JP5876766B2 - Nonaqueous electrolyte secondary battery separator and battery - Google Patents
Nonaqueous electrolyte secondary battery separator and battery Download PDFInfo
- Publication number
- JP5876766B2 JP5876766B2 JP2012104271A JP2012104271A JP5876766B2 JP 5876766 B2 JP5876766 B2 JP 5876766B2 JP 2012104271 A JP2012104271 A JP 2012104271A JP 2012104271 A JP2012104271 A JP 2012104271A JP 5876766 B2 JP5876766 B2 JP 5876766B2
- Authority
- JP
- Japan
- Prior art keywords
- separator
- glass fiber
- battery
- magnesium oxide
- nonwoven fabric
- 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 11
- 239000003365 glass fiber Substances 0.000 claims description 47
- 239000000654 additive Substances 0.000 claims description 24
- 230000000996 additive effect Effects 0.000 claims description 23
- 238000004438 BET method Methods 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 77
- 239000000395 magnesium oxide Substances 0.000 description 35
- 239000004745 nonwoven fabric Substances 0.000 description 30
- 239000002002 slurry Substances 0.000 description 29
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 15
- 239000011230 binding agent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 12
- 229910001928 zirconium oxide Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910014195 BM-400B Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Cell Separators (AREA)
- Secondary Cells (AREA)
Description
本発明は電池の高温保存特性を改善し、汎用されている樹脂製セパレータ材を用いた電池の高温保存特性と同程度まで向上させることができる非水電解液二次電池用セパレータとそれを用いた電池に関する。 INDUSTRIAL APPLICABILITY The present invention improves the high-temperature storage characteristics of the battery, and can be improved to the same level as the high-temperature storage characteristics of the battery using a widely used resin separator material. Related to the battery.
従来から、非水電解液二次電池の各種の特性を向上させるために色々な試みがされてきている。
耐熱性を付与するために、例えば、特許文献１にガラス繊維からなる耐熱セパレータが開示されているが、電池の高温保存特性において樹脂製のセパレータと比べて劣るという問題がある。これは、高温保存時に電解液が熱分解してフッ酸（ＨＦ）が発生し、セパレータを構成するガラス繊維と化学反応を起こすためである。
レート特性及びサイクル特性を向上させるために、例えば、特許文献２に、マグネシア（ＭｇＯ）をポリプロピレンに混合してセパレータとすることが提案されているが、マグネシア表面がポリプロピレン材で被覆されるため、フッ酸を捕捉する効率が低下するという問題があった。これを解消するために、セパレータ表面にＭｇＯ又はＺｒＯ２を添加することが特許文献３において提案されている。特許文献３では、予め形成された微細な孔を有する多孔質の薄膜等の表面に、無機粒子を適量振りかけた後、前記薄膜を形成する樹脂が軟化する程度の適度な温度でプレス加工することにより無機微粒子を圧着することが開示されている。
しかしながら、特許文献３において、セパレータに含まれる無機粒子は０．１〜９９質量％の範囲とされているだけで、無機粒子について他に示唆する記載はない。
Conventionally, various attempts have been made to improve various characteristics of the nonaqueous electrolyte secondary battery.
In order to impart heat resistance, for example, Patent Document 1 discloses a heat-resistant separator made of glass fiber, but has a problem that it is inferior to a resin separator in high-temperature storage characteristics of a battery. This is because the electrolytic solution is thermally decomposed during high temperature storage to generate hydrofluoric acid (HF) and cause a chemical reaction with the glass fibers constituting the separator.
In order to improve rate characteristics and cycle characteristics, for example, Patent Document 2 proposes to mix magnesia (MgO) with polypropylene to form a separator, but because the magnesia surface is coated with a polypropylene material, There was a problem that the efficiency of capturing hydrofluoric acid was lowered. In order to solve this problem, Patent Document 3 proposes to add MgO or ZrO 2 to the separator surface. In Patent Document 3, an appropriate amount of inorganic particles is sprinkled on the surface of a porous thin film having fine pores formed in advance, and then pressed at an appropriate temperature such that the resin forming the thin film is softened. Is disclosed for pressure bonding inorganic fine particles.
However, in patent document 3, the inorganic particle contained in a separator is only made into the range of 0.1-99 mass%, and there is no description which suggests other about an inorganic particle.
本発明は、このような従来の問題点に着目してなされたもので、ガラス繊維製セパレータを用いた電池の高温保存特性を改善し、汎用されている樹脂製セパレータ材を用いた電池の高温保存特性と同程度まで向上させることを目的とする。 The present invention has been made paying attention to such conventional problems, and improves the high-temperature storage characteristics of a battery using a glass fiber separator, and the high temperature of a battery using a widely used resin separator material. The purpose is to improve the storage characteristics to the same extent.
本発明者等は鋭意検討の結果、下記の解決手段を見出した。
即ち、本発明の非水電解液二次電池用セパレータの第１の解決手段は、ガラス繊維から構成されるセパレータに、添加物としてＭｇＯを添加した非水電解液二次電池用セパレータであって、前記添加物はＢＥＴ法による比表面積（ｍ２／ｇ）が１７．４０〜１７６．００であり、前記ガラス繊維全体に対する添加重量割合（ｗｔ％）が１．９６〜８６．６７であり、前記比表面積と前記添加重量割合との積が４０００［（ｍ２／ｇ）・（ｗｔ％）］以上となるように添加されたものであることを特徴とする。
また、本発明の電池の第１の解決手段は、電池のセパレータとして、前記第１の解決手段における非水電解液二次電池用セパレータを用いることを特徴とする。
As a result of intensive studies, the present inventors have found the following solution.
That is, the first solution of the non-aqueous electrolyte secondary battery separator of the present invention is a non-aqueous electrolyte secondary battery separator in which MgO is added as an additive to a separator made of glass fiber. The additive has a specific surface area (m 2 / g) according to the BET method of 17.40 to 176.00, and an added weight ratio (wt%) based on the whole glass fiber of 1.96 to 86.67. The product of the specific surface area and the weight ratio is 4000 [(m 2 / g) · (wt%)] or more.
Moreover, the 1st solution means of the battery of this invention uses the separator for nonaqueous electrolyte secondary batteries in the said 1st solution means as a battery separator.
本発明によれば、添加したマグネシア（ＭｇＯ）が効率よくフッ酸を捕捉するため、ガラス繊維製セパレータを用いた電池の高温保存特性を改善し、汎用されている樹脂製セパレータ材を用いた電池の高温保存特性と同程度まで向上させることができる。 According to the present invention, since the added magnesia (MgO) efficiently captures hydrofluoric acid, the high-temperature storage characteristics of the battery using the glass fiber separator are improved, and the battery using the widely used resin separator material Can be improved to the same extent as the high-temperature storage characteristics.
本発明の非水電解液二次電池用セパレータは、ガラス繊維からなるセパレータにマグネシア（ＭｇＯ）を添加して非水電解液二次電池用セパレータとするものである。
これにより、添加した材料がフッ酸を捕捉するため、ガラス繊維からなる耐熱セパレータ材を用いた電池の高温保存特性を改善できる。
The separator for non-aqueous electrolyte secondary batteries of the present invention is a separator for non-aqueous electrolyte secondary batteries by adding magnesia (MgO) to a separator made of glass fiber.
Thereby, since the added material capture | acquires hydrofluoric acid, the high temperature storage characteristic of the battery using the heat-resistant separator material which consists of glass fibers can be improved.
また、添加物として、マグネシア（ＭｇＯ）をガラス繊維からなるセパレータに添加するにあたり、マグネシア（ＭｇＯ）のＢＥＴ法による比表面積（ｍ２／ｇ）と、これら添加物のガラス繊維の総重量に対する添加重量割合（ｗｔ％）との積が４０００［（ｍ２／ｇ）・（ｗｔ％）］以上となるように添加する。前記積が、好ましくは６０００［（ｍ２／ｇ）・（ｗｔ％）］以上となるように添加する。
前記添加重量割合（ｗｔ％）は、ガラス繊維重量と添加物重量の和に対する添加物の重量比率を表し、ＢＥＴ法による比表面積（ｍ２／ｇ）と添加重量割合（ｗｔ％）との積はガラス繊維の単位重量当たりの添加物の表面積を意味する。即ち、電解液中に存在するガラス繊維の単位重量当たり、添加物がどれだけ効果を有するかを意味する。
このようにすることにより、発生したフッ酸を効率よく捕捉し、フッ酸のガラス基材への影響を軽減することができる。その結果、ガラス繊維からなる耐熱セパレータ材を用いた電池の高温保存特性を改善できる。
尚、前記セパレータの作成においてＳＢＲバインダー樹脂を添加すれば、フッ酸の捕捉に影響を与えることなくセパレータの強度を高めることができる。
本発明の電池は電池のセパレータとして、前記本発明の非水電解液二次電池用セパレータを用いるものである。
In addition, when adding magnesia (MgO) to the separator made of glass fiber as an additive, the specific surface area (m 2 / g) of the magnesia (MgO) by the BET method and addition of these additives to the total weight of the glass fiber It adds so that the product with a weight ratio (wt%) may become 4000 [(m < 2 > / g) * (wt%)] or more . It is added so that the product is preferably 6000 [(m 2 / g) · (wt%)] or more.
The additive weight ratio (wt%) represents the weight ratio of the additive to the sum of the glass fiber weight and the additive weight, and is the product of the specific surface area (m 2 / g) and the additive weight ratio (wt%) by the BET method. Means the surface area of the additive per unit weight of glass fiber. That is, it means how effective the additive is per unit weight of the glass fiber present in the electrolytic solution.
By doing in this way, the generated hydrofluoric acid can be captured efficiently and the influence of hydrofluoric acid on the glass substrate can be reduced. As a result, it is possible to improve the high-temperature storage characteristics of the battery using the heat-resistant separator made of glass fiber.
If an SBR binder resin is added in the production of the separator, the strength of the separator can be increased without affecting the capture of hydrofluoric acid.
The battery of the present invention uses the non-aqueous electrolyte secondary battery separator of the present invention as a battery separator.
［参考例１］
平均直径０．７μｍ、平均長さ約３ｍｍのガラス短繊維を水中で解きほぐし、硫酸でｐＨ２．５に調製した水溶液中で充分に解離、分散させ、ガラス繊維スラリーを作製した。このスラリーを原料として、湿式抄紙装置を用いて、ガラス繊維不織布を得た。得られたガラス繊維不織布は、厚みが５０μｍであり、目付量は１０ｇ／ｍ２であった。また添加物として酸化マグネシウム粉末（株式会社高純度化学研究所、ＭＧＯ１１ＰＢ 平均粒径３．６μｍ、ＢＥＴ法による比表面積１８．２０ｍ２／ｇ）を攪拌機を用いて水に分散し、１０ｗｔ％のスラリーを作製した。ガラス繊維不織布をこの酸化マグネシウムスラリー（１０ｗｔ％）に１回ディッピングした。この後120℃で２時間乾燥させ、ディッピング〜乾燥までの操作を４回繰り返してセパレータを作製した。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化マグネシウムは８６．６７ｗｔ％であった。
[ Reference Example 1 ]
Glass short fibers having an average diameter of 0.7 μm and an average length of about 3 mm were thawed in water and sufficiently dissociated and dispersed in an aqueous solution adjusted to pH 2.5 with sulfuric acid to prepare a glass fiber slurry. Using this slurry as a raw material, a glass fiber nonwoven fabric was obtained using a wet papermaking machine. The obtained glass fiber nonwoven fabric had a thickness of 50 μm and a basis weight of 10 g / m 2 . As an additive, magnesium oxide powder (High Purity Chemical Laboratory Co., Ltd., MGO11PB average particle size 3.6 μm, specific surface area 18.20 m 2 / g by BET method) is dispersed in water using a stirrer, and a 10 wt% slurry. Was made. The glass fiber nonwoven fabric was dipped once in this magnesium oxide slurry (10 wt%). Then, it was dried at 120 ° C. for 2 hours, and the operation from dipping to drying was repeated 4 times to produce a separator. When the obtained separator was dried at 120 ° C. for 12 hours and weighed, the magnesium oxide supported on the separator was 86.67 wt%.
［参考例２］
参考例１と同様にして厚み５０μｍ、目付量１０ｇ／ｍ２のガラス繊維不織布を得た。添加物として酸化マグネシウム粉末（宇部マテリアルズ株式会社、ＵＣＭ−１５０ 平均粒径３．３μｍ、ＢＥＴ法による比表面積１７６．００ｍ２／ｇ）を攪拌機を用いて水に分散し、１ｗｔ％のスラリーを作製した。ガラス繊維不織布をこの酸化マグネシウムスラリー（１ｗｔ％）に１回ディッピングした。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化マグネシウムは１．９６ｗｔ％であった。
[ Reference Example 2 ]
In the same manner as in Reference Example 1 , a glass fiber nonwoven fabric having a thickness of 50 μm and a basis weight of 10 g / m 2 was obtained. As an additive, magnesium oxide powder (Ube Materials Co., Ltd., UCM-150 average particle size 3.3 μm, specific surface area 176.00 m 2 / g by BET method) is dispersed in water using a stirrer, and 1 wt% slurry is dispersed. Produced. The glass fiber nonwoven fabric was dipped once in this magnesium oxide slurry (1 wt%). When the obtained separator was dried at 120 ° C. for 12 hours and then weighed, the magnesium oxide supported on the separator was 1.96 wt%.
［参考例３］
参考例２において、酸化マグネシウムスラリーのディッピングと乾燥を２回繰り返し、セパレータを作製した。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化マグネシウムは４．７６ｗｔ％であった。
[ Reference Example 3 ]
In Reference Example 2 , dipping and drying of the magnesium oxide slurry were repeated twice to produce a separator. When the obtained separator was dried at 120 ° C. for 12 hours and weighed, the magnesium oxide supported on the separator was 4.76 wt%.
［実施例４］
参考例１と同様にして厚み５０μｍ、目付量１０ｇ／ｍ２のガラス繊維不織布を得た。添加物として酸化マグネシウム粉末（宇部マテリアルズ株式会社、ＵＣＭ−１５０ 平均粒径３．３μｍ、ＢＥＴ法による比表面積１７６．００ｍ２／ｇ）を攪拌機を用いて水に分散し、１０ｗｔ％のスラリーを作製した。ガラス繊維不織布をＳＢＲバインダー樹脂（日本ゼオン株式会社、ＢＭ−４００Ｂ，以後同じ）の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらにガラス繊維不織布をこの酸化マグネシウムスラリーに１回ディッピングした後、１２０℃で２時間乾燥させ、セパレータを作製した。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化マグネシウムは２３．０８ｗｔ％であった。
[Example 4]
In the same manner as in Reference Example 1 , a glass fiber nonwoven fabric having a thickness of 50 μm and a basis weight of 10 g / m 2 was obtained. As an additive, magnesium oxide powder (Ube Materials Co., Ltd., UCM-150 average particle size 3.3 μm, specific surface area 176.00 m 2 / g by BET method) is dispersed in water using a stirrer, and a 10 wt% slurry is prepared. Produced. After dipping the glass fiber nonwoven fabric in an aqueous solution (SBR concentration 3 wt%) of SBR binder resin (Nippon ZEON Co., Ltd., BM-400B, the same applies hereinafter), dipping the glass fiber nonwoven fabric once in this magnesium oxide slurry, 120 The separator was dried at 2 ° C. for 2 hours. When the obtained separator was dried at 120 ° C. for 12 hours and weighed, magnesium oxide supported on the separator was 23.08 wt%.
［実施例５］
参考例２において、ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらに酸化マグネシウムスラリーのディッピングと乾燥を２回繰り返し、セパレータを作製した。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化ジルコニウムは３７．５０ｗｔ％であった。
[Example 5]
In Reference Example 2 , the glass fiber nonwoven fabric was dipped into an aqueous solution of SBR binder resin (SBR concentration: 3 wt%), and then dipping and drying of the magnesium oxide slurry were repeated twice to produce a separator. When the obtained separator was dried at 120 ° C. for 12 hours and weighed, the zirconium oxide supported on the separator was 37.50 wt%.
［実施例６］
参考例２において、ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらに酸化マグネシウムスラリーのディッピングと乾燥を３回繰り返し、セパレータを作製した。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化ジルコニウムは５７．４５ｗｔ％であった。
[Example 6]
In Reference Example 2 , the glass fiber nonwoven fabric was dipped into an aqueous solution of SBR binder resin (SBR concentration: 3 wt%), and then dipping and drying of the magnesium oxide slurry were repeated three times to produce a separator. The obtained separator was dried at 120 ° C. for 12 hours and weighed. As a result, the zirconium oxide supported on the separator was 57.45 wt%.
［実施例７］
参考例２において、ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらに酸化マグネシウムスラリーのディッピングと乾燥を４回繰り返し、セパレータを作製した。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化ジルコニウムは７５．００ｗｔ％であった。
[Example 7]
In Reference Example 2 , the glass fiber nonwoven fabric was dipped into an aqueous solution of SBR binder resin (SBR concentration: 3 wt%), and then dipping and drying of the magnesium oxide slurry were repeated four times to produce a separator. When the obtained separator was dried at 120 ° C. for 12 hours and weighed, the zirconium oxide supported on the separator was 75.00 wt%.
［参考例８］
参考例１と同様にして厚み５０μｍ、目付量１０ｇ／ｍ２のガラス繊維不織布を得た。添加物として酸化ジルコニウム粉末（株式会社高純度化学研究所、ＺＲ００２ＰＡ、平均粒径１．０μｍ、比表面積１７．４０ｍ２／ｇ）を攪拌機を用いて水に分散し、１０ｗｔ％のスラリーを作製した。ガラス繊維不織布を酸化ジルコニウムスラリー（１０ｗｔ％）に１回ディッピングした。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化マグネシウムは２０．００ｗｔ％であった。
[ Reference Example 8 ]
In the same manner as in Reference Example 1 , a glass fiber nonwoven fabric having a thickness of 50 μm and a basis weight of 10 g / m 2 was obtained. Zirconium oxide powder (High Purity Chemical Laboratory Co., Ltd., ZR002PA, average particle size 1.0 μm, specific surface area 17.40 m 2 / g) was dispersed in water using an agitator as an additive to prepare a 10 wt% slurry. . The glass fiber nonwoven fabric was dipped once in a zirconium oxide slurry (10 wt%). When the obtained separator was dried at 120 ° C. for 12 hours and weighed, the magnesium oxide supported on the separator was 20.00 wt%.
［参考例９］
参考例８において、ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらに酸化ジルコニウムスラリー（１０ｗｔ％）に２回ディッピングした。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化ジルコニウムは３３．３３ｗｔ％であった。
[ Reference Example 9 ]
In Reference Example 8 , the glass fiber nonwoven fabric was dipped in an aqueous solution of SBR binder resin (SBR concentration: 3 wt%), and then dipped twice in a zirconium oxide slurry (10 wt%). When the obtained separator was dried at 120 ° C. for 12 hours and weighed, the zirconium oxide supported on the separator was 33.33 wt%.
［参考例１０］
参考例８において、ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらに酸化ジルコニウムスラリー（１０ｗｔ％）に３回ディッピングした。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化ジルコニウムは５０．００ｗｔ％であった。
[ Reference Example 10 ]
In Reference Example 8 , the glass fiber nonwoven fabric was dipped in an aqueous solution of SBR binder resin (SBR concentration: 3 wt%), and then dipped in a zirconium oxide slurry (10 wt%) three times. When the obtained separator was dried at 120 ° C. for 12 hours and then weighed, zirconium oxide supported on the separator was 50.00 wt%.
［参考例１１］
参考例８において、ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらに酸化ジルコニウムスラリー（１０ｗｔ％）に４回ディッピングした。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化ジルコニウムは６０．００ｗｔ％であった。
[ Reference Example 11 ]
In Reference Example 8 , the glass fiber nonwoven fabric was dipped in an aqueous solution of SBR binder resin (SBR concentration 3 wt%), and then dipped in a zirconium oxide slurry (10 wt%) four times. When the obtained separator was dried at 120 ° C. for 12 hours and weighed, the zirconium oxide supported on the separator was 60.00 wt%.
［比較例１］
参考例１と同様にして厚み５０μｍ、目付量１０ｇ／ｍ２のガラス繊維不織布を得た。
ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングし、添加物を付与していないセパレータを作製した。
[Comparative Example 1]
In the same manner as in Reference Example 1 , a glass fiber nonwoven fabric having a thickness of 50 μm and a basis weight of 10 g / m 2 was obtained.
The glass fiber nonwoven fabric was dipped in an aqueous solution of SBR binder resin (SBR concentration 3 wt%) to produce a separator to which no additive was applied.
［比較例２］
参考例１と同様にして厚み５０μｍ、目付量１０ｇ／ｍ２のガラス繊維不織布を得た。添加物として酸化マグネシウム粉末（株式会社高純度化学研究所、ＭＧＯ１１ＰＢ 平均粒径３．６μｍ、ＢＥＴ法による比表面積１８．２０ｍ２／ｇ）を攪拌機を用いて水に分散し、１０ｗｔ％のスラリーを作製した。ガラス繊維不織布をこの酸化マグネシウムスラリー（１０ｗｔ％）に１回ディッピングした。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化マグネシウムは１３．０４ｗｔ％であった。
[Comparative Example 2]
In the same manner as in Reference Example 1 , a glass fiber nonwoven fabric having a thickness of 50 μm and a basis weight of 10 g / m 2 was obtained. As an additive, magnesium oxide powder (High Purity Chemical Laboratory Co., Ltd., MGO11PB average particle size 3.6 μm, specific surface area 18.20 m 2 / g by BET method) is dispersed in water using a stirrer, and a 10 wt% slurry is dispersed. Produced. The glass fiber nonwoven fabric was dipped once in this magnesium oxide slurry (10 wt%). When the obtained separator was dried at 120 ° C. for 12 hours and then weighed, the magnesium oxide supported on the separator was 13.04 wt%.
［比較例３］
参考例１と同様にして厚み５０μｍ、目付量１０ｇ／ｍ２のガラス繊維不織布を得た。添加物として酸化マグネシウム粉末（宇部マテリアルズ株式会社、ＵＣ−９５Ｓ 平均粒径３．１μｍ、ＢＥＴ法による比表面積９．１０ｍ２／ｇ）を攪拌機を用いて水に分散し、１０ｗｔ％のスラリーを作製した。ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらにこの酸化マグネシウムスラリー（１０ｗｔ％）に１回ディッピングした。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化マグネシウムは１３．０４ｗｔ％であった。
[Comparative Example 3]
In the same manner as in Reference Example 1 , a glass fiber nonwoven fabric having a thickness of 50 μm and a basis weight of 10 g / m 2 was obtained. As an additive, magnesium oxide powder (Ube Materials Co., Ltd., UC-95S average particle size 3.1 μm, specific surface area 9.10 m 2 / g by BET method) is dispersed in water using a stirrer, and 10 wt% slurry is prepared. Produced. The glass fiber nonwoven fabric was dipped in an aqueous solution of SBR binder resin (SBR concentration 3 wt%), and then dipped once in this magnesium oxide slurry (10 wt%). When the obtained separator was dried at 120 ° C. for 12 hours and then weighed, the magnesium oxide supported on the separator was 13.04 wt%.
［比較例４］
参考例１と同様にして厚み５０μｍ、目付量１０ｇ／ｍ２のガラス繊維不織布を得た。添加物として酸化マグネシウム粉末（宇部マテリアルズ株式会社、ＵＣ−９５Ｍ 平均粒径３．１μｍ、比表面積９．１０ｍ２／ｇ）を攪拌機を用いて水に分散し、１０ｗｔ％のスラリーを作製した。ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらに酸化マグネシウムスラリー（１０ｗｔ％）に１回ディッピングした。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化マグネシウムは１６．６７ｗｔ％であった。
[Comparative Example 4]
In the same manner as in Reference Example 1 , a glass fiber nonwoven fabric having a thickness of 50 μm and a basis weight of 10 g / m 2 was obtained. As an additive, magnesium oxide powder (Ube Materials Co., Ltd., UC-95M average particle diameter 3.1 μm, specific surface area 9.10 m 2 / g) was dispersed in water using a stirrer to prepare a 10 wt% slurry. The glass fiber nonwoven fabric was dipped in an aqueous solution of SBR binder resin (SBR concentration 3 wt%), and then dipped once in a magnesium oxide slurry (10 wt%). When the obtained separator was dried at 120 ° C. for 12 hours and weighed, the magnesium oxide supported on the separator was 16.67 wt%.
［比較例５］
参考例１と同様にして厚み５０μｍ、目付量１０ｇ／ｍ２のガラス繊維不織布を得た。添加物として酸化マグネシウム粉末（宇部マテリアルズ株式会社、ＵＣ−９５Ｈ 平均粒径３．３μｍ、比表面積５．６６ｍ２／ｇ）を攪拌機を用いて水に分散し、１０ｗｔ％のスラリーを作製した。ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらに酸化マグネシウムスラリー（１０ｗｔ％）に２回ディッピングした。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化マグネシウムは２８．５７ｗｔ％であった。
[Comparative Example 5]
In the same manner as in Reference Example 1 , a glass fiber nonwoven fabric having a thickness of 50 μm and a basis weight of 10 g / m 2 was obtained. As an additive, magnesium oxide powder (Ube Materials Co., Ltd., UC-95H average particle size 3.3 μm, specific surface area 5.66 m 2 / g) was dispersed in water using a stirrer to prepare a 10 wt% slurry. The glass fiber nonwoven fabric was dipped in an aqueous solution of SBR binder resin (SBR concentration 3 wt%), and then dipped twice in a magnesium oxide slurry (10 wt%). When the obtained separator was dried at 120 ° C. for 12 hours and weighed, the magnesium oxide supported on the separator was 28.57 wt%.
［比較例６］
参考例１と同様にして厚み５０μｍ、目付量１０ｇ／ｍ２のガラス繊維不織布を得た。添加物として酸化マグネシウム粉末（宇部マテリアルズ株式会社、ＵＣＭ−１５０ 平均粒径３．３μｍ、比表面積１７６．００ｍ２／ｇ）を攪拌機を用いて水に分散し、１．０ｗｔ％のスラリーを作製した。ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらに酸化マグネシウムスラリー（１．０ｗｔ％）に1回ディッピングした。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化マグネシウムは０．９９ｗｔ％であった。
[Comparative Example 6]
In the same manner as in Reference Example 1 , a glass fiber nonwoven fabric having a thickness of 50 μm and a basis weight of 10 g / m 2 was obtained. As an additive, magnesium oxide powder (Ube Materials Co., Ltd., UCM-150 average particle size 3.3 μm, specific surface area 176.00 m 2 / g) is dispersed in water using a stirrer to produce a 1.0 wt% slurry. did. The glass fiber nonwoven fabric was dipped in an aqueous solution of SBR binder resin (SBR concentration 3 wt%), and then dipped once in a magnesium oxide slurry (1.0 wt%). When the obtained separator was dried at 120 ° C. for 12 hours and weighed, the magnesium oxide supported on the separator was 0.99 wt%.
［比較例７］
参考例１と同様にして厚み５０μｍ、目付量１０ｇ／ｍ２のガラス繊維不織布を得た。添加物として酸化ジルコニウム粉末（株式会社高純度化学研究所、ＺＲ００２ＰＡ、平均粒径１．０μｍ、比表面積１７．４０ｍ２／ｇ）を攪拌機を用いて水に分散し、１０ｗｔ％のスラリーを作製した。ガラス繊維不織布をＳＢＲバインダー樹脂の水溶液（ＳＢＲ濃度３ｗｔ％）にディッピングした後、さらに酸化マグネシウムスラリー（１０ｗｔ％）に1回ディッピングした。得られたセパレータを１２０℃で１２時間乾燥後に重量測定した所、セパレータに担持された酸化マグネシウムは９．０９ｗｔ％であった。
[Comparative Example 7]
In the same manner as in Reference Example 1 , a glass fiber nonwoven fabric having a thickness of 50 μm and a basis weight of 10 g / m 2 was obtained. Zirconium oxide powder (High Purity Chemical Laboratory Co., Ltd., ZR002PA, average particle size 1.0 μm, specific surface area 17.40 m 2 / g) was dispersed in water using an agitator as an additive to prepare a 10 wt% slurry. . The glass fiber nonwoven fabric was dipped in an aqueous solution of SBR binder resin (SBR concentration 3 wt%), and then dipped once in a magnesium oxide slurry (10 wt%). When the obtained separator was dried at 120 ° C. for 12 hours and weighed, magnesium oxide supported on the separator was 9.09 wt%.
実施例、参考例及び比較例のセパレータを、直径１９ｍｍ、重量２ｍｇに形成して以下の形式の電池に使用した。
電池形式：ＣＲ２０３２型コイン電池（スペーサ厚み：１．０ｍｍ） 宝泉製
正極材：コバルト酸リチウム（理論容量：１．５ｍＡｈ／ｃｍ２） 宝泉製
負極材：グラファイト（理論容量：１．６ｍＡｈ／ｃｍ２） 宝泉製
電解液組成：１Ｍ ＬｉＰＦ６／（ＥＣ：ＤＥＣ＝１：３ｖｏｌ％）＋２ｗｔ％ ＶＣ キシダ化学製
正極径：１５ｍｍ／セパレータ径：１９ｍｍ／負極径：１６ｍｍ／電解液量１６０μＬ
作製時の雰囲気：グローブボックス内 アルゴン雰囲気下
そして、上記形式の電池を以下の条件にして充放電を繰り返し行った。
大気下、室温（２５℃）で充放電休止時間を１０分とし、充電（定電流方式、０．２、０．５Ｃ電流レート、４．２Ｖ cutoff at room temp.）と放電（定電流方式、０．２、０．５Ｃ電流レート、２．８Ｖ cutoff at room temp.）とを繰り返した。
そして、満充電（ＳＯＣ＝１００％）後、６０℃にて５日間保存し、その後の放電容量を測定、容量維持率を以下の式で算出した。
容量維持率（％）＝（高温保存後の放電容量）／（保存前の放電容量）×１００
The separators of Examples, Reference Examples and Comparative Examples were formed in a diameter of 19 mm and a weight of 2 mg and used for batteries of the following types.
Battery type: CR2032-type coin battery (spacer thickness: 1.0 mm) Hohosen positive electrode material: lithium cobalt oxide (theoretical capacity: 1.5 mAh / cm 2 ) Hosen made negative electrode material: graphite (theoretical capacity: 1.6 mAh / cm 2 ) Hosen made electrolyte composition: 1M LiPF 6 / (EC: DEC = 1: 3 vol%) + 2 wt% manufactured by VC Kishida Chemical Positive electrode diameter: 15 mm / separator diameter: 19 mm / negative electrode diameter: 16 mm / electrolyte amount 160 μL
Atmosphere at the time of production: Inside the glove box Under an argon atmosphere Then, the battery of the above type was repeatedly charged and discharged under the following conditions.
Charging (constant current method, 0.2, 0.5C current rate, 4.2V cutoff at room temp.) And discharging (constant current method, 0.2, 0.5C current rate, 2.8V cutoff at room temp.).
And after full charge (SOC = 100%), it preserve | saved at 60 degreeC for 5 days, the subsequent discharge capacity was measured, and the capacity | capacitance maintenance factor was computed with the following formula | equation.
Capacity retention rate (%) = (discharge capacity after storage at high temperature) / (discharge capacity before storage) × 100
また、電池高温特性の劣化原因を把握するため、電解液中の電解液中のフッ素イオン濃度を評価した。試験方法は、実施例又は比較例のセパレータを電解液に浸漬して６０℃で１日保持した後、電解液０．５［ｍＬ］にイオン交換水を加えて５０［ｍＬ］とし、容器ごとよく振り混ぜて電解液を水に溶解させる。そして、この水溶液をイオンクロマトグラフ装置で測定した。 Moreover, in order to grasp the cause of deterioration of the battery high temperature characteristics, the fluorine ion concentration in the electrolytic solution in the electrolytic solution was evaluated. The test method is to immerse the separator of Example or Comparative Example in an electrolytic solution and hold it at 60 ° C. for 1 day, and then add ion exchange water to 0.5 [mL] of the electrolytic solution to make 50 [mL]. Shake well to dissolve the electrolyte in water. And this aqueous solution was measured with the ion chromatograph apparatus.
実施例、参考例及び比較例の結果を以下の表１にまとめる。表１から明らかなように添加物のＢＥＴ法による比表面積（ｍ２／ｇ）と添加重量割合（ｗｔ％）との積が、３００［（ｍ２／ｇ）・（ｗｔ％）］以上となる場合、容量維持率は７０％以上で良好な特性を得られたが、３００［（ｍ２／ｇ）・（ｗｔ％）］未満では容量維持率が７０％未満となり良好な特性を得られなかった。またフッ素イオン濃度においては添加重量割合（ｗｔ％）の積が、３００［（ｍ２／ｇ）・（ｗｔ％）］以上となる場合、フッ素イオン濃度が低いが、３００［（ｍ２／ｇ）・（ｗｔ％）］未満ではフッ素イオン濃度が高くなっていることが分かる。また、前記積が４０００［（ｍ２／ｇ）・（ｗｔ％）］以上になると容量維持率が７２％以上となり、前記積が６０００［（ｍ２／ｇ）・（ｗｔ％）］以上になるとフッ素イオン濃度が２６％未満となることが分かる。
これはマグネシア（ＭｇＯ）が電解液中のフッ素イオンを捕捉するため、電解液中のフッ素イオンのガラスセパレータへの影響を軽減し、高温保存において良好な特性を示したと考えられる。
The results of Examples, Reference Examples and Comparative Examples are summarized in Table 1 below. As apparent from Table 1, the product of the specific surface area (m 2 / g) of the additive by the BET method and the added weight ratio (wt%) is 300 [(m 2 / g) · (wt%)] or more. In this case, good characteristics can be obtained when the capacity retention ratio is 70% or more. However, if the capacity retention ratio is less than 300 [(m 2 / g) · (wt%)], the capacity retention ratio is less than 70% and good characteristics are obtained. There wasn't. In addition, when the product of the weight ratio (wt%) of the fluorine ion concentration is 300 [(m 2 / g) · (wt%)] or more, the fluorine ion concentration is low, but 300 [(m 2 / g ) · (Wt%)], it can be seen that the fluorine ion concentration is high. Further, when the product is 4000 [(m 2 / g) · (wt%)] or more, the capacity maintenance ratio is 72% or more, and the product is 6000 [(m 2 / g) · (wt%)] or more. Then, it can be seen that the fluorine ion concentration is less than 26%.
This is thought to be because magnesia (MgO) captures fluorine ions in the electrolyte solution, thereby reducing the influence of the fluorine ions in the electrolyte solution on the glass separator and exhibiting good characteristics during high-temperature storage.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012104271A JP5876766B2 (en) | 2012-04-30 | 2012-04-30 | Nonaqueous electrolyte secondary battery separator and battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012104271A JP5876766B2 (en) | 2012-04-30 | 2012-04-30 | Nonaqueous electrolyte secondary battery separator and battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2013232357A JP2013232357A (en) | 2013-11-14 |
| JP5876766B2 true JP5876766B2 (en) | 2016-03-02 |
Family
ID=49678623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012104271A Active JP5876766B2 (en) | 2012-04-30 | 2012-04-30 | Nonaqueous electrolyte secondary battery separator and battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5876766B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016009579A (en) * | 2014-06-24 | 2016-01-18 | 三菱製紙株式会社 | Separator for lithium ion secondary battery |
| JP6390917B2 (en) * | 2015-11-05 | 2018-09-19 | トヨタ自動車株式会社 | Non-aqueous electrolyte secondary battery |
| US20190097198A1 (en) * | 2016-03-01 | 2019-03-28 | Nippon Sheet Glass Company, Limited | Separator for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| JP6186548B1 (en) * | 2016-03-01 | 2017-08-23 | 日本板硝子株式会社 | Nonaqueous electrolyte secondary battery separator and nonaqueous electrolyte secondary battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03152860A (en) * | 1989-11-09 | 1991-06-28 | Matsushita Electric Ind Co Ltd | Separator for lead-acid battery |
| JP4270411B2 (en) * | 1998-03-09 | 2009-06-03 | 日本板硝子株式会社 | Nonaqueous electrolyte battery and separator for nonaqueous electrolyte battery |
| JP4075866B2 (en) * | 2004-06-25 | 2008-04-16 | 松下電器産業株式会社 | Flat organic electrolyte battery |
| JP2011210413A (en) * | 2010-03-29 | 2011-10-20 | Konica Minolta Holdings Inc | Separator for electrochemical element and nonaqueous electrolyte secondary battery |
-
2012
- 2012-04-30 JP JP2012104271A patent/JP5876766B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013232357A (en) | 2013-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lai et al. | Three-dimension hierarchical Al2O3 nanosheets wrapped LiMn2O4 with enhanced cycling stability as cathode material for lithium ion batteries | |
| JP5266861B2 (en) | Method for producing positive electrode active material for lithium secondary battery | |
| KR101494715B1 (en) | Negative active material for rechargeable lithium battery, method of preparing the same, and negative electrode and rechargeable lithium battery including the same | |
| JP5754855B2 (en) | Anode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery | |
| JP5879761B2 (en) | Lithium composite compound particle powder, method for producing the same, and nonaqueous electrolyte secondary battery | |
| JP5890886B1 (en) | Lithium manganese iron phosphate positive electrode active material and method for producing the same | |
| JP6724292B2 (en) | Positive electrode active material for non-aqueous secondary battery | |
| KR20160091172A (en) | Manufacturing method of positive active material containing reduced residual lithium and positive active material manufactured by the same | |
| KR20160043979A (en) | Improved lithium metal oxide rich cathode materials and method to make them | |
| JP2015508559A (en) | Silicon-based composite and method for producing the same | |
| JP5820521B1 (en) | Positive electrode material for lithium secondary battery and method for producing the same | |
| KR101588652B1 (en) | Positive active material, lithium secondary battery having the same and manufacturing method thereof | |
| KR20200053521A (en) | Silicon anode material for lithium ion batteries | |
| JP5876766B2 (en) | Nonaqueous electrolyte secondary battery separator and battery | |
| JP5953624B2 (en) | Method for producing Si / C composite | |
| JP2016033854A (en) | Positive electrode active material for nonaqueous electrolyte secondary battery | |
| JP2013030420A (en) | Negative electrode material for lithium ion battery containing surface-fluorinated b-type titanium oxide and manufacturing method thereof, and lithium ion battery using the same | |
| JP5890885B1 (en) | Positive electrode active material for lithium secondary battery and method for producing the same | |
| JP6232931B2 (en) | A method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery. | |
| JP6265521B2 (en) | ELECTRODE FOR LITHIUM SECONDARY BATTERY, ITS MANUFACTURING METHOD, AND LITHIUM SECONDARY BATTERY USING THE SAME | |
| CN106848254B (en) | Sodium-ion battery negative electrode material, preparation method thereof and sodium-ion battery | |
| JP6307127B2 (en) | Method for producing lithium phosphate positive electrode active material | |
| JP2016184568A (en) | Positive electrode active material for secondary battery and manufacturing method of the same | |
| JP5809200B2 (en) | Silicon-based negative electrode active material | |
| JP2017004805A (en) | Negative electrode material for battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20141027 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150414 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150415 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150526 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20151006 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151217 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20151224 |
|
| 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: 20160119 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160122 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5876766 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 |
|
| 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 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |