JP5238153B2 - Coin-cell battery - Google Patents
Coin-cell battery Download PDFInfo
- Publication number
- JP5238153B2 JP5238153B2 JP2006268013A JP2006268013A JP5238153B2 JP 5238153 B2 JP5238153 B2 JP 5238153B2 JP 2006268013 A JP2006268013 A JP 2006268013A JP 2006268013 A JP2006268013 A JP 2006268013A JP 5238153 B2 JP5238153 B2 JP 5238153B2
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- binder
- coin
- electrode plate
- electrolyte 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.)
- Expired - Fee Related
Links
- 239000011230 binding agent Substances 0.000 claims description 55
- 239000008151 electrolyte solution Substances 0.000 claims description 23
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 23
- 239000000565 sealant Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000005060 rubber Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 238000000034 method Methods 0.000 description 26
- 230000008569 process Effects 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 239000003575 carbonaceous material Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000007423 decrease Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005476 soldering Methods 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y02E60/12—
Description
本発明は、プリント配線基板上に配される非水電解質電池に関する。 The present invention relates to a non-aqueous electrolyte battery disposed on a printed wiring board.
コイン型の非水電解質電池は、他の電池に比べてエネルギー密度が高く、軽量であるという特徴を備えていることから、電気機器のバックアップ用電源として広く採用されている。
従来のコイン型電池では、カーボン材料を外装缶内表面に焼付け（特許文献１を参照）、あるいはカーボン材料を混合した導電性接着剤を塗布して電極の集電体を形成している（特許文献２を参照）。
Coin-type non-aqueous electrolyte batteries are widely used as a backup power source for electric devices because they have features of higher energy density and lighter weight than other batteries.
In a conventional coin-type battery, a carbon material is baked on the inner surface of an outer can (see Patent Document 1), or a conductive adhesive mixed with a carbon material is applied to form an electrode current collector (patent) Reference 2).
上記コイン型電池と電気機器との接続手法は、量産性の観点から、電気機器に内包されるプリント配線基板上の配設予定位置に予めクリーム状の半田を塗布しておき、そこに当該電池および他の半導体素子を載置して同時に加熱することにより一括してこれらの半田付けを行うリフロー法が主流となりつつある。
しかし、上記リフロー法を用いてコイン型電池をプリント配線基板に実装すると、加熱によって集電体のカーボン材料が電解液と反応する等して、リフロー工程後の当該電池において、その内部抵抗が著しく上昇して、集電性能が低下するという問題が生じた。
本発明は、上記問題点に鑑みてなされたものであり、集電性能の低下を抑制することのできるコイン型の非水電解質電池を提供することを目的とする。
However, when a coin-type battery is mounted on a printed wiring board using the reflow method, the internal resistance of the battery after the reflow process is remarkably increased because the carbon material of the current collector reacts with the electrolyte solution by heating. As a result, the current collection performance deteriorated.
The present invention has been made in view of the above problems, and an object of the present invention is to provide a coin-type non-aqueous electrolyte battery that can suppress a decrease in current collecting performance.
上記目的を達成するため、本発明に係るコイン型非水電解質電池では、正極ケースおよび負極ケースが、ガスケットを挟みながら嵌合した状態で、正極板、負極板および電解液を包含しているコイン型の非水電解質電池に対し、電解液は、プロピレンカーボネート及びジメトキシエタンを含有し、オレフィン系炭化水素を主成分とする多孔膜状の結着剤で、少なくとも一方の極板と、当該極板と対向する少なくとも一方の極ケースとを結着させた。
In order to achieve the above object, in the coin-type nonaqueous electrolyte battery according to the present invention, a coin including a positive electrode plate, a negative electrode plate, and an electrolyte solution in a state where the positive electrode case and the negative electrode case are fitted with a gasket interposed therebetween. For a non-aqueous electrolyte battery of the type, the electrolytic solution is a porous film-like binder containing propylene carbonate and dimethoxyethane and containing olefinic hydrocarbon as a main component , at least one electrode plate, and the electrode plate And at least one pole case facing each other.
カーボン材料を集電体に用いた場合、あるいはカーボン材料を混合してなる導電性接着剤を集電体に用いた場合には、リフロー半田工程においてカーボン材料が電解液と反応し、集電体の導電性が失われることがある。
上記コイン型の非水電解質電池では、カーボンとの反応性が高い電解液に対して、反応性が低い結着剤で正極板と正極ケースとを結着させたので、カーボン材料を集電体に用いた場合、あるいはカーボン材料を混合してなる導電性接着剤を集電体に用いた場合と比べて、リフロー半田工程において結着剤が電解液と反応することを抑制することができ、リフロー工程前に比べてリフロー工程後に内部抵抗が上昇することを抑制することができて集電性能の低下を抑制することができる。
When a carbon material is used for the current collector or when a conductive adhesive made by mixing carbon materials is used for the current collector, the carbon material reacts with the electrolyte in the reflow soldering process, and the current collector Conductivity may be lost.
In the above coin-type non-aqueous electrolyte battery, the positive electrode plate and the positive electrode case are bound to the electrolytic solution having a high reactivity with carbon with a binding agent having a low reactivity. Compared to the case where the conductive adhesive formed by mixing the carbon material or the current collector is used for the current collector, the binder can be prevented from reacting with the electrolyte in the reflow soldering process, Compared with before the reflow process, it is possible to suppress an increase in internal resistance after the reflow process, and it is possible to suppress a decrease in current collecting performance.
そのうえ、本発明に係るコイン型非水電解質電池では、製造ばらつきによって正極板の厚みにばらつきがあっても、正極板と正極ケースとが結着剤によって結着されているので、正極板と正極ケースとの接触圧の低い領域が抑制され、リフロー工程前において内部抵抗のばらつきを抑制することができる。
リフロー工程では、カーボン材料が電解液と反応する以外に、電解液が蒸発して密閉された電池の内圧上昇を招き、これに起因してケースが膨張し、正極板と正極ケースとの接触面積が減少し、接触抵抗（内部抵抗）が上昇して集電性能が低下することも考えられる。本発明に係るコイン型非水電解質電池では、当該内圧上昇が起こっても、正極板と正極ケースとを結着する結着剤によって、正極板と正極ケースとの接触面積が維持され、リフロー工程前に比べてリフロー工程後に内部抵抗が上昇することを抑制することができて集電性能の低下を抑制することができる。
Moreover, in the coin-type non-aqueous electrolyte battery according to the present invention, the positive electrode plate and the positive electrode case are bonded by the binder even if the thickness of the positive electrode plate varies due to manufacturing variations. A region having a low contact pressure with the case is suppressed, and variations in internal resistance can be suppressed before the reflow process.
In the reflow process, in addition to the carbon material reacting with the electrolytic solution, the electrolytic solution evaporates to increase the internal pressure of the sealed battery, which causes the case to expand, and the contact area between the positive electrode plate and the positive electrode case It is also conceivable that the current collection performance decreases due to a decrease in contact resistance (internal resistance). In the coin-type non-aqueous electrolyte battery according to the present invention, even if the internal pressure rises, the contact area between the positive electrode plate and the positive electrode case is maintained by the binder that binds the positive electrode plate and the positive electrode case, and the reflow process It is possible to suppress an increase in internal resistance after the reflow process compared to before, and it is possible to suppress a decrease in current collecting performance.
本発明に係るコイン型非水電解質電池では、上記結着剤がカーボン材料と比べて電解液と反応しにくいので、上記作用・効果が電解液によって損なわれることを抑制することができる。
上記結着剤が室温以上３００［℃］未満において弾性を有すると、上記リフロー工程での加熱に対しても結着剤の弾性が損なわれず、上記接触面積維持の作用ならびに効果を確実にすることができる。
In the coin-type non-aqueous electrolyte battery according to the present invention, since the binder is less likely to react with the electrolytic solution than the carbon material, it is possible to suppress the effects and effects from being impaired by the electrolytic solution.
When the binder has elasticity at room temperature or more and less than 300 [° C.], the elasticity of the binder is not impaired even by heating in the reflow process, and the action and effect of maintaining the contact area are ensured. Can do.
上記正極ケースと上記ガスケットとの間に膜状のシール剤が形成されており、上記結着剤が上記シール剤と同じ成分からなれば、製造時においてシール剤と結着剤とを同時に形成することができるので、シール剤と結着剤とを個別に形成する煩雑さがなくなり、製造工程を簡略化することができ、量産性を向上させることができる。 A film-like sealant is formed between the positive electrode case and the gasket, and if the binder is composed of the same components as the sealant, the sealant and the binder are simultaneously formed during manufacturing. Therefore, the complexity of forming the sealing agent and the binder separately can be eliminated, the manufacturing process can be simplified, and mass productivity can be improved.
（実施の形態１）
以下、図面を適宜用いて本発明の実施の形態１に係るコイン型非水電解質電池について説明する。
図１は、本実施の形態に係るコイン型非水電解質電池の概略断面図である。
図１に示すように、本実施の形態に係るコイン型電池１０では、リング状のガスケット６が皿状の正極缶４および負極缶５それぞれの縁部同士の間に挟まれており、リチウムを主成分とする皿状の負極板２と、二酸化マンガンを主成分としかつ粉体を押し固めて成形した円筒状の正極板１とが円盤状のガスケット３を挟んでなる電極体が内包されている。
(Embodiment 1)
Hereinafter, the coin-type nonaqueous electrolyte battery according to Embodiment 1 of the present invention will be described with reference to the drawings as appropriate.
FIG. 1 is a schematic cross-sectional view of a coin-type nonaqueous electrolyte battery according to the present embodiment.
As shown in FIG. 1, in the coin-
ガスケット６と正極缶４との間には、電池１０の密封性能を向上させるため、膜状のシール剤７が形成されている。正極板１と正極缶４との間には、ブチレンゴム系の多孔膜状の結着剤８が形成され、結着剤８が正極板１と正極缶４とを結着している。
本実施の形態に係る電池は、具体的には、オレフィン系炭化水素を主成分とするスリーボンド社製のＴＢ１１７１と、キシレンとを１：２の割合で混合してなるものを正極缶４の内側面の全体に塗布し、そして、１２０［℃］雰囲気下で１分間乾燥させてキシレンを揮発させ、さらに、６０［℃］雰囲気下で４時間乾燥させて水分を揮発させた後、乾燥雰囲気（水分値３００［ｐｐｍ］以下）下で４時間放置することによって残存するキシレンおよび水分を十分に揮発させて、シール剤７および結着剤８形成済みの正極缶４を完成させ、予めその内面に負極板２およびセパレータ３をこの順で積層済みの負極缶５を準備しておき、この負極缶５の内側に下記成分の電解液を注入した後に正極板１を載置し、上記の完成した正極缶４を正極板１に被せた状態でカシメて封口されたものである。
A film-
Specifically, the battery according to the present embodiment includes a battery made by mixing TB1171 made by Three Bond, whose main component is an olefinic hydrocarbon, and xylene in a ratio of 1: 2. It was applied to the entire side surface and dried in an atmosphere of 120 [° C.] for 1 minute to volatilize xylene, and further dried in an atmosphere of 60 [° C.] for 4 hours to volatilize moisture, and then the drying atmosphere ( The remaining xylene and moisture are sufficiently volatilized by leaving them under a moisture value of 300 ppm or less) for 4 hours to complete the positive electrode can 4 in which the
〔電解液〕
プロピレンカーボネート（PC）とジメトキシエタン（DME）の１：１混合溶媒に電解質としてトリフルオロメタンスルホン酸リチウム（LiCF3SO3）を１mol/ｌで溶解させている。
なお、上記工程は一例であって、キシレンならびに水分を十分に揮発させることのできる工程であれば、上記工程には限定されない。
[Electrolyte]
Lithium trifluoromethanesulfonate (LiCF3SO3) is dissolved at 1 mol / l as an electrolyte in a 1: 1 mixed solvent of propylene carbonate (PC) and dimethoxyethane (DME).
In addition, the said process is an example, Comprising: If it is a process which can volatilize xylene and a water | moisture content enough, it will not be limited to the said process.
ＴＢ１１７１は、オレフィン系炭化水素を主成分とすることから熱可塑性を有し、したがって、高温に晒されると弾性を失っていく傾向を有するが、発明者らは、ＴＢ１１７１が約３００［℃］雰囲気下において初めて分解すること、すなわち当該温度になって初めて弾性を失い始めることを確認している。
本実施の形態に係るコイン型非水電解質電池は、バックアップ用の電池としてプリント配線基板上にリフロー半田で実装される場合、約２６０［℃］の温度雰囲気に晒されるが、上記のようにＴＢ１１７１は、約３００［℃］雰囲気下において初めて弾性を失うので、リフロー半田工程を経ても弾性を失わない。
TB1171 has thermoplasticity because it has an olefinic hydrocarbon as a main component, and therefore has a tendency to lose elasticity when exposed to high temperatures. It has been confirmed that it decomposes for the first time below, that is, it begins to lose its elasticity only at that temperature.
The coin-type non-aqueous electrolyte battery according to the present embodiment is exposed to a temperature atmosphere of about 260 [° C.] when mounted on a printed wiring board as a backup battery by reflow soldering, but as described above, TB1171 Loses elasticity for the first time in an atmosphere of about 300 [° C.], and therefore does not lose elasticity even after a reflow soldering process.
オレフィン系炭化水素は、有機材料であるので導電性が低く、そして、カーボンを含んでいない。なお、「カーボン」は黒鉛粉末等の導電性を有するカーボンを意味しており、オレフィン系炭化水素のように炭素と水素等とが結合してなる有機材料を含まない。そのうえ、オレフィン系炭化水素は、シール剤７の主成分となっていることからも分かるように、電解液に対して高い耐性を備えており、すなわち、電解液と反応しにくい特性を備えている。したがって、結着剤８は、カーボンを含んでおらず、かつ電解液に対して反応し難いという特性を有する。
Olefinic hydrocarbons are organic materials and therefore have low electrical conductivity and do not contain carbon. “Carbon” means conductive carbon such as graphite powder, and does not include organic materials in which carbon and hydrogen are combined, such as olefinic hydrocarbons. In addition, as can be seen from the fact that the olefinic hydrocarbon is the main component of the
上記のように結着剤８が正極缶４と正極板１との間に形成されているので、図１の部分拡大図に示すように、結着剤８は完全な被膜の状態となっておらず、所々で正極板１と正極缶４とが接触している状態となっている。
本実施の形態では、シール剤７と結着剤８とが同じ成分であるが、既述のように電解液に対して耐性を備え、かつ熱耐性を備えている材料であれば、結着剤８がシール剤７と同じ成分でなくても良い。シール剤７と結着剤８とが同じ成分であると、既述のように正極缶４の内側面の全体にこれらを同時に形成することができるので、好ましい。
Since the binder 8 is formed between the positive electrode can 4 and the positive electrode plate 1 as described above, as shown in the partially enlarged view of FIG. In other words, the positive electrode plate 1 and the positive electrode can 4 are in contact with each other.
In the present embodiment, the
本実施の形態では、結着剤８として、ＴＢ１１７１を用いているが、これに限定されず、カーボンを含んでおらず、電解液に対して耐性があり、かつリフロー工程での加熱温度である約２６０［℃］においても分解されず、弾性を維持できる材料であれば良い。例えば、結着剤８が延伸多孔質ポリテトラフルオロエチレン（ｅＰＴＦＥ）やスチレンブタジエンゴム（ＳＢＲ）エチレンプロピレンゴム（ＥＰＤＭ）フッ素ゴム（ＦＥＰＭ）などを主成分としていても良い。
《本実施の形態におけるコイン型非水電解質電池の効果》
本実施の形態では、結着剤８と電解液との反応性がカーボンと電解液との反応性に比べて低いので、カーボン材料を集電体として用いたもの、カーボン材料を混合してなる導電性接着剤を集電体に用いたものに比べて、リフロー半田工程において結着剤８が電解液と反応することを抑制することができ、リフロー工程前に比べてリフロー工程後に内部抵抗が上昇することを抑制することができて集電性能の低下を抑制することができる。
In the present embodiment, TB1171 is used as the binder 8, but the present invention is not limited to this, and does not include carbon, is resistant to the electrolytic solution, and is the heating temperature in the reflow process. Any material that does not decompose even at about 260 [° C.] and can maintain elasticity can be used. For example, the binder 8 may be mainly composed of expanded porous polytetrafluoroethylene (ePTFE), styrene butadiene rubber (SBR), ethylene propylene rubber (EPDM), fluorine rubber (FEPM), or the like.
<< Effects of coin-type nonaqueous electrolyte battery in this embodiment >>
In the present embodiment, since the reactivity between the binder 8 and the electrolytic solution is lower than the reactivity between the carbon and the electrolytic solution, the carbon material is used as a current collector, and the carbon material is mixed. Compared to the case where a conductive adhesive is used for the current collector, the binder 8 can be prevented from reacting with the electrolyte in the reflow soldering process, and the internal resistance is less after the reflowing process than before the reflowing process. It is possible to suppress the increase, and it is possible to suppress a decrease in current collecting performance.
上記電池では、完成後に所望の寸法が得られるように各構成部材の寸法が規定され、正極缶４と負極缶５とで形成される内包空間も所望の寸法になるようにこれらの押圧も規定されているが、正極板と正極缶とを直接接触させる構造を採用したとき、製造ばらつきによって正極板１の厚みにばらつきが生じると、規定の圧力で正極缶４と負極缶５とを嵌合させた場合、正極板１と正極缶４との接触面積にばらつきが生じ、結果、内部抵抗にばらつきが生じ、集電性能にばらつきが生じる。 In the battery described above, the dimensions of the constituent members are defined so that desired dimensions can be obtained after completion, and the pressures are also defined so that the internal space formed by the positive electrode can 4 and the negative electrode can 5 also has the desired dimensions. However, when the structure in which the positive electrode plate and the positive electrode can are directly contacted is adopted, and the thickness of the positive electrode plate 1 varies due to manufacturing variations, the positive electrode can 4 and the negative electrode can 5 are fitted with a specified pressure. In this case, the contact area between the positive electrode plate 1 and the positive electrode can 4 varies, and as a result, the internal resistance varies and the current collection performance varies.
これに対して、本実施の形態では、結着剤８が弾性を有するので、製造ばらつきによって正極板１の厚みにばらつきがあっても、正極板と正極缶とを直接接触させる構造のコイン型電池に比べて、結着剤８の弾性が正極板１と正極缶４との接触面積のばらつきを抑制するように働き、その結果、内部抵抗のばらつきを抑制して集電性能にばらつきが生じることを抑制することができる。 On the other hand, in the present embodiment, since the binder 8 has elasticity, even if the thickness of the positive electrode plate 1 varies due to manufacturing variations, the coin type has a structure in which the positive electrode plate and the positive electrode can are in direct contact with each other. Compared to the battery, the elasticity of the binder 8 works to suppress the variation in the contact area between the positive electrode plate 1 and the positive electrode can 4, and as a result, the variation in the internal resistance is suppressed and the current collection performance varies. This can be suppressed.
本実施の形態に係る電池１０を、バックアップ用の電池としてプリント配線基板上にリフロー半田で実装する場合、カーボン材料が電解液と反応する以外に、電解液が蒸発して密閉された電池１０の内圧上昇を招き、これに起因して接触抵抗（内部抵抗）が上昇して集電性能が低下することも考えられる。本実施の形態に係るコイン型非水電解質電池１０では、当該内圧上昇が起こっても、正極板１と正極缶４とを結着する結着剤８によって、正極板１と正極缶４との接触面積が維持され、リフロー工程前に比べてリフロー工程後に内部抵抗が上昇することを抑制することができて集電性能の低下を抑制することができる。
When the
本実施の形態に係るコイン型非水電解質電池１０では、結着剤８がカーボン材料と比べて電解液と反応しにくいので、上記作用・効果が電解液によって損なわれることを抑制することができる。
結着剤８は、室温以上３００［℃］未満において弾性を有するので、上記リフロー工程での加熱に対しても弾性が損なわれず、したがって、本実施の形態に係るコイン型非水電解質電池１０では、上記接触圧の維持の作用ならびに効果を確実にすることができる。
In the coin-type
Since the binder 8 has elasticity at room temperature or more and less than 300 [° C.], the elasticity is not impaired even by heating in the reflow process. Therefore, in the coin-type
本実施の形態では、結着剤８がシール剤７と同じ成分からなるので、シール剤７と結着剤８とを同時に形成することができ、シール剤７と結着剤８とを個別に形成する煩雑さがなくなり、製造工程を簡略化することができ、量産性を向上させることができる。
〔評価試験〕
本発明のコイン型非水電解質電池の効果を検証するべく、実施の形態１に係るコイン型の非水電解質電池と、比較の対象としてカーボンを焼き付けてなる集電体を備えたコイン型電池および集電体を備えていないコイン型電池とを各３０個用意し、評価試験を行った。評価試験に用いるサンプルとして実施例１、比較例１,２を用意した。
In this embodiment, since the binder 8 is composed of the same components as the
〔Evaluation test〕
In order to verify the effect of the coin-type non-aqueous electrolyte battery of the present invention, the coin-type non-aqueous electrolyte battery according to Embodiment 1 and a coin-type battery including a current collector formed by baking carbon as a comparison target, and Thirty coin-type batteries each without a current collector were prepared and subjected to an evaluation test. Example 1 and Comparative Examples 1 and 2 were prepared as samples used for the evaluation test.
（実施例１）
実施例１のコイン型電池は、実施の形態１で示したコイン型電池の構成と同じで、直径Ｄが約４．８［ｍｍ］，厚みが約１．４［ｍｍ］、であり、その他の構成は実施の形態１と同様であるので、ここでの説明は省略する。
（比較例１）
比較例１のコイン型電池は、炭素系導電性塗料であるＪＥＭ−８８６を正極缶の内側のうち正極板と接触する部分に塗布し、これを１５０［℃］で１時間乾燥させて集電体としており、正極缶とガスケットとの間に形成されたシール剤と集電体とは間隙を開けて正極缶の内側面に形成されている点のみが実施例１と異なり、その他の構成については実施例１と同様であるので、ここでの説明は省略する。
Example 1
The coin-type battery of Example 1 has the same configuration as that of the coin-type battery shown in Embodiment 1, has a diameter D of about 4.8 [mm] and a thickness of about 1.4 [mm]. Since this configuration is the same as that of the first embodiment, description thereof is omitted here.
(Comparative Example 1)
In the coin-type battery of Comparative Example 1, the carbon-based conductive paint JEM-886 is applied to the inside of the positive electrode can on the portion that comes into contact with the positive electrode plate, and this is dried at 150 [° C.] for 1 hour to collect current. The only difference is that the sealing agent and the current collector formed between the positive electrode can and the gasket are formed on the inner surface of the positive electrode can with a gap therebetween. Since this is the same as that of the first embodiment, description thereof is omitted here.
（比較例２）
比較例２のコイン型電池は、正極缶の内面にうち正極板と接触する部分に何も形成されておらず、正極缶と正極板とが直接接触している点が実施例１と異なり、その他の構成については実施例１と同様であるので、ここでの説明は省略する。
＜耐リフロー試験＞
電池の表面温度が、１５０［℃］以上の状態が２３０秒、２００［℃］以上の状態が９０秒、２５０「℃」以上の状態が４０秒（最大２６０［℃］）となるように設定したリフロー炉内に実施例１、比較例１,２の各電池を投入した。全ての電池を２度、リフロー炉内に投入した。その理由は、プリント配線基板の一方の面に電池を実装した後、他方の面に他の電子部品が実装されることを想定したからである。
(Comparative Example 2)
The coin-type battery of Comparative Example 2 is different from Example 1 in that nothing is formed on the inner surface of the positive electrode can in the portion in contact with the positive electrode plate, and the positive electrode can and the positive electrode plate are in direct contact. Since other configurations are the same as those in the first embodiment, description thereof is omitted here.
<Reflow resistance test>
The battery surface temperature is set to be 230 seconds when the surface temperature is 150 [° C] or higher, 90 seconds when the temperature is 200 [° C] or higher, and 40 seconds (maximum 260 [° C]) when the temperature is 250 “° C” or higher The batteries of Example 1 and Comparative Examples 1 and 2 were put into the reflow furnace. All the batteries were put into the reflow furnace twice. The reason is that it is assumed that after mounting the battery on one surface of the printed wiring board, another electronic component is mounted on the other surface.
＜作動電圧の測定＞
実施例１、比較例１,２の各コイン型電池に対して、上記耐リフロー試験の前後それぞれにおいて、標準抵抗（１２［ｋΩ］）を接続して通電し、１秒後の作動電圧を測定した。
＜内部抵抗の測定＞
実施例１、比較例１,２のコイン型電池に対して、上記耐リフロー試験の前後それぞれにおいて、１［ｋＨｚ］の交流内部抵抗値を測定した。
<Measurement of working voltage>
For each of the coin-type batteries of Example 1 and Comparative Examples 1 and 2, a standard resistor (12 [kΩ]) was connected and energized before and after the reflow resistance test, and the operating voltage after 1 second was measured. did.
<Measurement of internal resistance>
For the coin batteries of Example 1 and Comparative Examples 1 and 2, an AC internal resistance value of 1 [kHz] was measured before and after the reflow resistance test.
〔試験結果〕
以上の各測定値を表１に示す。なお、表１には、実施例１、比較例１，２それぞれのサンプルにつき、３０個の平均値を記載している。
〔Test results〕
Table 1 shows the above measured values. In Table 1, 30 average values are shown for each sample of Example 1 and Comparative Examples 1 and 2.
表１に示すように、実施例１の作動電圧が、比較例１,２それぞれの作動電圧と比べて、同等の電圧を維持していることが確認できる。このことから、実施例１においては、比較例１,２と同等の通電性能を発揮できることが分かった。その理由として、結着剤８は、絶縁性を有するが、有機溶媒に分散させて塗布する工程を経て形成されているため、正極缶４の内側にて完全な被膜を形成できず、その結果、正極板１と正極缶４とを散点的に接触させたと考えられる。
As shown in Table 1, it can be confirmed that the operating voltage of Example 1 maintains an equivalent voltage as compared with the operating voltages of Comparative Examples 1 and 2. From this, it was found that in Example 1, the energization performance equivalent to that of Comparative Examples 1 and 2 can be exhibited. The reason is that the binder 8 has an insulating property, but is formed through a process of dispersing and coating in an organic solvent, so that a complete coating cannot be formed inside the positive electrode can 4, and as a result. It is considered that the positive electrode plate 1 and the positive electrode can 4 were brought into contact in a scattered manner.
また、有機溶媒揮発後において結着剤８が被膜を形成していても、正極缶４は金属製であって、その内表面が微視的に見て粗く、かつ正極板１も粉体を押し固めてなるので、正極板１のうち正極缶４と対向する面も微視的に見て粗く、柔軟な結着剤８が正極缶４のカシメに伴って、これら粗面同士に突き破られ、その結果、正極板１と正極缶４とが散点的に接触できると考えられる。 Even if the binder 8 forms a film after volatilization of the organic solvent, the positive electrode can 4 is made of metal and its inner surface is microscopically rough, and the positive electrode plate 1 is also made of powder. Since the surface of the positive electrode plate 1 facing the positive electrode can 4 is microscopically rough because it is pressed, the flexible binder 8 breaks into the rough surfaces with the caulking of the positive electrode can 4. As a result, it is considered that the positive electrode plate 1 and the positive electrode can 4 can come into contact in a scattered manner.
実施例１のリフロー前の作動電圧が比較例２のリフロー前の作動電圧と比べて大きいことが確認できる。
上記各試験を実施する際に、各サンプルは全て同じ規定寸法で作製しているが、製造ばらつきによって正極板の厚みにばらつきが生じ、正極板と正極缶との接触面積にばらつきが生じる。比較例２のコイン型電池では、この正極板の製造ばらつきに起因する接触面積のばらつきが直接作動電圧に影響したのに対して、実施例１のコイン型電池では、正極板１と正極缶４との間に膜状の結着剤８が形成されているため、結着剤８の弾性が正極板１と正極缶４との接触面積のばらつきを抑制するように働き、その結果、比較例２と比べてリフロー前の作動電圧が小さくなったと考えられる。これにより、結着剤８には製造ばらつきに起因する当該接触面積ばらつき抑制効果があることが確認できた。
It can be confirmed that the operating voltage before reflow in Example 1 is larger than the operating voltage before reflow in Comparative Example 2.
When the above tests are carried out, all the samples are produced with the same specified dimensions, but the thickness of the positive electrode plate varies due to manufacturing variations, and the contact area between the positive electrode plate and the positive electrode can varies. In the coin-type battery of Comparative Example 2, the contact area variation due to the manufacturing variation of the positive electrode plate directly affected the operating voltage, whereas in the coin-type battery of Example 1, the positive electrode plate 1 and the positive electrode can 4 Since the film-like binder 8 is formed between the positive electrode plate 1 and the positive electrode can 4, the elasticity of the binder 8 acts to suppress variation in the contact area between the positive electrode plate 1 and the positive electrode can 4. Compared to 2, the operating voltage before reflowing is considered to be smaller. Thereby, it has confirmed that the binder 8 had the said contact area variation inhibitory effect resulting from manufacturing variation.
表１に示すように、実施例１、比較例１,２の全てにおいて、リフロー後におけるそれらの内部抵抗がリフロー前に比べて大きくなっているが、実施例１では、比較例１,２と比べて、その上昇率が小さいことが確認できる。
その理由として、比較例１では、導電性塗料がリフロー時の加熱および電解液の作用によって分解され、かつ当該加熱によって電解液が揮発し、これに起因して電池内圧が上昇して正極缶が内側から押されて、集電体にクラックが伸展し、リフロー後の接触抵抗がリフロー前に比べて増加したと考えられる。
As shown in Table 1, in all of Example 1 and Comparative Examples 1 and 2, their internal resistance after reflow is larger than that before reflow, but in Example 1, Comparative Examples 1 and 2 and In comparison, it can be confirmed that the rate of increase is small.
The reason for this is that in Comparative Example 1, the conductive paint is decomposed by heating during reflow and the action of the electrolytic solution, and the electrolytic solution is volatilized by the heating. It is considered that cracks were extended in the current collector when pushed from the inside, and the contact resistance after reflow increased compared to that before reflow.
そして、比較例２では、もともと製造ばらつきによる接触抵抗のばらつきが大きいうえに、既述した電解液の揮発によって電池内圧が上昇し、正極缶が内側から押されて、正極板と正極缶との接触面積がさらに低下し、リフロー後の接触抵抗がリフロー前に比べて増加したと考えられる。
これらに対して、実施例１では、結着剤８が電解液に対して反応し難い特性を備えていることから、比較例１と比べて、分解されるおそれが低く、したがって、電解液の揮発により電池内圧が上昇しても、結着剤８の弾性によって、正極缶４が内側から押されることを抑制することができ、リフロー前後において正極缶４と正極板１との接触面積を維持することができたと考えられる。
In Comparative Example 2, the contact resistance due to manufacturing variation was originally large, and the internal pressure of the battery increased due to the volatilization of the electrolyte, and the positive electrode can was pushed from the inside. It is considered that the contact area further decreased, and the contact resistance after reflow increased compared with that before reflow.
On the other hand, in Example 1, since the binder 8 has a property that hardly reacts with the electrolytic solution, the possibility of being decomposed is lower than that in Comparative Example 1. Even if the battery internal pressure rises due to volatilization, the elasticity of the binder 8 can suppress the positive electrode can 4 from being pushed from the inside, and the contact area between the positive electrode can 4 and the positive electrode plate 1 is maintained before and after reflow. It is thought that it was possible.
つまり、結着剤８は、製造時、乾燥状態で正極缶４および正極板１に圧着されているが、結着剤８は弾力性を有するので、正極缶４、正極板１双方の表面の微細な凹凸が結着剤８の表面に食い込む。部分的には図１の部分拡大図に示すように正極板４と正極板１とが直接接触することになる。結果として結着剤８は多孔膜となる。
そして、結着の意味は、本来の接着状態のものであってもよいし（この場合は半乾燥状態と考えられる。）、上述の結着剤８が弾力性を有することで、ここに正極缶４および正極板１の微細な凹凸が食い込んで、結果として正極缶４と正極板１とが結合状態になるとの意味を持つ。
That is, the binder 8 is pressure-bonded to the positive electrode can 4 and the positive electrode plate 1 in a dry state at the time of manufacture. However, since the binder 8 has elasticity, both the surfaces of both the positive electrode can 4 and the positive electrode plate 1 are bonded. Fine irregularities bite into the surface of the binder 8. In part, the
The meaning of the binding may be the original adhesion state (in this case, it is considered to be a semi-dry state), or the above-described binding agent 8 has elasticity, so that the positive electrode here. It has the meaning that the fine irregularities of the
既述のように、正極缶４と負極缶５とを嵌合させる前に正極缶４の内表面に塗られた結着剤８は十分にキシレン・水分を揮発させているが、正極板１のうち、正極缶４と対向する面が粗く、そして、結着剤８は、溶媒に溶かされたものを揮発させてなるため、正極板１と対向する面が粗く、なおかつ正極缶４をカシメる際に適度な圧力が加わることによって、結着剤８の粗面を構成するゴム繊維が正極板１の粗面に入り込み、絡み合って、結着剤８が、正極板１と結着して、上記作用を奏していると考えられる。 As described above, the binder 8 applied to the inner surface of the positive electrode can 4 before the positive electrode can 4 and the negative electrode can 5 are fitted to each other sufficiently volatilizes xylene and moisture. Among them, the surface facing the positive electrode can 4 is rough, and the binder 8 is formed by volatilizing the material dissolved in the solvent. Therefore, the surface facing the positive electrode plate 1 is rough and the positive electrode can 4 is caulked. When a suitable pressure is applied, the rubber fibers constituting the rough surface of the binder 8 enter the rough surface of the positive electrode plate 1 and become entangled, and the binder 8 is bonded to the positive electrode plate 1. It is considered that the above-mentioned action is exerted.
以上の結果から、実施例１のコイン型電池では、結着剤８に絶縁性があるにもかかわらず、比較例１，２と同様に正極板１と正極缶４との通電を確保でき、比較例２と比べて製造ばらつきに起因する接触ばらつきを抑制でき、比較例１,２に比べてリフロー工程による集電性能の低下を抑制できることが確認できた。 From the above results, in the coin-type battery of Example 1, it is possible to ensure the energization of the positive electrode plate 1 and the positive electrode can 4 as in Comparative Examples 1 and 2, although the binder 8 has an insulating property. Compared with Comparative Example 2, it was confirmed that contact variation due to manufacturing variation could be suppressed, and that compared with Comparative Examples 1 and 2, reduction in current collecting performance due to the reflow process could be suppressed.
本発明に係るコイン型電池では、リフロー半田工程による悪影響を抑制できるので、量産性の向上が要求される電気機器に広く適用することができ、その産業上の利用可能性が非常に広く、且つ大きい。 In the coin-type battery according to the present invention, the adverse effects due to the reflow soldering process can be suppressed, so that it can be widely applied to electrical equipment that requires improvement in mass productivity, and its industrial applicability is very wide, and large.
１ 正極板
２ 負極板
３ セパレータ
４ 正極缶
５ 負極缶
６ ガスケット
７ シール剤
８ 結着剤
１０ コイン型電池
DESCRIPTION OF SYMBOLS 1 Positive electrode plate 2 Negative electrode plate 3
Claims (4)
前記電解液は、プロピレンカーボネート及びジメトキシエタンを含有し、
オレフィン系炭化水素を主成分とする多孔膜状の結着剤が、少なくとも一方の極板と、当該極板と対向する少なくとも一方の極ケースとを結着していることを特徴とするコイン型の非水電解質電池。 A coin-type nonaqueous electrolyte battery including a positive electrode plate, a negative electrode plate, and an electrolyte solution in a state where the positive electrode case and the negative electrode case are fitted with a gasket interposed therebetween,
The electrolytic solution contains propylene carbonate and dimethoxyethane,
A coin type, characterized in that a porous membrane binder mainly composed of an olefinic hydrocarbon binds at least one electrode plate and at least one electrode case facing the electrode plate. Non-aqueous electrolyte battery.
前記結着剤は、前記シール剤と同じ成分からなることを特徴とする請求項１または２に記載のコイン型非水電解質電池。 Between the positive electrode case and the gasket, a film-like sealing agent is inserted,
The coin-type non-aqueous electrolyte battery according to claim 1, wherein the binder is made of the same component as the sealant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006268013A JP5238153B2 (en) | 2006-09-29 | 2006-09-29 | Coin-cell battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006268013A JP5238153B2 (en) | 2006-09-29 | 2006-09-29 | Coin-cell battery |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2008091081A JP2008091081A (en) | 2008-04-17 |
| JP2008091081A5 JP2008091081A5 (en) | 2009-11-05 |
| JP5238153B2 true JP5238153B2 (en) | 2013-07-17 |
Family
ID=39375042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006268013A Expired - Fee Related JP5238153B2 (en) | 2006-09-29 | 2006-09-29 | Coin-cell battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5238153B2 (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62115661A (en) * | 1985-11-14 | 1987-05-27 | Matsushita Electric Ind Co Ltd | Sealed battery |
| JP3197553B2 (en) * | 1990-07-31 | 2001-08-13 | 三洋電機株式会社 | Non-aqueous secondary battery |
| JPH05121055A (en) * | 1991-10-24 | 1993-05-18 | Seiko Electronic Components Ltd | Coin type cell and its manufacture |
| JP2000138042A (en) * | 1998-11-02 | 2000-05-16 | Matsushita Electric Ind Co Ltd | Organic electrolyte battery |
| JP4785282B2 (en) * | 2000-10-11 | 2011-10-05 | セイコーインスツル株式会社 | Manufacturing method of electric double layer capacitor capable of reflow soldering mounting |
| JP2004079355A (en) * | 2002-08-19 | 2004-03-11 | Sony Corp | Nonaqueous electrolyte battery and its manufacturing method |
| JP2005332657A (en) * | 2004-05-19 | 2005-12-02 | Sii Micro Parts Ltd | Non-aqueous electrolyte secondary battery |
| JP2005347100A (en) * | 2004-06-03 | 2005-12-15 | Hitachi Maxell Ltd | Coin type battery |
| JP2006040596A (en) * | 2004-07-23 | 2006-02-09 | Hitachi Maxell Ltd | Flat battery and its manufacturing method |
-
2006
- 2006-09-29 JP JP2006268013A patent/JP5238153B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008091081A (en) | 2008-04-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101877410B (en) | Lithium primary battery and method for producing same | |
| JP2010186682A (en) | Method of manufacturing solid electrolyte layer | |
| EP1241720A3 (en) | Process for fabricating continuously coated electrodes on a porous current collector and cell designs incorporating said electrodes | |
| JP6032628B2 (en) | Thin battery | |
| US7758782B2 (en) | Method and device for producing electrodes for batteries | |
| JP2010061825A (en) | Current collector foil for battery and method of manufacturing the same, as well as battery | |
| JP2019192596A (en) | Sulfide solid state battery and sulfide solid state battery system including the same | |
| JP2008084742A (en) | Lithium-ion secondary battery | |
| JP2017073328A (en) | Nonaqueous electrolyte secondary battery | |
| US20040219424A1 (en) | Non-aqueous electrolyte secondary battery | |
| JP2001266941A (en) | Manufacturing method of gel electrolyte battery | |
| KR20200017486A (en) | Batteries and Electrodes Containing Different Carbon Black Particles | |
| JP2015220102A (en) | Battery mounting substrate | |
| JP6819533B2 (en) | Negative electrode mixture for all-solid-state lithium-ion secondary batteries | |
| JP5238153B2 (en) | Coin-cell battery | |
| WO2015141120A1 (en) | Lithium primary battery | |
| KR19990030265A (en) | Gel electrolyte secondary battery | |
| JP5716543B2 (en) | Lithium ion secondary battery and manufacturing method thereof | |
| US10236477B2 (en) | Electrochemical cells construction and packaging for high temperature applications | |
| JP3879220B2 (en) | Explosion-proof sealing device for secondary batteries | |
| US20020177037A1 (en) | Method for producing a separator/electrode assembly for electrochemical elements | |
| JP2003331836A (en) | Nonaqueous electrolyte secondary battery and method of manufacturing the secondary battery | |
| JP2002117896A (en) | Flat lithium secondary battery | |
| JP7133749B1 (en) | solid electrolytes and batteries | |
| JPWO2019003770A1 (en) | Secondary battery and method of manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090916 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090916 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120731 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120921 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130319 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130401 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5238153 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160405 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |