JP5216961B2 - Non-aqueous electrolyte primary battery - Google Patents
Non-aqueous electrolyte primary battery Download PDFInfo
- Publication number
- JP5216961B2 JP5216961B2 JP2007000318A JP2007000318A JP5216961B2 JP 5216961 B2 JP5216961 B2 JP 5216961B2 JP 2007000318 A JP2007000318 A JP 2007000318A JP 2007000318 A JP2007000318 A JP 2007000318A JP 5216961 B2 JP5216961 B2 JP 5216961B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- positive electrode
- aqueous electrolyte
- primary battery
- electrolyte primary
- 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.)
- Active
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 67
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 15
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 14
- 238000003466 welding Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 26
- 239000002184 metal Substances 0.000 description 26
- 230000007797 corrosion Effects 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 17
- 239000011888 foil Substances 0.000 description 15
- 239000011572 manganese Substances 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 13
- -1 polypropylene Polymers 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 230000007774 longterm Effects 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 238000004804 winding Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- Y02E60/12—
Landscapes
- Sealing Battery Cases Or Jackets (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、非水電解液一次電池に関し、更に詳しくは、長期貯蔵特性に優れた非水電解液一次電池に関するものである。 The present invention relates to a non-aqueous electrolyte primary battery, and more particularly to a non-aqueous electrolyte primary battery having excellent long-term storage characteristics.
二酸化マンガンを活物質として含有する正極を用いた非水電解液一次電池では、外装缶および電池蓋（封口板）には、ステンレス鋼を用いるのが一般的である（例えば、特許文献１）。 In a non-aqueous electrolyte primary battery using a positive electrode containing manganese dioxide as an active material, stainless steel is generally used for the outer can and the battery lid (sealing plate) (for example, Patent Document 1).
ステンレス鋼は、例えば鉄に比べて高価であるため、このようなステンレス鋼を外装缶などに適用することは、非水電解液一次電池のコストダウンの阻害要因となっている。しかし、外装缶や電池蓋のうち、正極の電位になる部位は酸化されるため、かかる箇所には、腐食され易い鉄などの金属を適用することはできない。 Since stainless steel is more expensive than, for example, iron, application of such stainless steel to an outer can or the like is an impediment to cost reduction of the nonaqueous electrolyte primary battery. However, since the portion of the outer can and the battery lid that becomes the potential of the positive electrode is oxidized, a metal such as iron that is easily corroded cannot be applied to the portion.
他方、外装缶や電池蓋のうち、負極の電位になる部位に対しては鉄などを使用することもできるため、このような材質の変更によってコストダウンや生産性向上を図り得る可能性がある。 On the other hand, since iron or the like can be used for the portion that becomes the potential of the negative electrode in the outer can and the battery lid, there is a possibility that cost reduction and productivity improvement can be achieved by such a material change. .
上記の事情の下、本発明者が外装缶や電池蓋が負極の電位になる非水電解液一次電池について、材質が鉄の外装缶を用いて検討を進めた結果、電位とは別の原因で外装缶に腐食が生じることが判明した。上記の腐食は、使用期間が短い用途に適用される場合には殆ど問題とならないが、火災警報器や各種メーター（ガスメーター、電気メーターなど）などの電源など、使用期間が１０年を超えるような極めて長期の用途に適用される電池においては、その寿命が縮められてしまうため、上記の腐食の発生を抑制することは非常に重要な課題である。 Under the circumstances described above, the present inventor investigated the non-aqueous electrolyte primary battery in which the outer can and the battery lid have a negative potential using the outer can made of iron. It was found that the outer can was corroded. The above-mentioned corrosion is hardly a problem when applied to applications where the usage period is short, but the usage period exceeds 10 years, such as power sources for fire alarms and various meters (gas meters, electric meters, etc.). In a battery applied to an extremely long-term use, since its life is shortened, it is a very important issue to suppress the occurrence of the corrosion.
本発明は上記事情に鑑みてなされたものであり、その目的は、長期貯蔵特性に優れた非水電解液一次電池を提供することにある。 This invention is made | formed in view of the said situation, The objective is to provide the nonaqueous electrolyte primary battery excellent in the long-term storage characteristic.
上記目的を達成し得た本発明の非水電解液一次電池は、二酸化マンガンを含有する正極、リチウムまたはリチウム合金を含有する負極、セパレータおよび非水電解液を、外装缶と電池蓋とにより形成された空間内に有する非水電解液一次電池であって、上記外装缶の材質が鉄であり、上記外装缶と上記電池蓋とが溶接により封止されており、上記非水電解液が、エチレンカーボネート、プロピレンカーボネートおよびジメトキシエタンを含有し、上記非水電解液の全溶媒中において、エチレンカーボネートの含有量が２〜５０体積％であり、かつエチレンカーボネートおよびプロピレンカーボネートを含むエステル成分の含有量が７０体積％以下であることを特徴とするものである。 The non-aqueous electrolyte primary battery of the present invention that has achieved the above object is formed of a positive electrode containing manganese dioxide, a negative electrode containing lithium or a lithium alloy, a separator, and a non-aqueous electrolyte solution by an outer can and a battery lid. A non-aqueous electrolyte primary battery in the space formed, wherein the material of the outer can is iron, the outer can and the battery lid are sealed by welding, and the non-aqueous electrolyte is The content of the ester component containing ethylene carbonate , propylene carbonate and dimethoxyethane , wherein the content of ethylene carbonate is 2 to 50% by volume in all the solvents of the non-aqueous electrolyte, and ethylene carbonate and propylene carbonate are contained. There is characterized in der Rukoto 70% by volume or less.
本発明者は、材質が鉄の外装缶を用いた非水電解液一次電池について、電位とは別の理由で生じる腐食の原因について検討したところ、まず、電池外部から電池内へ侵入する水分が、上記腐食の原因となっていることを見出した。従来から汎用されている非水電解液一次電池の多くは、外装缶と電池蓋との間にガスケットを挟み、外装缶をかしめることで封止を行っているが、このような電池を長期間貯蔵していると、このガスケット部分から水分が電池内に侵入し、これが外装缶の腐食を引き起こしているのである。 The present inventor examined the cause of corrosion caused by a reason different from the potential for a non-aqueous electrolyte primary battery using an iron outer can, and firstly, moisture entering the battery from the outside of the battery. And found that it is the cause of the corrosion. Many non-aqueous electrolyte primary batteries that have been widely used in the past are sealed by sandwiching a gasket between the outer can and the battery lid and caulking the outer can. When stored for a long period of time, moisture enters the battery from this gasket portion, which causes corrosion of the outer can.
そこで、本発明の非水電解液一次電池では、電池内への水分の侵入経路となるガスケットを使用せずに、外装缶と電池蓋とを溶接により封止することとし、外装缶の腐食の原因となる水分の電池内への侵入を防止した。 Therefore, in the non-aqueous electrolyte primary battery of the present invention, the outer can and the battery lid are sealed by welding without using a gasket that becomes a moisture intrusion path into the battery, and the outer can is corroded. Prevents moisture from entering the battery.
しかしながら、外装缶と電池蓋とを溶接により封止する構成を採用した場合でも、外装缶に腐食が生じることが判明した。この腐食の原因について更に検討を進めた結果、二酸化マンガンを活物質とする正極を用いた電池では、放電した際に二酸化マンガンから水分が放出され、これが外装缶の腐食を引き起こしていることを見出した。 However, it has been found that even when the configuration in which the outer can and the battery lid are sealed by welding is adopted, the outer can can be corroded. As a result of further investigation on the cause of this corrosion, it was found that in batteries using a positive electrode made of manganese dioxide as an active material, moisture was released from the manganese dioxide when discharged, which caused corrosion of the outer can. It was.
二酸化マンガンを活物質とする正極を用いた電池では、放電により二酸化マンガンの結晶格子中にＬｉ（リチウム）イオンが挿入され、二酸化マンガンの結晶構造が変化して、二酸化マンガンの一部が非水電解液中に溶解する。特に７０℃程度の高温環境下においては、この現象が生じ易くなる。この際、二酸化マンガンの結晶中に存在していた構造水が非水電解液中に放出される。 In a battery using a positive electrode with manganese dioxide as an active material, Li (lithium) ions are inserted into the crystal lattice of manganese dioxide by discharge, and the crystal structure of manganese dioxide changes, so that part of the manganese dioxide is non-aqueous. Dissolves in the electrolyte. In particular, this phenomenon easily occurs in a high temperature environment of about 70 ° C. At this time, the structural water present in the manganese dioxide crystals is released into the non-aqueous electrolyte.
また、放電時には、二酸化マンガン中のＭｎは、下記の反応により、４価から３価に変化する。
ＭｎＯ２（IV）＋ Ｌｉ → ＭｎＯＯＬｉ（III）
At the time of discharge, Mn in manganese dioxide changes from tetravalent to trivalent by the following reaction.
MnO 2 (IV) + Li → MnOOLi (III)
上記反応により生成した３価のＭｎ（III）は、更に２価のＭｎ（II）と４価のＭｎ（IV）とになるが、このうち２価のＭｎ（II）が非水電解液に解けてイオン化しＭｎ２＋となる。そして、Ｍｎ２＋は、外装缶（負極缶）と接触することで還元されて金属Ｍｎとして外装缶内面に析出するため、外装缶内面ではＭｎとＦｅとにより局部電池が形成される。 The trivalent Mn (III) produced by the above reaction further becomes divalent Mn (II) and tetravalent Mn (IV). Of these, divalent Mn (II) is converted into the non-aqueous electrolyte. It melts and ionizes to become Mn 2+ . And since Mn <2+> is reduce | restored by contacting with an exterior can (negative electrode can) and deposits on the inner surface of an exterior can as metal Mn, a local battery is formed by Mn and Fe in an exterior can inner surface.
上記のような放電時の二酸化マンガンの反応に伴って発生する水分が電池内に存在するだけでは、鉄製の外装缶の腐食反応は生じ難いが、かかる水分が、上記のようにＭｎとＦｅとにより局部電池が形成されている箇所に接すると、外装缶が容易に腐食してしまうのである。 The corrosion reaction of the iron outer can is difficult to occur when the moisture generated by the reaction of manganese dioxide at the time of discharge is present in the battery. However, the moisture is Mn and Fe as described above. If it contacts the location where the local battery is formed, the outer can easily corrodes.
そこで、本発明の非水電解液一次電池では、非水電解液にエチレンカーボネートを含有させる構成を採用した。非水電解液がエチレンカーボネートを含有することにより、３価のＭｎ（III）から２価のＭｎ（II）が生成する反応を抑制することができるため、外装缶内面における金属Ｍｎの析出を防止できる。そのため、喩え放電によって二酸化マンガンから構造水が電池内に放出されたとしても、外装缶内面の腐食の発生を抑制することができる。 Therefore, in the nonaqueous electrolyte primary battery of the present invention, a configuration in which ethylene carbonate is contained in the nonaqueous electrolyte is adopted. By containing ethylene carbonate in the non-aqueous electrolyte, the reaction of generating divalent Mn (II) from trivalent Mn (III) can be suppressed, preventing the precipitation of metal Mn on the inner surface of the outer can. it can. Therefore, even if the structural water is released from the manganese dioxide into the battery by analogy discharge, the occurrence of corrosion on the inner surface of the outer can can be suppressed.
このように、本発明では、外装缶と電池蓋とを溶接により封止することによる電池外からの水分の侵入防止作用と、非水電解液にエチレンカーボネートを含有させることによる放電に伴って生じる水分による腐食の抑制作用とを相乗的に機能させることで、鉄製の外装缶を採用しつつ、その腐食を抑制して、電池の長期貯蔵特性の向上を達成している。 As described above, in the present invention, the outer can and the battery lid are sealed by welding to prevent moisture from entering from the outside of the battery, and the non-aqueous electrolyte contains ethylene carbonate in the discharge. By synergistically functioning to suppress the corrosion caused by moisture, the iron outer can is adopted, while the corrosion is suppressed and the long-term storage characteristics of the battery are improved.
本発明によれば、鉄製の外装缶を備えつつ、長期貯蔵特性に優れた非水電解液一次電池を提供することができる。よって、本発明によれば、安価な外装缶を使用することで、製造コストを低減して、非水電解液一次電池の生産性を高めることが可能である。 ADVANTAGE OF THE INVENTION According to this invention, the nonaqueous electrolyte primary battery excellent in the long-term storage characteristic can be provided, providing an iron exterior can. Therefore, according to the present invention, it is possible to reduce the manufacturing cost and increase the productivity of the non-aqueous electrolyte primary battery by using an inexpensive outer can.
図１に、本発明の非水電解液電池の一実施形態を表す縦断側面図を示す。図１において、非水電解液電池１は、上方開口部を有する有底円筒状の外装缶２と、外装缶２内に装填されたシート状正極４とシート状負極５とをセパレータ６を介して巻回してなる電極巻回体３と、非水電解液（以下、単に「電解液」という場合がある）と、外装缶２の上方開口部を封止する電池蓋８を有している。言い換えれば、図１の非水電解液電池１は、外装缶２と外装缶２の上方開口部を封止する電池蓋８とで囲まれる空間内に、シート状正極４とシート状負極５とをセパレータ６を介して巻回してなる電極巻回体３や電解液といった発電要素を有するものである。
In FIG. 1, the vertical side view showing one Embodiment of the nonaqueous electrolyte battery of this invention is shown. In FIG. 1, a nonaqueous electrolyte battery 1 includes a bottomed cylindrical outer can 2 having an upper opening, a sheet-like
外装缶２は、その材質を鉄とするものであるが、例えば、メッキ（Ｎｉメッキなど）を施した鉄板により構成することが好ましい。これにより、従来のステンレス鋼製外装缶を備えた非水電解液一次電池に比べて製造コストを低減して、その生産性を高めることができる。外装缶２の形状としては、円筒形や角筒形などの筒形が挙げられる。 Although the outer can 2 is made of iron, it is preferable that the outer can 2 is made of, for example, an iron plate plated (Ni plating or the like). Thereby, compared with the nonaqueous electrolyte primary battery provided with the conventional stainless steel exterior can, manufacturing cost can be reduced and its productivity can be increased. Examples of the shape of the outer can 2 include cylindrical shapes such as a cylindrical shape and a rectangular tube shape.
外装缶２の上方開口部には電池蓋８が配されており、電池蓋８は、外装缶２の上方開口部の内周縁に溶接されることにより、外装缶２と電池蓋８とで密閉空間を形成している。このように本発明の非水電解液一次電池では、封口構造に、電池外部から電池内への水分の侵入経路となり得るガスケットを使用しないため、電池外部からの水分の侵入を防止して、外装缶の腐食を抑制することができる。外装缶と電池蓋との溶接は、例えばレーザー溶接法により行うことが好ましい。 A battery lid 8 is disposed at the upper opening of the outer can 2, and the battery lid 8 is sealed between the outer can 2 and the battery lid 8 by being welded to the inner periphery of the upper opening of the outer can 2. A space is formed. As described above, in the non-aqueous electrolyte primary battery of the present invention, since a gasket that can be a moisture intrusion path from the outside of the battery to the inside of the battery is not used for the sealing structure, Can corrosion can be suppressed. The welding between the outer can and the battery lid is preferably performed by a laser welding method, for example.
電池蓋２には、その中央部に開設された開口に、ポリプロピレンなどを素材とする絶縁パッキング９を介して装着された端子体１０が設置されている。また、電池蓋８の下部には絶縁板１１が配置されており、該絶縁板１１は、円盤状のベース部１２の周縁に環状の側壁１３を立設した上向きに開口する丸皿形状に形成されていて、ベース部１２の中央にはガス通口１４が開設されている。
The battery cover 2 is provided with a
正極４と端子体１０の下面とは、正極リード体１５で接続されている。また、負極５に取り付けられた負極リード体１６は、外装缶２の上部内面に溶接されている。よって、端子体１０は正極の電位となり、外装缶２および電池蓋８は負極の電位となる。そのため、電池蓋８も、外装缶２と同様に、鉄を材質とすることが可能であり、例えば、メッキ（Ｎｉメッキなど）を施した鉄板により構成することが好ましい。他方、正極の電位となる端子体１０については、その腐食を防止するためにステンレス鋼などが使用される。
The
また、電池内圧が急激に上昇したときの対策として、電池蓋８または外装缶２の缶底２ａには、薄肉部（ベント）を設けることができる。 Further, as a countermeasure when the battery internal pressure suddenly increases, a thin wall portion (vent) can be provided on the battery lid 8 or the can bottom 2a of the outer can 2.
なお、図１は、本発明の非水電解液一次電池の一例を示すものであって、本発明の非水電解液一次電池は図１に示す構造のものに限定される訳ではない。また、図１は、本発明の非水電解液一次電池の構造の理解を容易にするためのものであり、各構成要素のサイズなどは必ずしも正確ではない。 FIG. 1 shows an example of the nonaqueous electrolyte primary battery of the present invention, and the nonaqueous electrolyte primary battery of the present invention is not limited to the structure shown in FIG. Moreover, FIG. 1 is for facilitating understanding of the structure of the nonaqueous electrolyte primary battery of the present invention, and the size of each component is not necessarily accurate.
本発明の非水電解液一次電池に使用できる正極としては、例えば、図１に示すように、２枚の正極合剤シートが集電体を介して積層されてなる構成のシート状正極が挙げられる。 As the positive electrode that can be used in the nonaqueous electrolyte primary battery of the present invention, for example, as shown in FIG. 1, a sheet-like positive electrode having a structure in which two positive electrode mixture sheets are laminated via a current collector is mentioned. It is done.
正極合剤シートとしては、例えば、正極活物質に、導電助剤やバインダーを配合し、必要に応じて水などを添加してなる正極合剤（スラリー）を、ロールなどを用いて圧延するなどして予備シート化し、これを乾燥・粉砕したものを再度ロール圧延などしてシート形状に成形したものが使用できる。正極活物質には、二酸化マンガンを使用する。また、導電助剤としては、例えば、黒鉛、カーボンブラック、アセチレンブラック、ケッチェンブラックなどが挙げられ、これらを１種単独で用いる他、２種以上を併用してもよい。バインダーとしては、ポリフッ化ビニリデン（ＰＶＤＦ）、ゴム系バインダーなどが使用できる。なお、ＰＶＤＦの場合、ディスパージョンタイプのものでもよいし、粉末状のものでもよいが、ディスパージョンタイプのものが特に好適である。正極合剤シートの厚みとしては、例えば、０．５〜１．０ｍｍであることが望ましい。 As the positive electrode mixture sheet, for example, a positive electrode mixture (slurry) obtained by blending a positive electrode active material with a conductive additive or a binder and adding water or the like as necessary is rolled using a roll or the like. Then, a pre-sheet can be formed, and a product obtained by drying and pulverizing the sheet can be roll-rolled again to form a sheet shape. Manganese dioxide is used for the positive electrode active material. Moreover, as a conductive support agent, graphite, carbon black, acetylene black, ketjen black etc. are mentioned, for example, These may be used individually by 1 type, and may use 2 or more types together. As the binder, polyvinylidene fluoride (PVDF), a rubber-based binder, or the like can be used. In the case of PVDF, a dispersion type may be used or a powder type may be used, but a dispersion type is particularly suitable. As thickness of a positive mix sheet, it is desirable that it is 0.5-1.0 mm, for example.
正極合剤シートにおいては、例えば、正極活物質の含有量を９２〜９７質量％、導電助剤の含有量を２〜４質量％、およびバインダーの含有量を１〜４質量％とすることが好ましい。 In the positive electrode mixture sheet, for example, the content of the positive electrode active material is 92 to 97% by mass, the content of the conductive additive is 2 to 4% by mass, and the content of the binder is 1 to 4% by mass. preferable.
正極に用いる集電体としては、例えば、ＳＵＳ３１６、ＳＵＳ４３０、ＳＵＳ４４４などのステンレス鋼を素材とするものが挙げられ、その形態としては、平織り金網、エキスパンドメタル、ラス網、パンチングメタル、箔（板）などが例示できる。集電体の厚みとしては、例えば、０．１〜０．４ｍｍであることが好ましい。 Examples of the current collector used for the positive electrode include those made of stainless steel such as SUS316, SUS430, and SUS444, and the forms thereof include plain weave metal mesh, expanded metal, lath net, punching metal, and foil (plate). Etc. can be exemplified. The thickness of the current collector is preferably, for example, 0.1 to 0.4 mm.
なお、正極集電体の表面には、ペースト状の導電材を塗布しておくことが望ましい。正極集電体として立体構造を有する網状のものを用いた場合も、金属箔やパンチングメタルなどの本質的に平板からなる材料を用いた場合と同様に、導電材の塗布により集電効果の著しい改善が認められる。これは、網状の集電体の金属部分が正極合剤シートと直接的に接触する経路のみならず、網目内に充填された導電材を介しての経路が有効に利用されていることによるものと推定される。 Note that it is desirable to apply a paste-like conductive material to the surface of the positive electrode current collector. When a positive electrode current collector having a three-dimensional structure is used, as in the case of using an essentially flat material such as a metal foil or a punching metal, the current collecting effect is remarkable by applying a conductive material. Improvement is observed. This is because the route through the conductive material filled in the mesh is effectively used as well as the route in which the metal part of the mesh current collector is in direct contact with the positive electrode mixture sheet. It is estimated to be.
導電材としては、例えば、銀ペーストやカーボンペーストなどを用いることができる。特にカーボンペーストは、銀ペーストに比べて材料費が安く済み、しかも銀ペーストと略同等の接触効果が得られるため、非水電解液一次電池の製造コストの低減化を図る上で好適である。導電材のバインダーとしては、水ガラスやイミド系のバインダーなどの耐熱性の材料を用いることが好ましい。これは正極合剤シート中の水分を除去する際に２００℃を超える高温で乾燥処理するためである。 As the conductive material, for example, silver paste or carbon paste can be used. In particular, the carbon paste is suitable for reducing the manufacturing cost of the non-aqueous electrolyte primary battery because the material cost is lower than that of the silver paste and the contact effect is almost the same as that of the silver paste. As the binder for the conductive material, it is preferable to use a heat resistant material such as water glass or an imide binder. This is because the drying treatment is performed at a high temperature exceeding 200 ° C. when moisture in the positive electrode mixture sheet is removed.
本発明に使用できる負極としては、図１に示すようなシート状負極が挙げられ、このシート状負極は、例えば、負極活物質である金属リチウム箔と、負極集電体である金属箔とで構成される。金属リチウム箔の材料としては金属リチウムのみならず、リチウム−アルミニウムなどのリチウム合金を挙げることができる。金属リチウム箔の厚みとしては、例えば、０．１５〜０．４ｍｍであることが好ましい。 Examples of the negative electrode that can be used in the present invention include a sheet-like negative electrode as shown in FIG. 1. The sheet-like negative electrode includes, for example, a metal lithium foil that is a negative electrode active material and a metal foil that is a negative electrode current collector. Composed. Examples of the material for the metal lithium foil include not only metal lithium but also lithium alloys such as lithium-aluminum. The thickness of the metal lithium foil is preferably 0.15 to 0.4 mm, for example.
負極集電体の素材としては、銅、ニッケル、鉄、ステンレスなどを挙げることができる。負極集電体の厚み分だけ外装缶の内部体積が減少するため、負極集電体の厚み寸法は可及的に小さいことが好ましく、具体的には、例えば、０．１ｍｍ以下とすることが推奨される。すなわち、負極集電体が厚すぎると、負極活物質である金属リチウム箔などの仕込み量を少なくせざるを得ず、電池容量の低下を招く虞がある。また、負極集電体が薄すぎると、破れやすくなるため、負極集電体の厚みは、０．００５ｍｍ以上とすることが望ましい。また、負極集電体は、その幅が金属リチウム箔の幅と同じか、それよりも広いことが好ましく、また、その面積が片面に配置される金属リチウム箔の面積の１００〜１３０％であることが好ましい。負極集電体の面積を上記のようにすることによって、負極集電体の幅が金属リチウム箔の幅と同じかまたは広く、長さが長くなるため、負極集電体の周囲に沿って金属リチウム箔が切れて電気的接続が断たれることを防ぐことができる。 Examples of the material for the negative electrode current collector include copper, nickel, iron, and stainless steel. Since the internal volume of the outer can decreases by the thickness of the negative electrode current collector, the thickness dimension of the negative electrode current collector is preferably as small as possible, specifically, for example, 0.1 mm or less. Recommended. That is, if the negative electrode current collector is too thick, the amount of metal lithium foil or the like that is the negative electrode active material must be reduced, which may lead to a decrease in battery capacity. Moreover, since it will be easy to tear when a negative electrode collector is too thin, it is desirable that the thickness of a negative electrode collector be 0.005 mm or more. The width of the negative electrode current collector is preferably the same as or wider than the width of the metal lithium foil, and the area is 100 to 130% of the area of the metal lithium foil arranged on one side. It is preferable. By making the area of the negative electrode current collector as described above, the width of the negative electrode current collector is the same as or wider than the width of the metal lithium foil, and the length becomes longer. It is possible to prevent the lithium foil from being cut and the electrical connection from being cut off.
本発明に係る電解液としては、有機溶媒などの非水系溶媒に電解質としてＬｉＰＦ６、ＬｉＣｌＯ４、ＬｉＣＦ３ＳＯ３などを溶解して調製したものが挙げられるが、溶媒として、エチレンカーボネート（ＥＣ）を使用する。電解液がＥＣを含有することで、二酸化マンガンの放電反応に伴う電解液中でのＭｎ２＋の生成を抑えて、外装缶内面での金属Ｍｎの析出を抑制し、これによる外装缶の腐食を防止することができる。 Examples of the electrolytic solution according to the present invention include those prepared by dissolving LiPF 6 , LiClO 4 , LiCF 3 SO 3 and the like as an electrolyte in a non-aqueous solvent such as an organic solvent. As the solvent, ethylene carbonate (EC) is used. Is used. Since the electrolytic solution contains EC, the generation of Mn 2+ in the electrolytic solution accompanying the discharge reaction of manganese dioxide is suppressed, and the precipitation of metal Mn on the inner surface of the outer can is suppressed, thereby causing corrosion of the outer can. Can be prevented.
電解液の溶媒には、ＥＣと他の非水系溶媒とを併用することが好ましい。エチレンカーボネートと併用し得る非水系溶媒としては、ジメチルカーボネートなどの鎖状エステル；プロピレンカーボネート（ＰＣ）などの環状エステル；ジメトキシエタン（ＤＭＥ）などの鎖状エーテルなどが挙げられる。良好な特性の電池を構成できる点で、ＥＣとＤＭＥとＰＣとを併用することが特に好ましい。 It is preferable to use EC and another non-aqueous solvent in combination as the solvent of the electrolytic solution. Non-aqueous solvents that can be used in combination with ethylene carbonate include chain esters such as dimethyl carbonate; cyclic esters such as propylene carbonate (PC); chain ethers such as dimethoxyethane (DME). It is particularly preferable to use EC, DME, and PC in combination in that a battery having good characteristics can be configured.
電解液溶媒中のＥＣの含有量は、ＥＣを電解液に含有させることによる作用をより有効に発揮させる観点から、２体積％以上とすることが好ましく、５体積％以上とすることがより好ましい。なお、ＥＣの含有量が多すぎると、電池の低温特性が低下することがあるため、電解液溶媒中のＥＣの含有量は、５０体積％以下とすることが好ましく、３０体積％以下とすることがより好ましい。 The content of EC in the electrolyte solvent is preferably 2% by volume or more, and more preferably 5% by volume or more, from the viewpoint of more effectively exerting the effect of containing EC in the electrolyte solution. . In addition, since the low temperature characteristic of a battery may fall when there is too much content of EC, it is preferable that content of EC in electrolyte solution shall be 50 volume% or less, and shall be 30 volume% or less. It is more preferable.
なお、ＥＣに加えてＰＣなどのエステル成分および、ＤＭＥなどのエーテル成分を併用する場合には、ＥＣを含めた電解液溶媒中のエステル成分は、７０体積％以下とすることが好ましく、６０体積％以下とすることがより好ましい。電解液溶媒においてエステル成分量が多すぎると、電解液自体の粘度が高くなりすぎ、セパレータの電解液の吸液性が低下して電池の生産性が悪くなるとともに、低温特性が低下することがあるためである。 When an ester component such as PC and an ether component such as DME are used in addition to EC, the ester component in the electrolyte solution solvent including EC is preferably 70% by volume or less, and 60 volume. % Or less is more preferable. If the amount of the ester component in the electrolyte solution is too large, the viscosity of the electrolyte solution itself becomes too high, the liquid absorption property of the electrolyte solution of the separator is lowered and the productivity of the battery is deteriorated, and the low temperature characteristics may be lowered. Because there is.
また、電解液中の電解質の濃度は、０．３〜１．５ｍｏｌ／ｌとすることが好ましい。 Moreover, it is preferable that the density | concentration of the electrolyte in electrolyte solution shall be 0.3-1.5 mol / l.
セパレータとしては、従来公知の非水電解液一次電池に採用されている微孔性フィルム製のセパレータや不織布製のセパレータが適用できる。 As a separator, the separator made from a microporous film and the separator made from a nonwoven fabric which are employ | adopted as a conventionally well-known nonaqueous electrolyte primary battery are applicable.
セパレータとなる微孔性フィルムを構成する樹脂としては、例えば、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）などのポリオレフィン；ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）などのポリエステル；ポリフェニレンスルフィド（ＰＰＳ）；などが挙げられる。このような微孔性フィルムの市販品としては、例えば、旭化成株式会社製「ハイポア」（商品名）、東燃化学社製「セティーラ」（商品名）などが挙げられる。 Examples of the resin constituting the microporous film serving as the separator include polyolefins such as polyethylene (PE) and polypropylene (PP); polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyphenylene sulfide (PPS) And so on. Examples of such commercially available microporous films include “Hypore” (trade name) manufactured by Asahi Kasei Corporation, “Setilla” (trade name) manufactured by Tonen Chemical Co., Ltd., and the like.
また、セパレータとなる不織布としては、例えば、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）などのポリオレフィン；ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）などのポリエステル；ポリフェニレンスルフィド（ＰＰＳ）；などを素材とし、公知の各種製法で製造されたものを用いることができる。 Moreover, as a nonwoven fabric used as a separator, for example, polyolefins such as polyethylene (PE) and polypropylene (PP); polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); polyphenylene sulfide (PPS); Those produced by various known production methods can be used.
更に、上記微孔性フィルムと上記不織布とを積層した構造のセパレータを用いてもよい。 Furthermore, you may use the separator of the structure which laminated | stacked the said microporous film and the said nonwoven fabric.
セパレータの厚みは、例えば、１５〜５０μｍであることが好ましい。 The thickness of the separator is preferably 15 to 50 μm, for example.
電池を構成するにあたっては、例えば、正極と負極とを、セパレータを介して積層して電極積層体としたり、シート状正極とシート状負極とを、セパレータを介在させた状態で巻回して電極巻回体として用いることが好ましい。 In configuring a battery, for example, a positive electrode and a negative electrode are laminated via a separator to form an electrode laminate, or a sheet-like positive electrode and a sheet-like negative electrode are wound with a separator interposed therebetween to form an electrode. It is preferable to use it as a circular body.
本発明の非水電解液一次電池は、長期貯蔵特性に優れており、例えば、１０年を超えるような長期にわたって使用される用途（上述の火災警報器の電源用途や各種メーターの電源用途など）に好適に用いることができるが、これら以外にも、従来公知の非水電解液一次電池が適用されている各種用途に適用することができる。 The nonaqueous electrolyte primary battery of the present invention is excellent in long-term storage characteristics, and is used for a long period of time, for example, more than 10 years (such as the above-mentioned fire alarm power supply and various meter power supplies). In addition to these, it can be applied to various applications to which a conventionally known non-aqueous electrolyte primary battery is applied.
以下、実施例に基づいて本発明を詳細に述べる。ただし、下記実施例は、本発明を制限するものではなく、前・後記の趣旨を逸脱しない範囲で変更実施をすることは、全て本発明の技術的範囲に包含される。この実施例においては、非水電解液一次電池として、外径：１７ｍｍ、高さ：４５ｍｍの円筒形非水電解液一次電池を例に挙げて説明する。なお、本実施例で使用する「％」は、特に断らない限り質量基準（質量％）である。 Hereinafter, the present invention will be described in detail based on examples. However, the following examples are not intended to limit the present invention, and all modifications made without departing from the spirit of the preceding and following descriptions are included in the technical scope of the present invention. In this embodiment, a cylindrical nonaqueous electrolyte primary battery having an outer diameter of 17 mm and a height of 45 mm will be described as an example of the nonaqueous electrolyte primary battery. In addition, "%" used in a present Example is a mass reference | standard (mass%) unless there is particular notice.
実施例１
実施例１の非水電解液一次電池について、［正極の作製］、［負極の作製］、［電極巻回体の作製］、［電池組み立て］、［後処理（予備放電、エージング）］の順に説明する。
Example 1
About the nonaqueous electrolyte primary battery of Example 1, [Preparation of positive electrode], [Preparation of negative electrode], [Preparation of wound electrode body], [Assembly of battery], [Post-treatment (preliminary discharge, aging)] explain.
［正極の作製］
まず、以下の手順で、正極合剤（質量比で、固形分：水分＝１００：３０のもの）を調製した。カーボンブラック：３％と二酸化マンガン（東ソー社製）：９２％とを、プラネタリーミキサーを用いて乾式で５分間混合した後、水を固形分の２０％（質量比）となるように添加して５分間混合した。ＰＴＦＥディスパージョン（ダイキン工業社製「Ｄ−１」）を、固形分が、正極合剤の固形分で５％に当たる量だけ用意し、これを残りの水で希釈して、上記の混合物に添加し、５分間混合して正極合剤を得た。
[Production of positive electrode]
First, a positive electrode mixture (in mass ratio, solid content: water content = 100: 30) was prepared by the following procedure. Carbon black: 3% and manganese dioxide (manufactured by Tosoh Corporation): 92% were mixed using a planetary mixer in a dry process for 5 minutes, and then water was added to a solid content of 20% (mass ratio). And mixed for 5 minutes. Prepare PTFE dispersion ("D-1" manufactured by Daikin Industries, Ltd.) in an amount corresponding to 5% of the solid content of the positive electrode mixture, dilute it with the remaining water, and add to the above mixture And mixed for 5 minutes to obtain a positive electrode mixture.
上記の正極合剤を、直径：２５０ｍｍの２本ロールを用い、ロール温度を１２５±５℃に調整し、プレス圧：７トン／ｃｍ、ロール間隔：０．４ｍｍ、回転速度：１０ｒｐｍの条件で、ロール圧延してシート化した。ロールを通過した正極合剤（予備シート）を１０５±５℃で残水分が２％以下になるまで乾燥した。次いで乾燥後の予備シートを粉砕機を用いて粉砕した後、再度ロールによるシート化を行った。ロールの間隔は０．６±０．０５ｍｍに調整し、ロール温度：１２５±１０℃、プレス圧：７トン／ｃｍ、回転速度：１０ｒｐｍの条件でシート化して正極合剤層とするための正極合剤シートを得た。得られた正極合剤シートは、厚みが１．０ｍｍで、外装缶内径の５．９％に相当する。また、正極合剤シートの密度は２．５ｇ／ｃｍ３であり、上記手法により求めた空隙率は、４２％であった。この正極合剤シートを裁断して、幅：３７ｍｍ、長さ：５１ｍｍの内周用の正極合剤シートと、幅：３７ｍｍ、長さ：６２ｍｍの外周用の正極合剤シートを得た。 Using the above positive electrode mixture, two rolls having a diameter of 250 mm, adjusting the roll temperature to 125 ± 5 ° C., press pressure: 7 ton / cm, roll interval: 0.4 mm, rotation speed: 10 rpm The sheet was rolled and rolled. The positive electrode mixture (preliminary sheet) that passed through the roll was dried at 105 ± 5 ° C. until the residual moisture was 2% or less. Next, the dried preliminary sheet was pulverized using a pulverizer, and then formed into a sheet by a roll again. Positive electrode for adjusting the roll interval to 0.6 ± 0.05 mm, forming a positive electrode mixture layer by forming a sheet under the conditions of roll temperature: 125 ± 10 ° C., press pressure: 7 tons / cm, rotation speed: 10 rpm A mixture sheet was obtained. The obtained positive electrode mixture sheet has a thickness of 1.0 mm and corresponds to 5.9% of the inner diameter of the outer can. Moreover, the density of the positive mix sheet was 2.5 g / cm < 3 >, and the porosity calculated | required by the said method was 42%. The positive electrode mixture sheet was cut to obtain an inner periphery positive electrode mixture sheet having a width of 37 mm and a length of 51 mm, and an outer periphery positive electrode mixture sheet having a width of 37 mm and a length of 62 mm.
正極集電体には、ステンレス鋼（ＳＵＳ３１６）製のエキスパンドメタルを用いた。このエキスパンドメタルを、幅：３４ｍｍ、長さ：５６ｍｍに切断し、長さ方向の中央部に、厚み：０．１ｍｍ、幅；３ｍｍのステンレス鋼製のリボンを正極リード体として抵抗溶接により取り付けた。更にこのエキスパンドメタルに、カーボンペースト（日本黒鉛社製）を、網の目をつぶさない程度に塗布した後、１０５±５℃の温度で乾燥して正極集電体とした。なお、カーボンペーストの塗布量は、乾燥後の塗布量で５ｍｇ／ｃｍ２となるようにした。 As the positive electrode current collector, an expanded metal made of stainless steel (SUS316) was used. This expanded metal was cut to a width of 34 mm and a length of 56 mm, and a stainless steel ribbon having a thickness of 0.1 mm and a width of 3 mm was attached to the central portion in the length direction by resistance welding as a positive electrode lead body. . Further, a carbon paste (manufactured by Nippon Graphite Co., Ltd.) was applied to the expanded metal so as not to crush the mesh, and then dried at a temperature of 105 ± 5 ° C. to obtain a positive electrode current collector. The coating amount of the carbon paste was set to 5 mg / cm 2 after drying.
次に、内周用の正極合剤シートと外周用の正極合剤シートの間に正極集電体を介在させた状態で、長さ方向の片端部のみを固定して三者を一体化した。具体的には、内周用の正極合剤シートと外周用の正極合剤シートを、長さ方向の片端を揃えると共に、正極集電体の端部が、２枚の正極合剤シートの、両者を揃えた片端部からはみ出ないようにセットし、その状態で、２枚の正極合剤シートの、両者を揃えた片端部から５ｍｍの箇所をプレスにより圧着することで、三者を一体化した。その後、２枚の正極合剤シートと正極集電体とを一体化したものを２５０±１０℃で６時間熱風乾燥して、幅が３７ｍｍのシート状正極を得た。 Next, in a state where the positive electrode current collector is interposed between the positive electrode mixture sheet for the inner periphery and the positive electrode mixture sheet for the outer periphery, only one end in the length direction is fixed and the three parties are integrated. . Specifically, the positive electrode mixture sheet for the inner periphery and the positive electrode mixture sheet for the outer periphery are aligned with one end in the length direction, and the end of the positive electrode current collector is composed of two positive electrode mixture sheets. Set the two so that they do not protrude from one end, and in that state, press the 5mm part of the two positive electrode mixture sheets from the end where both are aligned, so that the three parties are integrated. did. Then, the two positive electrode mixture sheets and the positive electrode current collector were integrated with hot air at 250 ± 10 ° C. for 6 hours to obtain a sheet-like positive electrode having a width of 37 mm.
［負極の作製］
負極は、幅：３９ｍｍ、長さ：１７０ｍｍ、厚み：１０μｍの銅箔（負極集電体）上に、幅：３７ｍｍ、長さ：８７ｍｍ、厚み：０．３０ｍｍの金属リチウム箔と、幅：３７ｍｍ、長さ：５０ｍｍ、厚み：０．３０ｍｍの金属リチウム箔を配置して構成した。まず、長さが５０ｍｍの方の金属リチウム箔に、幅：３ｍｍ、長さ：２０ｍｍ、厚み：０．１ｍｍのニッケル製の負極リード体を圧着した。その後、上記の２枚の金属リチウム箔を、離間させた状態で上記銅箔上に配置し、シート状負極を作製した。
[Production of negative electrode]
The negative electrode has a width: 37 mm, a length: 170 mm, a thickness: 10 μm on a copper foil (negative electrode current collector), a width: 37 mm, a length: 87 mm, a thickness: 0.30 mm metal lithium foil, and a width: 37 mm. A metal lithium foil having a length of 50 mm and a thickness of 0.30 mm was arranged. First, a negative electrode lead made of nickel having a width of 3 mm, a length of 20 mm, and a thickness of 0.1 mm was pressure-bonded to a metal lithium foil having a length of 50 mm. Thereafter, the two metal lithium foils were placed on the copper foil in a separated state to produce a sheet-like negative electrode.
［巻回構造の電極体の作製］
セパレータとして、幅：４４ｍｍ、長さ：１７０ｍｍ、厚み：２５μｍの微孔性ポリエチレンフィルム［旭化成社製「ハイポア」（商品名）］を用意した。
[Preparation of wound electrode body]
As a separator, a microporous polyethylene film [“Hypore” (trade name) manufactured by Asahi Kasei Co., Ltd.] having a width of 44 mm, a length of 170 mm, and a thickness of 25 μm was prepared.
シート状負極の銅箔上に接着テープを貼り付け、この接着テープにセパレータを熱溶着によって貼り付けた。次に、セパレータの上記熱溶着部分を、２つ割の直径：３．５ｍｍの巻回芯に挟み、１周巻いた。次いで、負極をセパレータと共に１周巻き込んだ後、シート状正極の固定した側を巻回芯側に載置して巻回した。巻回終了後は、銅箔が最外周を覆う形となった。以上により、電極巻回体を得た。 Adhesive tape was affixed on the copper foil of a sheet-like negative electrode, and the separator was affixed on this adhesive tape by heat welding. Next, the heat-welded portion of the separator was sandwiched between two winding cores having a diameter of 3.5 mm and wound once. Next, after winding the negative electrode together with the separator once, the side on which the sheet-like positive electrode was fixed was placed on the winding core side and wound. After winding, the copper foil covered the outermost periphery. The electrode winding body was obtained by the above.
［電池組み立て］
非水電解液電池の組み立て工程を、図１を参照して説明する。Ｎｉメッキした鉄缶からなる有底円筒形の外装缶２の内底部２ａに、厚み：０．２ｍｍのポリプロピレン製の絶縁板を挿入し、その上に電極巻回体３を、正極リード体１５が上側を向く姿勢で挿入した。電極体３の負極リード体１６を外装缶２の内面に抵抗溶接し、正極リード体１５は、絶縁板１１を挿入した後に、電池蓋８の端子板１０の下面に抵抗溶接した。この時点で絶縁抵抗を測定し、短絡がないことを確認した。なお、電池蓋８には、Ｎｉメッキした鉄製のものを用いた。
[Battery assembly]
The assembly process of the nonaqueous electrolyte battery will be described with reference to FIG. An insulating plate made of polypropylene having a thickness of 0.2 mm is inserted into the inner bottom portion 2a of the bottomed cylindrical outer can 2 made of Ni-plated iron can, and the electrode winding body 3 and the positive
電解液には、ＥＣとＰＣとＤＭＥとを１０：５：８５（体積比）で混合した混合溶媒に、ＬｉＣＦ３ＳＯ３を０．５ｍｏｌ／ｌの濃度で溶解させた非水系の溶液を用意し、これを外装缶２内に３．５ｍｌ注入した。注入は３回に分け、最終工程で減圧しつつ全量を注入した。電解液の注入後、電池蓋８を外装缶２の上方開口部に嵌合し、レーザー溶接により外装缶２の開口端部の内周部と電池蓋８の外周部とを溶接して外装缶２の開口部を封口した。 As the electrolyte, a non-aqueous solution prepared by dissolving LiCF 3 SO 3 at a concentration of 0.5 mol / l in a mixed solvent in which EC, PC, and DME are mixed at a volume ratio of 10: 5: 85 is prepared. Then, 3.5 ml of this was injected into the outer can 2. Injection was divided into three times, and the whole amount was injected while reducing the pressure in the final step. After injecting the electrolytic solution, the battery lid 8 is fitted into the upper opening of the outer can 2, and the inner peripheral portion of the opening end of the outer can 2 and the outer peripheral portion of the battery lid 8 are welded by laser welding. 2 openings were sealed.
［後処理（予備放電、エージング）］
封口した電池を、１Ωの抵抗で３０秒間予備放電し、７０℃で６時間保管した後、１Ωの定抵抗で１分間、２次予備放電を行った。予備放電後の電池を、室温で７日間エージングし、開路電圧を測定して安定電圧が得られていることを確認して、外径：１７.０ｍｍ、総高：４５．０ｍｍの非水電解液一次電池を得た。この非水電解液一次電池の全溶媒中におけるＥＣの含有量は１０体積％である。
[Post-treatment (preliminary discharge, aging)]
The sealed battery was preliminarily discharged with a resistance of 1Ω for 30 seconds, stored at 70 ° C. for 6 hours, and then subjected to a secondary preliminary discharge with a constant resistance of 1Ω for 1 minute. The battery after the preliminary discharge was aged at room temperature for 7 days, the open circuit voltage was measured to confirm that a stable voltage was obtained, and non-aqueous electrolysis with an outer diameter of 17.0 mm and a total height of 45.0 mm A liquid primary battery was obtained. The content of EC in all the solvents of this non-aqueous electrolyte primary battery is 10% by volume.
実施例２
電解液溶媒を、ＥＣとＰＣとＤＭＥとを２：５：９３（体積比）で混合した混合溶媒に変更した以外は、実施例１と同様にして非水電解液一次電池を作製した。この非水電解液一次電池の全溶媒中におけるＥＣの含有量は２体積％である。
Example 2
A non-aqueous electrolyte primary battery was produced in the same manner as in Example 1 except that the electrolyte solvent was changed to a mixed solvent in which EC, PC, and DME were mixed at 2: 5: 93 (volume ratio). The content of EC in all solvents of this non-aqueous electrolyte primary battery is 2% by volume.
実施例３
電解液溶媒を、ＥＣとＰＣとＤＭＥとを５：５：９０（体積比）で混合した混合溶媒に変更した以外は、実施例１と同様にして非水電解液一次電池を作製した。この非水電解液一次電池の全溶媒中におけるＥＣの含有量は５体積％である。
Example 3
A non-aqueous electrolyte primary battery was produced in the same manner as in Example 1 except that the electrolyte solvent was changed to a mixed solvent in which EC, PC, and DME were mixed at 5: 5: 90 (volume ratio). The content of EC in all solvents of this non-aqueous electrolyte primary battery is 5% by volume.
実施例４
電解液溶媒を、ＥＣとＰＣとＤＭＥとを３０：５：６５（体積比）で混合した混合溶媒に変更した以外は、実施例１と同様にして非水電解液一次電池を作製した。この非水電解液一次電池の全溶媒中におけるＥＣの含有量は３０体積％である。
Example 4
A non-aqueous electrolyte primary battery was produced in the same manner as in Example 1 except that the electrolyte solution was changed to a mixed solvent obtained by mixing EC, PC, and DME at 30: 5: 65 (volume ratio). The content of EC in all the solvents of this non-aqueous electrolyte primary battery is 30% by volume.
実施例５
電解液溶媒を、ＥＣとＰＣとＤＭＥとを５０：５：４５（体積比）で混合した混合溶媒に変更した以外は、実施例１と同様にして非水電解液一次電池を作製した。この非水電解液一次電池の全溶媒中におけるＥＣの含有量は５０体積％である。
Example 5
A nonaqueous electrolyte primary battery was produced in the same manner as in Example 1 except that the electrolyte solvent was changed to a mixed solvent in which EC, PC, and DME were mixed at 50: 5: 45 (volume ratio). The EC content in all the solvents of the nonaqueous electrolyte primary battery is 50% by volume.
実施例６
電解液溶媒を、ＥＣとＰＣとＤＭＥとを７０：５：２５（体積比）で混合した混合溶媒に変更した以外は、実施例１と同様にして非水電解液一次電池を作製した。この非水電解液一次電池の全溶媒中におけるＥＣの含有量は７０体積％である。
Example 6
A nonaqueous electrolyte primary battery was produced in the same manner as in Example 1 except that the electrolyte solvent was changed to a mixed solvent in which EC, PC, and DME were mixed at a volume ratio of 70: 5: 25. The EC content in all the solvents of the non-aqueous electrolyte primary battery is 70% by volume.
実施例７
電解液溶媒を、ＥＣとＤＭＥとを１０：９０（体積比）で混合した混合溶媒に変更した以外は、実施例１と同様にして非水電解液一次電池を作製した。この非水電解液一次電池の全溶媒中におけるＥＣの含有量は１０体積％である。
Example 7
A non-aqueous electrolyte primary battery was produced in the same manner as in Example 1 except that the electrolyte solvent was changed to a mixed solvent in which EC and DME were mixed at 10:90 (volume ratio). The content of EC in all the solvents of this non-aqueous electrolyte primary battery is 10% by volume.
比較例１
外装缶の上方開口部の封口構造を、外装缶と電池蓋との間にガスケットを介在させ、外装缶をかしめることで封止するように変更した（すなわち、クリンプ封止した）以外は、実施例１と同様にして非水電解液一次電池を作製した。
Comparative Example 1
The sealing structure of the upper opening of the outer can was changed to be sealed by caulking the outer can with a gasket interposed between the outer can and the battery lid (ie, crimp sealed), A non-aqueous electrolyte primary battery was produced in the same manner as in Example 1.
比較例２
電解液溶媒を、ＰＣとＤＭＥとを５：９５（体積比）で混合した混合溶媒に変更した以外は、実施例１と同様にして非水電解液一次電池を作製した。この非水電解液一次電池では、電解液の全溶媒中にＥＣを含んでいない。
Comparative Example 2
A non-aqueous electrolyte primary battery was produced in the same manner as in Example 1 except that the electrolyte solvent was changed to a mixed solvent in which PC and DME were mixed at 5:95 (volume ratio). In this non-aqueous electrolyte primary battery, EC is not included in the entire solvent of the electrolyte.
＜長期信頼性試験＞
実施例１〜７および比較例１〜２の非水電解液一次電池について、８０℃で０．５ｈｒ保持した後、直ぐに−３０℃にし、この温度で０．５ｈｒ保持する操作を１サイクルとするヒートショック試験を５４００サイクル実施した。このヒートショック試験は、１サイクルが、１日に電池が曝され得る最大の温度差を想定したものであり、５４００サイクルは１５年分に相当する。
<Long-term reliability test>
For the non-aqueous electrolyte primary batteries of Examples 1 to 7 and Comparative Examples 1 and 2, after holding at 80 ° C. for 0.5 hr, immediately setting to −30 ° C. and holding at this temperature for 0.5 hr is one cycle. A heat shock test was conducted for 5400 cycles. In this heat shock test, one cycle assumes the maximum temperature difference at which a battery can be exposed to one day, and 5400 cycles corresponds to 15 years.
５４００サイクルのヒートショック試験を行った各電池を分解して、外装缶の内面の状態を観察し、下記基準に従ってランク付けを行った。結果を表１に示す。○のものが合格と判定できる。
○ ：外装缶内面に腐食の発生が認められない。
× ：外装缶内面を顕微鏡観察（倍率：１０倍）すると、腐食の発生が確認できる。
××：目視観察により外装缶内に腐食の発生が認められる。
Each battery subjected to a heat shock test of 5400 cycles was disassembled, the state of the inner surface of the outer can was observed, and ranking was performed according to the following criteria. The results are shown in Table 1. ○ can be determined to pass.
○: No corrosion was observed on the inner surface of the outer can.
X: The occurrence of corrosion can be confirmed by microscopic observation of the inner surface of the outer can (magnification: 10 times).
XX: Corrosion is observed in the outer can by visual observation.
表１から明らかなように、実施例１〜７の非水電解液一次電池は、５４００サイクルのヒートショック試験を経ても外装缶内面が腐食しておらず、長期貯蔵特性が非常に優れている。 As is clear from Table 1, the nonaqueous electrolyte primary batteries of Examples 1 to 7 are not corroded on the inner surface of the outer can even after the heat shock test of 5400 cycles, and have excellent long-term storage characteristics. .
＜放電容量測定＞
実施例１〜７および比較例２の非水電解液一次電池について、２０℃で４０ｍＡの連続放電を行い、終止電圧２Ｖとした場合の放電容量を測定した。なお、各電池の試料数は５個とし、その平均値を各実施例、比較例の電池の放電容量とした。結果を表２に示す。
<Discharge capacity measurement>
About the nonaqueous electrolyte primary battery of Examples 1-7 and Comparative Example 2, 40 mA of continuous discharge was performed at 20 ° C., and the discharge capacity when the final voltage was 2 V was measured. In addition, the number of samples of each battery was set to five, and the average value was made into the discharge capacity of the battery of each Example and a comparative example. The results are shown in Table 2.
表２から明らかなように、ＥＣの含有量が好適な範囲である実施例１〜５の非水電解液一次電池は良好な放電特性を有している。 As can be seen from Table 2, the nonaqueous electrolyte primary batteries of Examples 1 to 5 in which the EC content is in a suitable range have good discharge characteristics.
１ 非水電解液一次電池
２ 外装缶
３ 電極巻回体
８ 電池蓋
DESCRIPTION OF SYMBOLS 1 Nonaqueous electrolyte primary battery 2 Exterior can 3 Electrode winding body 8 Battery cover
Claims (1)
上記外装缶の材質が鉄であり、
上記外装缶と上記電池蓋とが溶接により封止されており、
上記非水電解液が、エチレンカーボネート、プロピレンカーボネートおよびジメトキシエタンを含有し、
上記非水電解液の全溶媒中において、エチレンカーボネートの含有量が２〜５０体積％であり、かつエチレンカーボネートおよびプロピレンカーボネートを含むエステル成分の含有量が７０体積％以下であることを特徴とする非水電解液一次電池。
A non-aqueous electrolyte primary battery having a positive electrode containing manganese dioxide, a negative electrode containing lithium or a lithium alloy, a separator and a non-aqueous electrolyte in a space formed by an outer can and a battery lid,
The material of the outer can is iron,
The outer can and the battery lid are sealed by welding,
The non-aqueous electrolyte contains ethylene carbonate , propylene carbonate and dimethoxyethane ,
In all solvent of the nonaqueous electrolytic solution, a content of ethylene carbonate 2-50% by volume, and the said der Rukoto content 70% by volume or less of the ester component comprising ethylene carbonate and propylene carbonate Non-aqueous electrolyte primary battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007000318A JP5216961B2 (en) | 2007-01-05 | 2007-01-05 | Non-aqueous electrolyte primary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007000318A JP5216961B2 (en) | 2007-01-05 | 2007-01-05 | Non-aqueous electrolyte primary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008166227A JP2008166227A (en) | 2008-07-17 |
| JP5216961B2 true JP5216961B2 (en) | 2013-06-19 |
Family
ID=39695402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2007000318A Active JP5216961B2 (en) | 2007-01-05 | 2007-01-05 | Non-aqueous electrolyte primary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5216961B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5252691B2 (en) * | 2008-04-28 | 2013-07-31 | 日立マクセル株式会社 | Cylindrical non-aqueous electrolyte primary battery and manufacturing method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2980618B2 (en) * | 1989-10-04 | 1999-11-22 | 日立マクセル株式会社 | Organic electrolyte primary battery |
| JP4765161B2 (en) * | 2000-11-30 | 2011-09-07 | パナソニック株式会社 | Non-aqueous electrolyte battery |
| JP4765160B2 (en) * | 2000-11-30 | 2011-09-07 | パナソニック株式会社 | Non-aqueous electrolyte battery |
| JP4129955B2 (en) * | 2003-03-17 | 2008-08-06 | 日立マクセル株式会社 | Battery and battery manufacturing method |
| JP4127520B2 (en) * | 2003-04-10 | 2008-07-30 | 日立マクセル株式会社 | battery |
| JP4257192B2 (en) * | 2003-12-02 | 2009-04-22 | 日立マクセル株式会社 | Non-aqueous electrolyte battery |
-
2007
- 2007-01-05 JP JP2007000318A patent/JP5216961B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008166227A (en) | 2008-07-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW504854B (en) | Flat non-aqueous electrolyte secondary cell | |
| KR20150126820A (en) | Lithium ion secondary battery | |
| JP2014035877A (en) | Nonaqueous electrolyte secondary battery manufacturing method | |
| CN110301062A (en) | Non-aqueous electrolyte secondary battery | |
| JP4968768B2 (en) | Cylindrical non-aqueous electrolyte battery | |
| WO2012132452A1 (en) | Lithium primary cell | |
| JP2021180064A (en) | Lithium primary battery | |
| JP4993860B2 (en) | Non-aqueous electrolyte primary battery | |
| JP2008192524A (en) | Cylindrical nonaqueous electrolyte solution primary battery | |
| US20190074519A1 (en) | Nonaqueous electrolyte battery and member for nonaqueous electrolyte battery | |
| JP2008192383A (en) | Cylindrical non-aqueous electrolytic liquid primary cell | |
| JP5216961B2 (en) | Non-aqueous electrolyte primary battery | |
| JP4993859B2 (en) | Non-aqueous electrolyte primary battery | |
| JP5620811B2 (en) | Cylindrical non-aqueous electrolyte primary battery | |
| JP5252691B2 (en) | Cylindrical non-aqueous electrolyte primary battery and manufacturing method thereof | |
| JP2006139918A (en) | Cylinder-shaped nonaqueous electrolyte battery | |
| JP2007207640A (en) | Cylindrical non-aqueous electrolytic solution primary battery | |
| JP5019557B2 (en) | Cylindrical non-aqueous electrolyte primary battery | |
| JP7182108B2 (en) | Cylindrical secondary battery | |
| JP4129955B2 (en) | Battery and battery manufacturing method | |
| JP4236193B2 (en) | Battery cover for cylindrical battery, cylindrical battery and method for manufacturing the same | |
| WO2020095500A1 (en) | Lithium primary battery | |
| EP3806208A1 (en) | Cylindrical non-aqueous electrolyte primary battery | |
| WO2022254983A1 (en) | Lithium primary battery | |
| JP4257192B2 (en) | Non-aqueous electrolyte battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20091015 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20110519 |
|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20110526 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120730 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120926 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121015 |
|
| 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: 20130109 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20130121 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130123 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160315 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5216961 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| 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 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| 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 |