JP2009277562A - Nonaqueous electrolyte secondary battery, and method for manufacturing the same - Google Patents
Nonaqueous electrolyte secondary battery, and method for manufacturing the same Download PDFInfo
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 43
- 239000000463 material Substances 0.000 claims abstract description 39
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 239000005001 laminate film Substances 0.000 claims abstract description 22
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 238000004020 luminiscence type Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- 239000005518 polymer electrolyte Substances 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 4
- 229910017639 MgSi Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 230000005283 ground state Effects 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910001719 melilite Inorganic materials 0.000 claims description 3
- 229910052950 sphalerite Inorganic materials 0.000 claims description 3
- 239000011029 spinel Substances 0.000 claims description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 17
- 230000002950 deficient Effects 0.000 abstract description 4
- 238000003466 welding Methods 0.000 abstract 1
- 238000007689 inspection Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 239000010949 copper Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- -1 nickel metal hydride Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
本発明は、漏液検知に適した非水電解液二次電池、およびその製造方法に関するものである。 The present invention relates to a non-aqueous electrolyte secondary battery suitable for leak detection and a method for manufacturing the same.
携帯電話やノートパソコン等移動情報端末などの発展は目覚しく、また、電気自動車やハイブリッド自動車などの実用化に伴って、一次電池のみならず電源として使用されるニッケル水素電池やリチウムイオン電池などの二次電池も大きく需要を伸ばしている。ところが、これらの電池において電解液またはポリマー電解質(以下、電解液と表記)漏れが生じると機器が損傷してしまう恐れがあるため、密閉性に優れ、電解液漏れを防止した電池が要求されている。 The development of mobile information terminals such as mobile phones and laptop computers is remarkable, and with the practical application of electric vehicles and hybrid vehicles, there are two types of batteries such as nickel metal hydride batteries and lithium ion batteries used as power sources as well as primary batteries. Secondary batteries are also in great demand. However, if an electrolyte or polymer electrolyte (hereinafter referred to as an electrolyte) leaks in these batteries, the device may be damaged. Therefore, a battery that has excellent hermeticity and prevents electrolyte leak is required. Yes.
非水電解液二次電池は、電池内部に水分が入ると水分とリチウムとが反応して、電池の容量が低下したり充放電特性が低下したりするため、必ず密閉型となっている。非水電解液二次電池は、アルミラミネートフィルム内に電極体などを収納した後、アルミラミネートフィルムの封口部を封止することにより作製されている。封止不良は電池特性の低下、電池使用機器の損傷等の原因となる電解液の漏出を招く。 Non-aqueous electrolyte secondary batteries are always sealed because moisture and lithium react with each other to reduce the capacity of the battery and charge / discharge characteristics. A non-aqueous electrolyte secondary battery is manufactured by enclosing an electrode body or the like in an aluminum laminate film and then sealing a sealing portion of the aluminum laminate film. Sealing failure leads to leakage of electrolyte that causes deterioration of battery characteristics, damage to battery-operated equipment, and the like.
そこで、電池作製後の出荷前に封止検査が行われ、封口部における電解液の存否に基づいて、封止の良否が判定されていた。 Therefore, a sealing inspection is performed before the shipment after the battery is manufactured, and the sealing quality is determined based on the presence or absence of the electrolytic solution in the sealing portion.
このため、電池を製造するにあたり、電解液漏れを精度良く検査する方法が求められており、この要求に応えるべく、さまざまな電解液漏れ検査方法が提案されている。 For this reason, in manufacturing a battery, a method for accurately inspecting electrolyte leakage is required, and various electrolyte leakage inspection methods have been proposed to meet this requirement.
例えば、特許文献1では、電池ケースの表面に電解液の存在下で所定の光を照射すると蛍光を発する蛍光体を被着し、被着部に所定の光を照射し、その検出結果から電解液漏れの有無を判定する電解液漏れ検査方法が開示されている。
For example, in
また、特許文献2では、封口体が挿入される前の電池缶の開口部を拡開変形させる加工を行った後、開口部での外形異常の有無をセンサー検知することにより開口部での亀裂の有無を検知する方法が開示されている。
Moreover, in
さらに、特許文献3では、電解液に蛍光体を混合しておき、封止後に封口部から漏出した電解液中の蛍光体に励起エネルギーを吸収させて発光させることで、電解液漏れを検出する手法を提案している。
Furthermore, in
漏出した電解液を直接検知することは容易ではなく、特に封止の不備が微小な場合には、漏液が微小なために看過されやすい。したがって、検査の結果、漏液なしと判定された電池であっても、出荷後に漏液が進行して封止不良となる可能性が存在するという問題点があった。 It is not easy to directly detect the leaked electrolyte, and when the sealing defect is very small, it is easy to overlook because the leakage is very small. Therefore, even if the battery is determined to have no leakage as a result of the inspection, there is a problem in that there is a possibility that the leakage will progress after shipment and a sealing failure may occur.
本発明の技術的課題は、漏液を正確に検知することができる非水電解液二次電池およびその製造方法を提供することにある。 The technical problem of the present invention is to provide a non-aqueous electrolyte secondary battery capable of accurately detecting leakage and a method for manufacturing the same.
本発明の非水電解液二次電池は、アルミラミネートフィルム外装体にリチウムを吸蔵・放出する正極材料、および負極材料からなる電極と、前記電極間に介装されたセパレータとを含む電極体を収納し、応力発光成分を有する応力発光材料を含有する電解液またはポリマー電解質を注入し封止したものである。 The non-aqueous electrolyte secondary battery of the present invention comprises an electrode body including a positive electrode material that occludes and releases lithium in an aluminum laminate film outer package, an electrode made of a negative electrode material, and a separator interposed between the electrodes. An electrolytic solution or a polymer electrolyte containing a stress luminescent material having a stress luminescent component is injected and sealed.
本発明の非水電解液二次電池は、応力発光材料としては、母体成分に機械的エネルギーによって励起された電子が基底状態に戻る場合に発光する希土類または遷移金属の1種類以上からなる応力発光成分を添加したものであることが好ましい。 The non-aqueous electrolyte secondary battery of the present invention is a stress-stimulated luminescent material, which is a stress-stimulated luminescent material composed of one or more rare earth elements or transition metals that emit light when electrons excited by mechanical energy return to the ground state. It is preferable that the component is added.
本発明の非水電解液二次電池は、応力発光材料の母体成分と応力発光成分との組み合わせがアルミナと炭酸ストロンチウム、ZnSとMn、ZnSとCu、またはスピネル構造を有するM1Al2O4とM2、もしくはM13Al2O6とM2、もしくはM1Al12O19とM2(ただし、M1=Mg、Ca、Sr、Ba;M2=Eu、Ce、Tb、Sm、Cu、Mn)、またはメリライト系構造酸化物としてのCa2Al2SiO7とM4、もしくはM3MgAl10O17とM4、もしくはM33MgSi2O8とM4(ここで、M3=Ba、Sr、Ca;M4=Eu、Ce、Sm、Cu、Mn)から選択される一種からなることが好ましい。 In the nonaqueous electrolyte secondary battery of the present invention, M1Al 2 O 4 and M2 in which the combination of the matrix component and the stress luminescent component of the stress luminescent material has alumina and strontium carbonate, ZnS and Mn, ZnS and Cu, or spinel structure. Or M1 3 Al 2 O 6 and M2, or M1Al 12 O 19 and M2 (where M1 = Mg, Ca, Sr, Ba; M2 = Eu, Ce, Tb, Sm, Cu, Mn), or melilite structure Ca 2 Al 2 SiO 7 and M4 as oxides, or M3MgAl 10 O 17 and M4, or M3 3 MgSi 2 O 8 and M4 (where M3 = Ba, Sr, Ca; M4 = Eu, Ce, Sm, It is preferably made of one kind selected from Cu, Mn).
本発明の非水電解液二次電池は、応力発光材料の応力発光成分となる希土類または遷移金属を0.01モル%以上、1モル%以下含有させることが好ましい。 The non-aqueous electrolyte secondary battery of the present invention preferably contains 0.01 mol% or more and 1 mol% or less of a rare earth or transition metal serving as a stress luminescent component of the stress luminescent material.
本発明の非水電解液二次電池は、母体成分および前記応力発光成分からなる、一種の応力発光材料を電解液に100ppm以上、1000ppm以下の範囲で含有させることが好ましい。 In the non-aqueous electrolyte secondary battery of the present invention, it is preferable that a kind of stress luminescent material composed of a base component and the stress luminescent component is contained in the electrolytic solution in a range of 100 ppm to 1000 ppm.
本発明の非水電解液二次電池は、応力発光材料の粒子径が、5μm以下であることが好ましい。 In the non-aqueous electrolyte secondary battery of the present invention, it is preferable that the particle size of the stress luminescent material is 5 μm or less.
本発明の非水電解液二次電池の製造方法は、アルミラミネートフィルム外装体にリチウムを吸蔵・放出する正極材料、および負極材料からなる電極と、前記電極間に介装されたセパレータとを含む電極体を収納し、応力発光成分を有する応力発光材料を含有する電解液またはポリマー電解質を注入し封止した非水電解液二次電池の封止辺の封口部に挟まれた応力発光材料の発光により漏液を検知する工程を含む。 A method for producing a nonaqueous electrolyte secondary battery of the present invention includes a positive electrode material that occludes and releases lithium in an aluminum laminate film outer package, an electrode made of a negative electrode material, and a separator interposed between the electrodes. A stress-stimulated luminescent material sandwiched between sealing portions of a nonaqueous electrolyte secondary battery in which an electrode body is housed and an electrolyte or polymer electrolyte containing a stress-stimulated luminescent material having a stress luminescent component is injected and sealed. A step of detecting leakage by luminescence.
本発明により、封止不良部が発光し、封止の良否を正確に判定することが可能な非水電解液二次電池およびその製造方法の提供が可能となった。 According to the present invention, it is possible to provide a non-aqueous electrolyte secondary battery capable of accurately determining sealing quality by emitting light from a poorly sealed portion and a manufacturing method thereof.
本発明によれば、出荷後に漏液が進行して封止不良となることのない非水電解液二次電池が得られる。 According to the present invention, it is possible to obtain a non-aqueous electrolyte secondary battery in which liquid leakage does not occur after shipment and no sealing failure occurs.
本発明によれば、電池の封止(密閉性)が良い場合は、封口部の発光は認められないが、電池の封止が良くない場合は、封口部に挟まった電解液中の応力発光材料が反応し、封口部が発光するので、漏液の判定が容易な非水電解液二次電池が得られる。 According to the present invention, when the battery sealing (sealing property) is good, no light emission is observed in the sealing part, but when the battery sealing is not good, the stress light emission in the electrolytic solution sandwiched between the sealing parts. Since the material reacts and the sealing portion emits light, a non-aqueous electrolyte secondary battery with easy leakage determination can be obtained.
本発明の実施の形態について図面を参照して説明する。図2は、本発明の非水電解液二次電池に用いる電極体の分解斜視図である。本発明の非水電解液二次電池の電極体は、正極2と負極3がセパレータ4を介して巻回されており、最外周に巻き止めテープ1を重ねてなり、正極2には正極タブ5が、負極3には負極タブ6が溶着されている。
Embodiments of the present invention will be described with reference to the drawings. FIG. 2 is an exploded perspective view of an electrode body used in the nonaqueous electrolyte secondary battery of the present invention. The electrode body of the non-aqueous electrolyte secondary battery of the present invention has a
図3は、本発明の非水電解液二次電池の封止前の斜視図である。非水電解液二次電池は、アルミラミネートフィルム外装体7の中に電極体を収納している。
FIG. 3 is a perspective view of the nonaqueous electrolyte secondary battery of the present invention before sealing. The non-aqueous electrolyte secondary battery has an electrode body housed in an aluminum laminate film
非水電解液二次電池は、電極体をアルミラミネートフィルム外装体7に収納してアルミラミネートフィルム外装電池を形成し、アルミラミネートフィルム外装体7の片側側辺部を加熱シールし、さらに正極タブ5および負極タブ6を外部に露出させた状態でタブ面を加熱シールした後、アルミラミネートフィルム外装体7の未封止側辺部から、調整した電解液をアルミラミネートフィルム外装体7内に注液後、未封止側辺部を加熱シールすることにより作製される。
In the nonaqueous electrolyte secondary battery, an electrode body is housed in an aluminum laminate film
非水電解液に添加する応力発光材料としては、母体成分に機械的エネルギーによって励起された電子が基底状態に戻る場合に発光する希土類または遷移金属の1種類以上からなる応力発光成分を添加したものであることが好ましい。 As a stress luminescent material added to the non-aqueous electrolyte, a stress luminescent component consisting of one or more of rare earth elements or transition metals that emit light when electrons excited by mechanical energy return to the ground state is added to the base component. It is preferable that
応力発光材料の母体成分と応力発光成分との組み合わせが、アルミナと炭酸ストロンチウム、ZnSとMn、ZnSとCu、またはスピネル構造を有するM1Al2O4とM2、もしくはM13Al2O6とM2、もしくはM1Al12O19とM2(ただし、M1=Mg、Ca、Sr、Ba;M2=Eu、Ce、Tb、Sm、Cu、Mn)、またはメリライト系構造酸化物としてのCa2Al2SiO7とM4、もしくはM3MgAl10O17とM4、もしくはM33MgSi2O8とM4(ここで、M3=Ba、Sr、Ca;M4=Eu、Ce、Sm、Cu、Mn)から選択される一種からなることが好ましい。 The combination of the matrix component and the stress luminescence component of the stress luminescent material is alumina and strontium carbonate, ZnS and Mn, ZnS and Cu, or M1Al 2 O 4 and M2 having a spinel structure, or M1 3 Al 2 O 6 and M2, Or M1Al 12 O 19 and M2 (where M1 = Mg, Ca, Sr, Ba; M2 = Eu, Ce, Tb, Sm, Cu, Mn), or Ca 2 Al 2 SiO 7 as a melilite structure oxide M4, or M3MgAl 10 O 17 and M4, or M3 3 MgSi 2 O 8 and M4 (where M3 = Ba, Sr, Ca; M4 = Eu, Ce, Sm, Cu, Mn) It is preferable.
応力発光材料の応力発光成分となる希土類または遷移金属を0.01モル%以上、1モル%以下含有させるのが好ましい。 It is preferable to contain 0.01 mol% or more and 1 mol% or less of a rare earth or transition metal that becomes a stress luminescent component of the stress luminescent material.
すなわち、0.01モル%未満であると、発光度が低下してしまい、1モル%を超えると、結晶構造を維持することができず、性能が低下するためである。 That is, when the amount is less than 0.01 mol%, the luminous intensity decreases, and when it exceeds 1 mol%, the crystal structure cannot be maintained and the performance decreases.
アルミラミネートフィルム外装体の封口部は、加熱シールバーを上下から加圧して封止する。その際、封止された封口部に、電解液に添加する応力発光材料が挟まれていると、応力発光材料が圧力に感応して発光し、画像認識検査にて封止不良部を検出するのが設計上好ましい。 The sealing portion of the aluminum laminate film exterior body is sealed by pressurizing the heat seal bar from above and below. At that time, if a stress-stimulated luminescent material to be added to the electrolyte is sandwiched between the sealed sealing portions, the stress-stimulated luminescent material emits light in response to pressure, and a defective sealing portion is detected by an image recognition inspection. Is preferable in terms of design.
図1は、電解液への応力発光材料含有量と、イオン伝導度および発光度の関係図である。電解液への応力発光材料の含有量をX軸、イオン伝導度をY1軸、発光度をY2軸に示した。本発明においてイオン伝導度が10mS/cm以上の範囲では電池特性に影響を与えることなく、発光度が100cd/m2以上の範囲では封止不良部を適切に検出できる。 FIG. 1 is a relationship diagram of stress luminescent material content, ionic conductivity, and luminous intensity in an electrolytic solution. The content of the stress luminescent material in the electrolyte is shown on the X axis, the ionic conductivity is shown on the Y1 axis, and the luminous intensity is shown on the Y2 axis. In the present invention, when the ionic conductivity is in the range of 10 mS / cm or higher, the poorly sealed portion can be appropriately detected in the range of the luminous intensity of 100 cd / m 2 or higher without affecting the battery characteristics.
したがって、応力発光材料は、電解液に100ppm以上、1000ppm以下の範囲で含有することが設計上好ましい。すなわち、100ppm未満であると、封止不良部を適切に検出できなくなり、1000ppmを超えると、電気特性に影響を与えるためである。 Therefore, the stress-stimulated luminescent material is preferably contained in the electrolytic solution in the range of 100 ppm or more and 1000 ppm or less. That is, if it is less than 100 ppm, it becomes impossible to properly detect the sealing failure portion, and if it exceeds 1000 ppm, the electrical characteristics are affected.
応力発光材料の粒子径は、5μm以下であることが設計上好ましい。すなわち、5μmを超えると、セパレータの穴を阻害してしまう恐れがあるためである。 The particle size of the stress-stimulated luminescent material is preferably 5 μm or less in design. That is, if the thickness exceeds 5 μm, the separator hole may be obstructed.
以下に本発明の実施例を詳述する。 Examples of the present invention are described in detail below.
(実施例1〜3)
(電解液の調製例)
エチレンカーボネート(EC)とジエチルカーボネート(DEC)が、体積比2:1の割合で混合された非水溶媒に、電解質塩である六フッ化リン酸リチウム(LiPF6)を1.0モル/lの濃度になるように溶解させた、電解液を調製した。
(Examples 1-3)
(Preparation example of electrolyte)
In a non-aqueous solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) are mixed in a ratio of 2: 1 by volume, lithium hexafluorophosphate (LiPF 6 ) as an electrolyte salt is added at 1.0 mol / l. An electrolytic solution was prepared so as to be dissolved to a concentration of.
(電解液に応力発光材料の添加)
上記調整電解液に、母体成分としてのアルミナに応力発光成分としての炭酸ストロンチウムを0.05モル%含有させた、粒子径1μm程度の応力発光材料を1000ppm混合した。
(Addition of stress luminescent material to electrolyte)
The adjusted electrolyte solution was mixed with 1000 ppm of a stress luminescent material having a particle diameter of about 1 μm, containing 0.05 mol% of strontium carbonate as a stress luminescent component in alumina as a base component.
(正極の作製)
コバルト酸リチウムを94質量部と、ポリビニリデンフルオライド(以下、PVDFと表記)を3質量部と、導電性カーボン3質量部を混合して、正極材料とした。この正極材料をN−メチル−2−ピロリドン(以下、NMPと表記)に分散させてスラリー状とした。得られたスラリーを厚さ15μmのアルミ箔上に塗布し、乾燥後、厚さ160μmの正極を得た。
(Preparation of positive electrode)
94 parts by mass of lithium cobaltate, 3 parts by mass of polyvinylidene fluoride (hereinafter referred to as PVDF), and 3 parts by mass of conductive carbon were mixed to obtain a positive electrode material. This positive electrode material was dispersed in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) to form a slurry. The obtained slurry was applied onto an aluminum foil having a thickness of 15 μm, and after drying, a positive electrode having a thickness of 160 μm was obtained.
(負極の作製)
炭素材料粉末を96質量部とPVDFを3質量部と、導電性カーボン1質量部を混合して、負極材料とした。この負極材料をNMPに分散させてスラリー状とした。得られたスラリーを厚さ10μmの銅箔上に塗布し乾燥後、厚さ110μmの負極を得た。
(Preparation of negative electrode)
96 parts by mass of carbon material powder, 3 parts by mass of PVDF, and 1 part by mass of conductive carbon were mixed to obtain a negative electrode material. This negative electrode material was dispersed in NMP to form a slurry. The obtained slurry was applied on a copper foil having a thickness of 10 μm and dried to obtain a negative electrode having a thickness of 110 μm.
(非水電解液二次電池の封止)
正極と負極を、セパレータを介して巻回し、最外周に巻き止めテープを重ねた。正極には正極タブを、負極には負極タブを溶着している。
(Sealing of non-aqueous electrolyte secondary battery)
The positive electrode and the negative electrode were wound through a separator, and an anti-winding tape was stacked on the outermost periphery. A positive electrode tab is welded to the positive electrode, and a negative electrode tab is welded to the negative electrode.
アルミラミネートフィルム外装体は、厚さ20μmのPET層(外層)と厚さ80μmのアルミニウム層(中層)と厚さ20μmのPP層(内層)とが積層されてなる。 The aluminum laminate film outer package is formed by laminating a PET layer (outer layer) having a thickness of 20 μm, an aluminum layer (middle layer) having a thickness of 80 μm, and a PP layer (inner layer) having a thickness of 20 μm.
非水電解液二次電池は、電極体にアルミラミネートフィルム外装体を巻回して、アルミラミネートフィルム外装電池を形成し、アルミラミネートフィルム外装体の片側辺部を加熱シールし、さらに正極タブおよび負極タブを外部に露出させた状態でタブ面を加熱シールした後、アルミラミネートフィルム外装体の未封止側辺部から、調整した電解液をアルミラミネートフィルム外装体内に注液後、未封止側辺部を加熱シールすることにより作製した。注液量は1.0g、1.5g、2.0gの3種類とし、表1においては、試料名をそれぞれ実施例1、実施例2、実施例3とした。 A non-aqueous electrolyte secondary battery is formed by winding an aluminum laminate film outer package around an electrode body to form an aluminum laminate film outer battery, heat-sealing one side of the aluminum laminate film outer package, and further forming a positive electrode tab and a negative electrode After the tab surface is heat-sealed with the tab exposed to the outside, the adjusted electrolyte is injected into the aluminum laminate film exterior from the unsealed side of the aluminum laminate film exterior, and then the unsealed side It was produced by heat-sealing the sides. There were three types of injections, 1.0 g, 1.5 g, and 2.0 g. In Table 1, the sample names were Example 1, Example 2, and Example 3, respectively.
(画像認識検査)
図4は、画像認識検査実施部の説明図である。非水電解液二次電池を作製後、注液側漏液検出辺8とタブ側漏液検出辺9の画像認識検査を行った。
(Image recognition inspection)
FIG. 4 is an explanatory diagram of the image recognition inspection execution unit. After producing the nonaqueous electrolyte secondary battery, an image recognition inspection of the liquid injection side
(比較例1〜3)
応力発光材料を含有していない電解液を用いた他は実施例1〜3と同様にして、非水電解液二次電池を作製した。表1においては、試料名をそれぞれ比較例1、比較例2、比較例3とした。
(Comparative Examples 1-3)
A non-aqueous electrolyte secondary battery was produced in the same manner as in Examples 1 to 3, except that an electrolytic solution containing no stress-stimulated luminescent material was used. In Table 1, the sample names are Comparative Example 1, Comparative Example 2, and Comparative Example 3, respectively.
(漏液検査1)
比較例1〜3にて作製した非水電解液二次電池の封口部にリトマス紙を接触させ、目視にて封口部における漏液の有無を調べた。
(Leakage inspection 1)
The litmus paper was brought into contact with the sealing portion of the nonaqueous electrolyte secondary battery produced in Comparative Examples 1 to 3, and the presence or absence of liquid leakage in the sealing portion was examined visually.
(漏液検査2)
本発明電池である実施例1〜3のうち漏液検査1で漏液なしと判定した電池について画像認識検査を行い、封口部の発光を調べて漏液の有無を調べた。この漏液検査は本発明による漏液検査である。なお封口部に発光を示した電池は漏液ありと判定した。
(Leakage inspection 2)
Among the batteries of Examples 1 to 3 which are the batteries of the present invention, an image recognition inspection was performed on the battery determined as having no liquid leakage in the
(漏液検査3)
本発明電池である実施例1〜3のうち漏液検査2で漏液なしと判定した電池、および比較例1〜3のうち漏液検査1で漏液なしと判定した電池を温度60℃−相対湿度90%の雰囲気下に10日間放置し、放置後の漏液の有無を調べた。この漏液検査で電池を高温多湿の雰囲気下に放置したのは、漏液が短期間に進行するようにするためである。この漏液検査により通常の雰囲気下に長期間放置した際の漏液の有無を推断することができる。したがって、この漏液検査での判定結果と一致した結果が得られる漏液検査方法は、信頼性の高い漏液検査方法といえる。
(Leakage inspection 3)
Among the batteries according to Examples 1 to 3 of the present invention, the battery determined to have no leakage in the
表2に、漏液検査1〜3での検査結果を示す。表2に示す分数は、分母が検査電池の個数を表し、分子が漏液ありと判定された電池の個数を表す。
Table 2 shows the test results in the
表2に示すように、本発明電池である実施例1〜3のうち本発明による漏液検査2で漏液なしと判定された電池(実施例1では100個、実施例2では16個)は全て漏液検査3でも漏液なしと判定されている。
As shown in Table 2, among Examples 1 to 3 which are the batteries of the present invention, the batteries judged as having no leakage in the
これに対して、比較例1〜3のうち従来の方法による漏液検査1で漏液なしと判定された電池は、それぞれ100個、98個、80個であるが、漏液検査3では、比較例2〜3のそれぞれ77個、80個が漏液ありと判定されており、封口部に、非水電解液に添加した応力発光材料の存在を確認した。
On the other hand, in Comparative Examples 1 to 3, the batteries determined to have no leakage in the
表2より、本発明方法によれば、従来の方法に比べて非水電解液二次電池の漏液を正確に検知することができることが分かる。 From Table 2, it can be seen that according to the method of the present invention, the leakage of the non-aqueous electrolyte secondary battery can be accurately detected as compared with the conventional method.
(実施例4〜6)
(ポリマー電解質の調製例)
実施例1〜3にて調製した電解液と、ポリマー主材としてポリビニリデンフルオライド−ヘキサフルオロプロピレン(PVDF−HFP)が重量比6:1の割合で混合させた、非水電解液を調製した。
(Examples 4 to 6)
(Preparation example of polymer electrolyte)
A non-aqueous electrolyte was prepared in which the electrolyte prepared in Examples 1 to 3 and polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) as a polymer main material were mixed at a weight ratio of 6: 1. .
実施例1〜3と同様に非水電解液に応力発光材料の添加、正極の作製、負極の作製、非水電解液二次電池の封止を行った。その後、110℃で加熱し、重合を行った。表3においては、試料名をそれぞれ実施例4、実施例5、実施例6とした。 In the same manner as in Examples 1 to 3, a stress luminescent material was added to the non-aqueous electrolyte, the positive electrode was produced, the negative electrode was produced, and the non-aqueous electrolyte secondary battery was sealed. Then, it heated at 110 degreeC and superposition | polymerization was performed. In Table 3, the sample names are Example 4, Example 5, and Example 6, respectively.
実施例1〜3と同様に画像認識検査を行った。 An image recognition test was performed in the same manner as in Examples 1 to 3.
(比較例4〜6)
応力発光材料を含有していない電解液を用いた他は実施例4〜6と同様にして、非水電解液二次電池を作製した。表3においては、試料名をそれぞれ比較例4、比較例5、比較例6とした。その後、比較例1〜3における漏液検査1、3を同様に行った。
(Comparative Examples 4-6)
Non-aqueous electrolyte secondary batteries were produced in the same manner as in Examples 4 to 6 except that an electrolyte containing no stress-stimulated luminescent material was used. In Table 3, the sample names are Comparative Example 4, Comparative Example 5, and Comparative Example 6, respectively. Thereafter,
表4に示すように、本発明電池である実施例4〜6のうち本発明による漏液検査2で漏液なしと判定された電池(実施例4では100個、実施例5では18個)は全て漏液検査3でも漏液なしと判定されている。
As shown in Table 4, among Examples 4 to 6 which are the batteries of the present invention, the batteries judged as having no leakage in the
これに対して、比較例4〜6のうち従来の方法による漏液検査1で漏液なしと判定された電池は、それぞれ100個、96個、76個であるが、漏液検査3では、比較例5〜6のそれぞれ71個、76個が漏液ありと判定されており、封口部に、非水電解液に添加した応力発光材料の存在を確認した。
On the other hand, in Comparative Examples 4 to 6, the batteries determined to have no leak in the
表4より、本発明方法によれば、従来の方法に比べて非水電解液二次電池の漏液を正確に検知することができることが分かる。 From Table 4, it can be seen that according to the method of the present invention, the leakage of the nonaqueous electrolyte secondary battery can be accurately detected as compared with the conventional method.
以上の実施例1〜6、比較例1〜6の結果である表2、表4のデータを総合して考慮すれば、本発明方法は、従来の方法に比べて非水電解液二次電池の漏液を正確に検知できることが分かる。 In consideration of the data in Tables 2 and 4 which are the results of Examples 1 to 6 and Comparative Examples 1 to 6 described above, the method of the present invention is a non-aqueous electrolyte secondary battery as compared with the conventional method. It can be seen that the liquid leakage can be accurately detected.
以上、実施例を用いて、この発明の実施の形態を説明したが、この発明は、これらの実施例に限られるものではなく、この発明の要旨を逸脱しない範囲の設計変更があっても本発明に含まれる。すなわち、当業者であれば、当然なしえるであろう各種変形、修正もまた本発明に含まれる。 The embodiments of the present invention have been described above using the embodiments. However, the present invention is not limited to these embodiments, and the present invention is not limited to the scope of the present invention. Included in the invention. That is, various changes and modifications that can be naturally made by those skilled in the art are also included in the present invention.
1 巻き止めテープ
2 正極
3 負極
4 セパレータ
5 正極タブ
6 負極タブ
7 アルミラミネートフィルム外装体
8 注液側漏液検出辺
9 タブ側漏液検出辺
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