically created through the following -L culm.
鉛をＬ成分とし、カルシウムを０．０６重量％、錫を０
．２４市蹴％含有する鉛−カルシウム−錫合金により鋳
造板を作成し、この鋳造板の一面に鉛を主成分とし、亜
鉛を０．１重ｈｉ％含有する鉛−亜鉛合金箔を市ね合わ
せて、圧延ローラを通過させることにより、前記鋳造板
」−に前記合金箔を圧着させた圧延シートを作成した。Lead is the L component, calcium is 0.06% by weight, and tin is 0.
．． A cast plate is made from a lead-calcium-tin alloy containing 24% by weight, and a lead-zinc alloy foil containing lead as a main component and 0.1% zinc is placed on one side of this cast plate. A rolled sheet was prepared by pressing the alloy foil onto the cast plate by passing it through a rolling roller.
この圧延シートにエキスパンド加工を施した後、活物質
ペーストを充填してエキスパンド極板格子を作成し、こ
のエキスパンド格子を用いて試料電池（Ａ）を作成した
。After expanding this rolled sheet, it was filled with an active material paste to create an expanded electrode grid, and a sample battery (A) was created using this expanded grid.
また、比較例として前記鉛−カルシウムー錫合金からな
る鋳造板のみを圧延ローラを通過させて圧延シートを作
成し、実施例と同様の工程を経て得られたエキスパンド
格−ｒを組込んだ試料電池（Ｂ）を作成した。In addition, as a comparative example, only the cast plate made of the lead-calcium-tin alloy was passed through a rolling roller to create a rolled sheet, and a sample battery incorporating expanded grade-r obtained through the same process as in the example was also prepared. (B) was created.
これらの試料電？ｔｌｌ（Ａ）（Ｂ）を用いて充放電サ
イクル試験を行った。試験は、２０Ａで１時間放電し、
５Ａで５時間充電を行う充放電を１サイクルとして、２
５サイクル毎に２０Ａで容はチエツクを行い、初期値の
５０％未満になったときを寿命とした。These sample electrons? A charge/discharge cycle test was conducted using tll(A)(B). The test was performed by discharging at 20A for 1 hour,
One cycle is charging and discharging at 5A for 5 hours, and 2
The capacity was checked at 20A every 5 cycles, and the life span was determined when the capacity became less than 50% of the initial value.
図面にその結果を示しており、この図から明らかなよう
に、実施例の電池（Ａ）は従来構成の比較例の電池（Ｂ
）と比べて、サイクル性能が大幅に向トしている。寿命
に達した比較例の電池（Ｂ）を分解したところ、正極活
物質の軟化は殆ど見られず、格子体上部の活物質が浮き
」二がっているように観察され、格子と活物質問の密着
性が低下したものと推察された。一方、この実施例の電
池（Ａ）を分解したところ、正極活物質の表面部分が軟
化していた。また、格子体と活物質との密着性も比較的
良好であった。The results are shown in the figure, and as is clear from this figure, the battery of the example (A) is different from the battery of the comparative example (B) with the conventional configuration.
), the cycle performance is significantly improved. When the comparative example battery (B) that had reached the end of its life was disassembled, there was almost no softening of the positive electrode active material, and the active material on the top of the lattice was observed to be floating, and the lattice and active material It was inferred that the relevance of the questions had deteriorated. On the other hand, when the battery (A) of this example was disassembled, the surface portion of the positive electrode active material was found to have softened. Furthermore, the adhesion between the lattice and the active material was also relatively good.
なお、前記実施例においては、亜鉛を多（Ａに含ｆ「す
る層を圧延シートの−・而に形成したものを例示したが
、亜鉛に富む表面層を同シートの両面に形成したものに
おいても同様の結果が確認された。In addition, in the above-mentioned example, a layer containing a large amount of zinc (A) was formed on a rolled sheet, but a surface layer rich in zinc was formed on both sides of the sheet. Similar results were confirmed.
また、表面層における亜鉛の含有量は０．０１重ｉｉ１
％以］−で格子体と活物質問の密着性向］＝、の効果が
顕著になり、２．０重量％を超えると電解液の減液１１
が増加し、メンテナンス性能の低下が著しくなるので、
好ましくは２．０ 市ｉＪ％以上である。 ・方、錫は
格子と活物質問の充電受入性を改冴する効果があり、■
、θ〜ｌＯ重眼％の範囲であれば充電受入性を改１リシ
、充放電反応のバランスを保持してサイクル寿命性能の
向］−にも若トの効果を奏するものと４えられる。In addition, the zinc content in the surface layer is 0.01 weight ii1
% or more] - the effect of adhesion between the lattice and the living material becomes remarkable, and when it exceeds 2.0% by weight, the electrolyte decreases 11
increases, and the deterioration of maintenance performance becomes significant.
Preferably it is 2.0 iJ% or more.・On the other hand, tin has the effect of improving the charge acceptance of the grid and living matter,■
, θ to 10% is considered to have a significant effect on improving the charge acceptability, maintaining the balance of charge and discharge reactions, and improving cycle life performance.
なお、格子体本体に亜鉛を多量に含有する表面層を形成
する手段としては、前述の圧着によるものが作業効率、
材料歩留り等の観点からみて工業的価値が大きいが、こ
の他、プラズマ溶射や鍍金などの方法を利用しても何等
問題はない。As a means of forming a surface layer containing a large amount of zinc on the lattice body, the above-mentioned pressure bonding method has a high work efficiency and
Although it has great industrial value from the viewpoint of material yield, etc., there is no problem in using other methods such as plasma spraying and plating.
以を説明したように本発明の鉛蓄電池用格子体によると
きは、格子体本体の表面に多用の亜鉛を含有する表面層
を形成するものとしたので、電解液の減液も少なくて優
れたメンテナンス性能を維持するものでありながら、格
子体と、これに付着させた活物質問の密着性が著しく向
上し、充放電サイクル寿命を著しく向」；させることが
できるに至った。As explained below, when using the grid body for lead-acid batteries of the present invention, a surface layer containing a large amount of zinc is formed on the surface of the grid body body, so that electrolyte loss is reduced and is excellent. While maintaining maintenance performance, the adhesion between the lattice and the living matter attached to it has been significantly improved, and the charge/discharge cycle life has been significantly improved.
図面は本発明の実施例と従来構成の比較例についての充
放電サイクル寿命試験の結果を示す線図である。
サ イ り ルThe drawing is a diagram showing the results of a charge/discharge cycle life test for an example of the present invention and a comparative example of a conventional configuration. Cyrille
Claims (5)
が形成されていることを特徴とする鉛蓄電池用格子体。(1) A lattice body for a lead-acid battery, characterized in that a surface layer containing a large amount of zinc is formed on the surface of the lattice body.
れている請求項１記載の鉛蓄電池用格子体。(2) The lattice body for a lead-acid battery according to claim 1, wherein the lattice body is made of an antimony-free lead alloy.
金シートであり、この合金シートの表面に表面層である
鉛−亜鉛系合金箔を圧着した状態で、エキスパンド加工
により成形されてなる請求項１記載の記載の鉛蓄電池用
格子体。(3) The constituent material of the lattice body is a lead-calcium-tin alloy sheet, and the surface layer of the lead-zinc alloy foil is crimped onto the surface of this alloy sheet, and then it is formed by expanding. A lattice body for a lead-acid battery according to claim 1.
る請求項１２または３記載の鉛蓄電池用格子体。(4) The lattice for a lead-acid battery according to claim 12 or 3, wherein the surface layer contains 0.01% by weight or more of zinc.
れている請求項（３）または（４）記載の鉛蓄電池用格
子体。(5) The lattice body for a lead-acid battery according to claim 3 or 4, wherein the surface layer is constituted by a ternary alloy layer of lead-zinc-tin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63314634A JPH02160369A (en) | 1988-12-12 | 1988-12-12 | Grating for lead-acid battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63314634A JPH02160369A (en) | 1988-12-12 | 1988-12-12 | Grating for lead-acid battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02160369A true JPH02160369A (en) | 1990-06-20 |
Family
ID=18055680
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63314634A Pending JPH02160369A (en) | 1988-12-12 | 1988-12-12 | Grating for lead-acid battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02160369A (en) |
-
1988
- 1988-12-12 JP JP63314634A patent/JPH02160369A/en active Pending
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