JPS5818865A - Sealed type battery - Google Patents
Sealed type batteryInfo
- Publication number
- JPS5818865A JPS5818865A JP56116356A JP11635681A JPS5818865A JP S5818865 A JPS5818865 A JP S5818865A JP 56116356 A JP56116356 A JP 56116356A JP 11635681 A JP11635681 A JP 11635681A JP S5818865 A JPS5818865 A JP S5818865A
- Authority
- JP
- Japan
- Prior art keywords
- sealing material
- chromium
- oxide layer
- chromium oxide
- 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
- 239000003566 sealing material Substances 0.000 claims abstract description 41
- 229910000423 chromium oxide Inorganic materials 0.000 claims abstract description 29
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000010410 layer Substances 0.000 claims description 32
- 229910052804 chromium Inorganic materials 0.000 claims description 17
- 239000011651 chromium Substances 0.000 claims description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 238000010248 power generation Methods 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- -1 polypropylene Polymers 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000002356 single layer Substances 0.000 claims 1
- 229920002994 synthetic fiber Polymers 0.000 claims 1
- 239000012209 synthetic fiber Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 27
- 238000007789 sealing Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- 241001474791 Proboscis Species 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 210000003323 beak Anatomy 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/186—Sealing members characterised by the disposition of the sealing members
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/191—Inorganic material
-
- 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)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
【発明の詳細な説明】 この発明は、密閉式−池に喘する。[Detailed description of the invention] This invention applies to closed ponds.
例えば、密閉式のアルカリ電池は、第１図ろるいはｇｇ
図に示すように、端子を兼ねる金爽委゛屯池ケース１内
に陽極活物質２ａ、アルカリ電解液を含むセパレータ２
ｂおよび嘴極活物質２Ｃを！−状に配列してなる発ＩＩ
要素２が装填されるとともに、電池ケース１が封口材８
で密封され、゛さらにその封口材８が心気４８縁性で′
るって、この封口材８によって陽極端子側と陰極端子間
とが互に絶縁隔離されてなる構成を有してい６゜
このような密閉式ＩＥ池において最も関心事となるのは
、その内部に封じ込めである発電要素２に含まれている
電解液を如何に安定に閉じ込め、外部へ漏出させないよ
うにするかである。For example, sealed alkaline batteries are
As shown in the figure, a separator 2 containing an anode active material 2a and an alkaline electrolyte is placed inside a metal case 1 that also serves as a terminal.
b and beak electrode active material 2C! II, which is arranged in a - shape.
While the element 2 is loaded, the battery case 1 is sealed with the sealing material 8.
The sealing material 8 is sealed with a
Therefore, the anode terminal side and the cathode terminal side are insulated and isolated from each other by the sealing material 8.What is of greatest concern in such a closed type IE pond is the internal The problem is how to stably confine the electrolyte contained in the power generation element 2 and prevent it from leaking outside.
特に、第１図あるいは第２図に示した如き蝙平伏あるい
はボタン型の小駿密閉式アルカリ電池においては、小型
化という目的を達成するために、アルカリ１を解液の漏
液を防止するためのシール構造は、どうしても簡単なも
のにせざるを痔ない、しかし、そこで使用されているア
ル芳り゛−電解液、周知の如く、きわめて滲出力が強く
、特に陰極側合４表面に旧ってクリープを生じさせやす
い、このため、従来においては、封口材８とこの封口材
８と接する陰蟻側金＠憾分４（またはｔｂ）との界面に
例えばエポキシ鋼脂とかａｓｈ質を層Ｂａ状に配し、こ
れによりアールカリ電解液のクリープを阻止せんとして
いた。しかしながら、エポキシ樹脂とか瀝青吻貞は経時
的に必ずしも安定な便質ではなく、少なくとも上記界［
ＩＫ層状に配した状態では、アルカリ電解液によるクリ
ープの発生を長期に亘って確実に阻止することはできな
い。また、封口材８がガラスあるいはセラミックス等の
場合には、そのエポキシ樹脂とか１ｉｕｒ物貞を封口材
と金属部分との界面に設けることは封−８１Ｍ度等の兼
ね合いから当然できない、すなわち、ハーメチックシー
ルタイプの密閉式アルカリ電池に適用することは不可能
である。ここで、上記封口材８として、ガラスやセラミ
ックス等を用いた、いわゆるハーメチッククールタイプ
のものにあっても、アルカリ電解液は、その封口材８と
金１１１部分４との界面に沿って、やけ９クリープを生
じさせ、これによシ漏液を生じさせる。In particular, in the folded or button-shaped sealed alkaline batteries shown in Figure 1 or Figure 2, in order to achieve the goal of miniaturization, alkali 1 is used to prevent leakage of the solution. The seal structure must be simple, but as is well known, the alkaline electrolyte used therein has a very strong leakage force, and especially on the surface of the cathode joint 4. For this reason, in the past, a Ba-like layer of epoxy steel or ash was applied to the interface between the sealing material 8 and the ant-side metal 4 (or tb) in contact with the sealing material 8. This was intended to prevent the creep of the alkaline electrolyte. However, epoxy resin and bituminous resin do not necessarily provide stable stool quality over time, and at least the above-mentioned [
When the IK layer is arranged, it is impossible to reliably prevent creep caused by the alkaline electrolyte over a long period of time. Furthermore, when the sealing material 8 is made of glass or ceramics, it is naturally impossible to provide the epoxy resin or 100% material at the interface between the sealing material and the metal part due to the sealing degree of -81M, that is, a hermetic seal. It is not possible to apply this type of sealed alkaline battery. Here, even if the sealing material 8 is of a so-called hermetic cool type using glass, ceramics, etc., the alkaline electrolyte may be mixed along the interface between the sealing material 8 and the gold 111 portion 4. 9 creep, which causes liquid leakage.
筐だ、上述した如＠笛閉式アルカリ寛池においては、電
池ケースｌ内に、おける電気化学的反応によって発生期
の水素が生じることが多いが、この発生期の水率が封口
材、８と金属部分との界面部分を便数し、これがアルカ
リ電解液の漏液原因となる場合も少なくない。また、電
池内で発生した水素は１［池内圧を高めて、上記封口材
８とこれに接する金属部分との密着性を破壊し、これに
よって漏液を生じさせることもめる。さシにまた、アル
カリ電池の多くは、陰極物質２Ｃとして未化犠鉛を用い
ているが、この未化犠鉛によって封口材８と金属部分と
の界面が東北され、この未化にともなって上記クリープ
が進行する士うにもなる。In the above-mentioned closed type alkaline pond, hydrogen is often produced in the battery case by an electrochemical reaction in the nascent stage, but the water rate during this nascent stage is the sealing material, The interface with the metal part is often the cause of alkaline electrolyte leakage. Further, the hydrogen generated within the battery increases the internal pressure of the battery and destroys the adhesion between the sealing material 8 and the metal parts in contact with it, thereby causing leakage. In addition, many alkaline batteries use unformed sacrificial lead as the cathode material 2C, but the interface between the sealing material 8 and the metal part is distorted by this unformed sacrificial lead, and with this unformed sacrificial lead. This will also prevent the creep described above from progressing.
以上のようなことを囲みると、第１図あるいは第２図に
示した如き比較的小型の・層間式電池においては、その
きわめて限られた容積内で、有効空電容積を損なうこと
なく電解液の漏液を確、夷に防止し轡るようにすること
は、著じ〈至雌なことである。 。Considering the above, in a relatively small interlayer type battery as shown in Figure 1 or Figure 2, electrolysis can be carried out within its extremely limited volume without loss of effective static capacity. It is extremely important to ensure that liquid leaks and prevents leakage. .
この発明の目的とするところ）ま、以上に述べたような
様々な要ト和によって生じる電解液の１敲を、第１図あ
るいは第２図に示した如き比較的小型の密閉式アルカリ
電池においても、その有効発１１Ｅ面積を少しも損なう
ことなく、かつ簡単なシール構造でもって、確実に防止
できるようにすることにある。The purpose of this invention is to use a relatively small sealed alkaline battery as shown in FIG. It is an object of this invention to be able to reliably prevent this problem without impairing the effective emitting area 11E in the slightest and with a simple sealing structure.
この発明による密閉式電池は、刃口材とこれに接する金
属部分との少なくとも陰極側界面に沿って厚与が０．１
〜２μのクロムの酸化物！−を設けたことを特徴とする
ものでｂシ、これにより、先ず機械的には、その酸化物
層と金属部分との間に強固かつ安定な結合状態を得、ま
た化学的および電気化学的には、アルカリ電解液および
電池内の種物質に対してもき、わめて安定で、さらに水
素過電圧が十分に高く、発生期の水素に対して十分に安
定で、シ卆も非常に東北され難く、これによシ前述した
如き種々の要因によるアルカリ電解液の漏液をも確実に
耐重し得るようにしたもの、でるる。The sealed battery according to the present invention has a thickness of 0.1 along at least the cathode-side interface between the cutting edge material and the metal portion in contact therewith.
~2μ chromium oxide! - This is characterized by providing a strong and stable bond between the oxide layer and the metal part mechanically, and also chemically and electrochemically. It is extremely stable against alkaline electrolytes and seed materials in batteries, has a sufficiently high hydrogen overvoltage, is sufficiently stable against nascent hydrogen, and is extremely stable against the hydrogen in the nascent stage. This makes it possible to reliably withstand leakage of alkaline electrolyte caused by various factors as mentioned above.
以下、この発明の実施例を添付図面を参照しながら詳コ
ポする。Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
哨３図は、この発明による密閉式′成池の一実施例を示
したものである。同図に示した電池は、電解液としてア
ルカリ水浴液を使用するものであり、また、・４１図に
示した従来のものとほぼ同型のもので、先ず、陽極端子
を兼ねる全構製電池ケース１内に陽極活物質２ａ、アル
カリ電解液を含むセパレータ２ｂおよび陰極活物質２Ｃ
からなる発酸要素２を装填するとともに、そのケースｌ
の上部中央に陰極端子を兼ねる金属裂果電リードが質通
し、ケース１とリード４との間の環状隙間部分５がガラ
スよりなる封口材８によって封止され、かつ両端子側間
が電気的に互に絶縁隔離されている。そして、上記ガラ
ス封口材８と接する金属部分すなわち封口材８と集電リ
ード４との接触界面には、クロムの酸１ヒ物層６が０．
１〜２μの厚みでもって形成されている。このクロムの
酸化物層６は、実施例では、金＠部分である上記果畦リ
ード４１１１１に予め形成されたものでめる。このクロ
ムの竣化吻１−６は、少なくとも上記封口材８と接する
部分に沿って設けられる。さらに、クロムの酸化物ｌ−
６は、少なくとも陰極端子側の金属部分には必ず設けな
ければならない。しかし、望ましくは、陽極熾子何にも
そのクロムの酸化物１６を設ける。Figure 3 shows an embodiment of the closed type growth pond according to the present invention. The battery shown in the same figure uses an alkaline water bath liquid as the electrolyte, and is almost the same type as the conventional one shown in Figure 41. 1 contains an anode active material 2a, a separator 2b containing an alkaline electrolyte, and a cathode active material 2C.
At the same time as loading the acid generating element 2 consisting of
A metal cracked electrical lead that also serves as a cathode terminal is pawned at the center of the upper part of the case 1, and an annular gap 5 between the case 1 and the lead 4 is sealed with a sealing material 8 made of glass, and the electrical connection between both terminal sides is They are insulated and isolated from each other. Then, on the metal portion in contact with the glass sealing material 8, that is, on the contact interface between the sealing material 8 and the current collecting lead 4, a chromium acid/arsenic layer 6 is applied.
It is formed with a thickness of 1 to 2 μm. In the embodiment, this chromium oxide layer 6 is formed in advance on the above-mentioned ridge leads 41111, which are gold@ portions. This chromium finished proboscis 1-6 is provided along at least the portion that contacts the sealing material 8. Furthermore, chromium oxide l-
6 must be provided at least on the metal part on the cathode terminal side. Preferably, however, the anode layer is provided with the chromium oxide 16.
クロムの酸化物層６の厚みは、後述するように、０．１
−より小さくても、あるいは２μより大きくても好まし
くない。The thickness of the chromium oxide layer 6 is 0.1 as described later.
- It is not preferable if it is smaller than 2μ or larger than 2μ.
ここで、上記クロムの酸化物層６を形成するためには、
封口材８が接する合間部分の少なくとも表面部分をクロ
ムもしくはクロムを含む合金で形成し、さらにその金属
部分の表面を酸化処理すればより、このとき、上記１電
リード４あるいは必要に応じて上記ケースｌは、少なく
ともその表面をクロムもしくはクロムを含む合金で形、
盛するために、その渠Ｋ ＩＪ−ド４とケースｌ全体を
クロムもしくはクロムを含む合金で形成するか、わるい
は果シリード４、ケースｌをクロムとは別の合端で形成
して、その必要な部分にクロムもしくはクロムを含む合
金全メッキ等によって被覆する。封口材８と接する金属
部分の表面に形成するクロムの酸化物＠６としては、Ｏ
ｒ ２０ ｇが適当で６□るが、ＱｒＯ、０ｒ０２、Ｏ
ｒ ２０６、Ｏｒ Ｏａ等でもよい、 、第４図
は、この発明の池の実施例を示したもので、同図に示す
電池は、禰２−に示したものと同型のものである。同図
に示し九′電池では、１イ池ケースｌが、ｌｉ＃ｌ極側
ケース部１＆と陰極側ケース部１ｂとに分割形成され、
両ケース部１ａ、ｌｂＯ間の環状の封口材８が介在する
ことによって、内部に装填された発電要素を密封してい
る。この場合、封口材８は、ナイロン、ポリプロピレン
、ポリエチレン等のように、電気恒数性でかつ弾力性を
有する合成樹脂が使用されている。陰極側ケース部１ａ
および陰極側ケース部１ｂは、共に金ｍ製でめって、゛
ケース部ｌａが陽極端子を、またケース部１ｂが陰極端
子をそれぞれ衣ねるようになっている。この実施−の場
合、封口材８に圧接する金属部分すなわち両ケース部１
ａ、ｌｂの各開口毫部付近には＠ｄ己のように厚み、が
０．１〜２μのクロムの酸化物層６が設けられている。Here, in order to form the chromium oxide layer 6,
At least the surface portion of the gap where the sealing material 8 contacts is made of chromium or an alloy containing chromium, and the surface of the metal portion is further oxidized. l is formed at least on the surface of chromium or an alloy containing chromium,
In order to increase the thickness, the entire conduit 4 and case 1 are made of chromium or an alloy containing chromium, or alternatively, the culvert 4 and case 1 are made of a joint end other than chromium, and the The necessary parts are coated with chromium or an alloy containing chromium, etc. by complete plating. The chromium oxide @6 formed on the surface of the metal part in contact with the sealing material 8 is O.
r 20 g is appropriate and 6□, but QrO, 0r02, O
Figure 4 shows an embodiment of the pond of the present invention, and the battery shown in the figure is of the same type as that shown in Figure 2-. In the 9' battery shown in the same figure, a single case l is divided into a li#l electrode side case part 1& and a cathode side case part 1b,
The annular sealing material 8 interposed between the case parts 1a and lbO seals the power generation element loaded inside. In this case, the sealing material 8 is made of a synthetic resin having electrical constant and elasticity, such as nylon, polypropylene, polyethylene, or the like. Cathode side case part 1a
Both the cathode side case part 1b are made of gold, and the case part la serves as an anode terminal, and the case part 1b serves as a cathode terminal. In this case, the metal parts that come into pressure contact with the sealing material 8, that is, both case parts 1
A chromium oxide layer 6 having a thickness of 0.1 to 2 μm is provided near each of the openings a and lb, as shown in d.
このクロムの酸化物層６は、少なくとも゛陰極側ケース
部ｔｂと封口材８との接触界面に沿った部分には設けな
ければならない、これは、前述の実施例と共通するが、
アルカリ電解液は、電池内の電位差によって特に陰極側
の金属部分表面に沿ってクリープを生じさせやすいとい
う理由による。こζでも、そのクロムの酸化物層６は、
陰極側のみならず陽極側にも設けることが一層好ましい
、また、このクロムの酸化物層６の形成は、前述の場合
と同様にして形成することができる。This chromium oxide layer 6 must be provided at least along the contact interface between the cathode side case part tb and the sealing material 8. This is common to the previous embodiment, but
This is because alkaline electrolytes tend to cause creep, especially along the surface of the metal part on the cathode side, due to the potential difference within the battery. Even in this case, the chromium oxide layer 6 is
It is more preferable to provide the chromium oxide layer 6 not only on the cathode side but also on the anode side, and the chromium oxide layer 6 can be formed in the same manner as described above.
さて、以上のように上記封口材８とこれに接する金ｓ部
分との界面に沿ってクロムの酸化物層６を設けると、こ
の酸化物４６は、前述したように、それが形成された金
属部分との間に非常に強固かつゲ定な結合状態を呈する
ようにな）、これによシ金１４部分の表面に沿って進行
するアルカリ、ｔＮ４液によるクリープが阻止される。Now, when the chromium oxide layer 6 is provided along the interface between the sealing material 8 and the gold s portion in contact with it as described above, this oxide 46 is formed by the metal on which it is formed. This forms a very strong and firm bond between the metal parts and the metal parts, thereby preventing the creep caused by the alkali and tN4 liquid from proceeding along the surface of the metal parts.
また、これとともに、そのクロムの准化物層６は、アル
カリ電解液に対しても安定でおり、かつ電池内で生ずる
ことの多い発生期水素に対しても非常に安定であシ、シ
かも十分に高い水素過電圧を呈することができ、従って
化学的および電気化学的な浸蝕作用に原因するアルカリ
電解液の／Ｉ液も確実に阻止できるようになる。さらに
また、そのクロムの酸化物層６は、非常に氷化され難い
という性質も有してシシ、従って陰極中質２Ｃとして水
化＠！１ｅｔ−用いたアルカリ電池で６って、その未化
岨鉛が封口材と金部部分との界面の端部に直接接触する
ようなことが６っても、それによってアルカリ電解液が
漏液するような状態に至ることはない。In addition, the chromium quasi-oxide layer 6 is stable against alkaline electrolytes and is also very stable against nascent hydrogen, which is often generated in batteries. It is possible to exhibit a high hydrogen overvoltage and thus to reliably prevent the /I solution of the alkaline electrolyte due to chemical and electrochemical corrosive effects. Furthermore, the chromium oxide layer 6 has the property of being extremely difficult to freeze, and therefore becomes hydrated as the cathode medium 2C! In an alkaline battery using 1 et-6, even if the unconverted lead comes into direct contact with the edge of the interface between the sealing material and the metal part, this will cause the alkaline electrolyte to leak. You will never reach such a state.
以上のようにして、シール部分にそれほどの複雑化ｔ＃
うことなく、きわめて簡略化し九クール構造のｔまでも
って、アルカリ電解液の漏液を確実に阻止することがで
きるように表る。As described above, the seal part is not so complicated.
It appears that leakage of the alkaline electrolyte can be reliably prevented with a very simplified nine-cooled structure.
ここで、第６図は、アルカリ電解液によるクリープ速度
を電池系外で調べるための試験方法を示したものである
。同図に示す方法では、陽極活物質として使用される氷
化岨鉛７とアルカリ電解液８を入れた容器９内に、金属
棒１０を立てる。この金属棒１０の上方には、封口材８
が、実際の電池のシール構造を形成する場合と−じよう
に、環状に取りまいて密着されている。そして、その封
口材８と金属棒１０との界面には、アルカリ電解液によ
るクリープを阻止するための耐クリープ材層１１が設け
られる。ここで、上記封口材８および上記耐クリープ材
層１１の橿急を色々変えて、その種類の組み合せ毎に、
上記アルカリ電解液が上記耐クリープ材１−１１の上側
に現われるまでの時間をそれぞれ計測したところ、下表
に示すような結果ｆ：４た。Here, FIG. 6 shows a test method for examining the creep rate of an alkaline electrolyte outside the battery system. In the method shown in the figure, a metal rod 10 is erected in a container 9 containing frozen lead 7 used as an anode active material and an alkaline electrolyte 8. Above this metal rod 10, a sealing material 8 is provided.
However, as in the case of forming the seal structure of an actual battery, they are surrounded in an annular shape and are closely attached. A creep-resistant material layer 11 is provided at the interface between the sealing material 8 and the metal rod 10 to prevent creep caused by the alkaline electrolyte. Here, by changing the thickness of the sealing material 8 and the creep-resistant material layer 11, for each type of combination,
When the time required for the alkaline electrolyte to appear on the upper side of the creep-resistant material 1-11 was measured, the results were f: 4 as shown in the table below.
ただし、アルカリ電解液の液面から封口材８の上筒まで
の距離２１は何れも２０■とし、また封口材８と耐クリ
ープ材層ａ１１の長さｔ２は等しく、その長さは何れも
５ｇとし、試験条件は常温、常温下である。なお、耐ク
リープ材層１１としてのクロム酸化物＋ｆｉの厚みは、
０．１〜２μでるる。However, the distance 21 from the liquid level of the alkaline electrolyte to the upper cylinder of the sealing material 8 is 20 cm, and the length t2 of the sealing material 8 and the creep-resistant material layer a11 is equal, and the length is 5 g. The test conditions are room temperature and normal temperature. Note that the thickness of chromium oxide + fi as the creep-resistant material layer 11 is:
It is 0.1 to 2μ.
以上の試験結果から明かなように、封口部材８とこれに
接する金一部分の界面に沿ってＯ０１〜２μ厚のクロム
酸化物層を設けたものは、アルカリ電解液によるクリー
プの阻ＬＩ１．能力が従来のエポキシやｔ、＊ Ｗ Ｉ
ＩＦ ’ｊｆ等を使用したものに比べて格段にすぐれて
いる。As is clear from the above test results, the chromium oxide layer with a thickness of 001 to 2 μm provided along the interface between the sealing member 8 and the gold portion in contact therewith inhibits creep caused by the alkaline electrolyte by LI1. The ability is conventional epoxy and *W I
It is much superior to those using IF 'jf etc.
そして、実際の電池系ｔ−構成した場合にも、この発明
による密閉式アルカリ電池では、以下に述べる試験結果
からも明かなように、電池系内における電気化学的作用
作用に対して、また電池内で生ずることの多い発生期の
水素に対しても、十分な耐久性をａｌｉｌａＩすること
ができた。Even when an actual battery system is configured, the sealed alkaline battery according to the present invention is resistant to electrochemical effects within the battery system, and as is clear from the test results described below. We were able to produce alilaI with sufficient durability even against nascent hydrogen that is often generated within the reactor.
藷に、実際の電池系においては、その電池系内の電気化
学的作用が加わるため、アルカリ電解液の１液が一層促
進され、しかもそれが陰極側合―部分の表面に沿って県
中的に生ずるという傾向がめったが、この発明による電
池では、その陰極側におけるアルカリ電解液の漏液を確
実に阻止することができる。In addition, in an actual battery system, electrochemical action within the battery system is added, so the alkaline electrolyte is further promoted, and moreover, it spreads throughout the area along the surface of the cathode side joint. However, in the battery according to the present invention, leakage of the alkaline electrolyte at the cathode side can be reliably prevented.
以下、そのｉ［池系内における試砿結果の一例を示す。An example of the test results in the pond system is shown below.
試験は、第１図あるいは第８図に示した偏平型の密閉式
アルカリ電池（タイプＡ）と、＠２図あるいは第４図に
示したボタン型の密閉式アルカリ電池（タイプＢ）の両
タイプについてそれぞれ、封口材の種類、この封口材と
合鴨部分との界面に沿って設けられる耐重液材の種類を
色々と変えて行なった。試験は、温［６０Ｃ，湿［９０
１１の環境下に保存して行ない、その結果は下表に示す
とおシであった。The test was conducted on both the flat sealed alkaline battery (type A) shown in Figure 1 or Figure 8 and the button type sealed alkaline battery (type B) shown in Figure 2 or Figure 4. For each case, the type of sealing material and the type of heavy liquid-resistant material provided along the interface between the sealing material and the duck part were varied. The test was carried out at temperature [60C, humidity [90C]
The results were shown in the table below.
上衣からも明らかなように、この発明によって１１１ｈ
ｋされた試料電池のグループ（４８〜）は、Ａ、Ｂ何れ
のタイプにおいて、従来構成の電池（ム１．２）に比べ
て、耐漏液性能が格段に向キしている。これは、上記封
口材８とこれに接する金属部分、特に陰極側余興部分と
の間の界面に沿ってクロムの酸化物層６を設けたことに
よる。As is clear from the jacket, this invention
The group of sample batteries (48~), both of types A and B, have much better leakage resistance than the conventionally configured batteries (group 1.2). This is because the chromium oxide layer 6 is provided along the interface between the sealing material 8 and the metal parts in contact with it, especially the entertainment part on the cathode side.
ところで、上記クロムの酸化物層６の厚みを、ｏ、ｉμ
より小さくした場合、おまりに薄すぎ２て金鋼部分の地
の表面が露出する確率が大となシ１その結果、このクロ
ム酸化′勿層６による漏液阻止効果が著しく低下してし
まう、また、上記クロム、の酸化物Ｆ−６の厚みを、２
μより太き−くした場合、あまりに厚すぎて酸化物層自
体がもろく卒シ、機械的、強度的安定性にかけるととも
に、凹凸を生じゃすくなシ、封口材８との密考性が悪化
する現象が見られ、その結果、やはシ漏液阻市効果が低
下する。この事実を第６図の実験結果のグラフが示して
いる。同図のグラフは、上記耐漏液材としてのクロム酸
化物層６の厚みを色々に変化させた同一構成の密閉式電
池について、温度↑Ｏｃ、湿度９０％の条件下で１４０
日間保存し、その結果漏液を生じ九電池の割合を示して
いる。同図から明かなように、クロム酸化物層６の厚み
１ｋｏ、 ｔ〜２μとした本発明による密閉式電池は、
漏液発生率は看しく低いものとなっている０、
なお、封口材８としてガラスを用いたものにあっては、
そのクロムの酸化物層６が、ガラスと良好な接着状態を
なすことができるとともに、金属部分′に対しての機械
的結合が安定かつ強固でるることにより、ガラス中にク
ラックが入ることによって生ずるアルタリ鑞解液の漏液
も確実に防止できるようになった。ｔた、封口材８とし
てガラスを用いたものにおいて、そのガラス９を金属部
分側から常、Ｐ８Ｅ縮す仝、ｈゎゆるコンプレッション
タイプのものにおいては、その圧縮によってガラス内に
常時歪が生じている友め、クラックが−１−入りゃすい
、、るるいは成長しやすい状態となるが、このようなコ
ンプレッションタイプのものにおいて、上記クロム酸化
物層６はそのガラスにクラックが入ったシ、おるいはす
でに生じている微小なりラックが大きく成長するのを阻
止する機能も兼ね漏えること第り
が１ｍ昭された。By the way, the thickness of the chromium oxide layer 6 is o, iμ
If it is made smaller, the pot is too thin2 and there is a high probability that the ground surface of the steel part will be exposed1.As a result, the leakage prevention effect of this chromium oxide layer6 will be significantly reduced. , and the thickness of the oxide F-6 of chromium is 2.
If it is thicker than μ, it is too thick and the oxide layer itself becomes brittle, resulting in poor mechanical and strength stability. As a result, the leakage prevention effect is reduced. This fact is illustrated by the graph of the experimental results in FIG. The graph in the figure shows the results of sealed batteries with the same configuration in which the thickness of the chromium oxide layer 6 as the leakage-resistant material was varied, under conditions of temperature ↑Oc and humidity 90%.
The percentage of nine batteries stored for days and resulting in leakage is shown. As is clear from the figure, the sealed battery according to the present invention in which the thickness of the chromium oxide layer 6 is 1ko and t~2μ,
The rate of leakage is surprisingly low.0 However, in cases where glass is used as the sealing material 8,
The chromium oxide layer 6 can form a good adhesion state with the glass, and the mechanical bond to the metal part' is stable and strong, which prevents cracks from forming in the glass. It is now possible to reliably prevent Altari melting liquid from leaking. In addition, in the case where glass is used as the sealing material 8, the glass 9 is always compressed from the metal part side, so in the case of a compression type, strain is constantly generated in the glass due to the compression. Dear friend, it is easy for cracks to form and grow easily, but in such compression type products, the chromium oxide layer 6 may be damaged if cracks are formed in the glass. The first reason was that the layer also had the function of preventing the microscopic racks that had already formed from growing larger.
以上、主に電解液としてアルカリ水溶液を使用する密閉
式電池の場合についで述べてきたが、この発明は、この
種の電池において％にすぐれ九効果を４たらすことがで
きる。しかし、アルカリ電池以外の密閉式電池、例えば
陰極にＬｌ等の軽金属を用１％着た非水電解質を用いた
密閉式電池において−も、その電池の耐漏液性能等を向
上させる上で非常に有効なものである。The case of a sealed battery that mainly uses an alkaline aqueous solution as an electrolyte has been described above, and the present invention can bring about an excellent effect of 4% in this type of battery. However, even in sealed batteries other than alkaline batteries, such as sealed batteries that use a non-aqueous electrolyte with 1% light metal such as Ll in the cathode, it is very important to improve the leakage resistance of the battery. It is valid.
以上のように、この発明による密閉式電池は、比做的簡
暎な構成でもって、特に小型化の丸めに構造上の簡略化
を止むなくされている密閉式％式％As described above, the sealed battery according to the present invention has a relatively simple structure, and the sealed battery has a relatively simple structure, and the structure is unavoidably simplified in order to achieve miniaturization.
第１図、第２図はそれぞれ従来の密閉式アルカリ電池の
例を示す断面図、第８図および第４図はこの発明による
密閉式アルカリ電池の実施例を示す断面図 第６図は従
来の電池とこの発明による電池のそれぞれのシール構造
の性能を比較するための試験方法の一例を示す断面図、
第６図はクロム酸化物１＃６のＩｇ−みと耐漏液性能と
の関係を示す実験結果のグラフである。
ｌ・・・・・・・・・金属＃電池ケース２・・・・・・
・・・発電要素
８・・・・・・・・・封口材
４・・・・・・・・・泉域リード
６・・・・・・・・・クロムの酸化物層特 許 出 願
人 富士電気化学株式会社代理人 弁理士 −色
健 輔FIGS. 1 and 2 are cross-sectional views showing examples of conventional sealed alkaline batteries, and FIGS. 8 and 4 are cross-sectional views showing examples of sealed alkaline batteries according to the present invention. FIG. 6 is cross-sectional views showing examples of conventional sealed alkaline batteries. A cross-sectional view showing an example of a test method for comparing the performance of the respective seal structures of a battery and a battery according to the present invention,
FIG. 6 is a graph of experimental results showing the relationship between Ig-contamination and leakage resistance of chromium oxide 1#6. l・・・・・・Metal #Battery case 2・・・・・・
...Power generation element 8 ... Sealing material 4 ... Spring area lead 6 ... Chrome oxide layer Patent applicant Fuji Electrochemical Co., Ltd. Representative Patent Attorney - Color
Kensuke
Claims (1)
が装填されるとと屯に１上記電池ケースが１４０材で＠
封され、さらにその封口材が電気絶縁性であって該封口
材によって陽極熾子側と陰極１子側とが互に絶縁隔離さ
れてなる密閉式電池において、上記封口材とこの封口材
に接する合繊部分との少なくとも陰極側の界面Ｋｉ９つ
て、ｉｔみが０．１〜２ｊ１のクロムの酸化物層を設け
たことを特徴とする密閉式電池。 （２） 前記クロムの酸化一層は、咄記匈口材が接す
る金属部分の少なくとも表面部分をり四ムまたはクロム
を含む合金で形成し、仁の金属部分の表面を酸化処理す
ることによって形成されたもので６る特ｆｆ１１１１求
の？ｉＡ囲第１項記載ＯＷｉ閉式電池。 （８）前記クロムの酸化物ｉ−は、前記金員部分の！１
面に形成されたクロムメッキ層を酸化したものでるる特
ＩＦＦ補求の範囲、４１項記載の密閉式電池。 （４）、前記封口材がガラスまたはセラミックスである
特許請求の範囲編１項、第２項または第８項記載の密閉
式電池。 （６）前記封口材がナイロン、ポリプロピレン、または
ポリエチレンでろる特許請求の範！］！ｌ第１項、４２
項ま九は第８項記載の密閉式電池。 （６）前記発電要素は、その陰極物質が永化曖鉛を主剤
とするものである特許請求の範囲第１項〜第６項の何れ
かに記載の密閉式電池。[Claims] (1) When a power generation element is loaded into a metal battery case that also serves as a terminal, the battery case is made of 140 material.
In a sealed battery, the sealing material is electrically insulating and the anode side and the cathode side are insulated and isolated from each other by the sealing material. A sealed battery characterized in that a chromium oxide layer having an it value of 0.1 to 2j1 is provided at least on the cathode side interface with the synthetic fiber portion. (2) The single layer of chromium oxidation is formed by forming at least the surface portion of the metal part that comes into contact with the metal part with chromium or an alloy containing chromium, and oxidizing the surface of the metal part. What are you looking for special ff1111? OWi closed-type battery described in Section 1 of the iA section. (8) The chromium oxide i- is in the metal portion! 1
42. A sealed battery according to item 41, which has a special IFF compensation range, which is made by oxidizing a chromium plating layer formed on the surface. (4) The sealed battery according to claim 1, 2, or 8, wherein the sealing material is glass or ceramics. (6) Claims in which the sealing material is made of nylon, polypropylene, or polyethylene! ]! l Paragraph 1, 42
Item 9 is the sealed battery described in item 8. (6) The sealed battery according to any one of claims 1 to 6, wherein the power generating element has a cathode material mainly composed of permanent lead.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56116356A JPS5818865A (en) | 1981-07-27 | 1981-07-27 | Sealed type battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56116356A JPS5818865A (en) | 1981-07-27 | 1981-07-27 | Sealed type battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5818865A true JPS5818865A (en) | 1983-02-03 |
Family
ID=14684926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56116356A Pending JPS5818865A (en) | 1981-07-27 | 1981-07-27 | Sealed type battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5818865A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60210196A (en) * | 1984-04-02 | 1985-10-22 | Mitsubishi Electric Corp | Operation system for variable frequency power source |
| US4758771A (en) * | 1985-10-30 | 1988-07-19 | Kabushiki Kaisha Toshiba | Apparatus for driving AC motor |
| JPH02250257A (en) * | 1989-03-22 | 1990-10-08 | Fuji Elelctrochem Co Ltd | Paper battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5541644A (en) * | 1978-09-18 | 1980-03-24 | Seiko Epson Corp | Small-type alkaline battery cell |
| JPS55117864A (en) * | 1979-03-01 | 1980-09-10 | Seiko Instr & Electronics Ltd | Enclosed type alkali cell |
-
1981
- 1981-07-27 JP JP56116356A patent/JPS5818865A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5541644A (en) * | 1978-09-18 | 1980-03-24 | Seiko Epson Corp | Small-type alkaline battery cell |
| JPS55117864A (en) * | 1979-03-01 | 1980-09-10 | Seiko Instr & Electronics Ltd | Enclosed type alkali cell |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60210196A (en) * | 1984-04-02 | 1985-10-22 | Mitsubishi Electric Corp | Operation system for variable frequency power source |
| JPH0353876B2 (en) * | 1984-04-02 | 1991-08-16 | ||
| US4758771A (en) * | 1985-10-30 | 1988-07-19 | Kabushiki Kaisha Toshiba | Apparatus for driving AC motor |
| JPH02250257A (en) * | 1989-03-22 | 1990-10-08 | Fuji Elelctrochem Co Ltd | Paper battery |
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