JP2013187138A - Method of manufacturing separator substrate for lithium ion secondary battery - Google Patents
Method of manufacturing separator substrate for lithium ion secondary battery Download PDFInfo
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- JP2013187138A JP2013187138A JP2012053119A JP2012053119A JP2013187138A JP 2013187138 A JP2013187138 A JP 2013187138A JP 2012053119 A JP2012053119 A JP 2012053119A JP 2012053119 A JP2012053119 A JP 2012053119A JP 2013187138 A JP2013187138 A JP 2013187138A
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- secondary battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000000758 substrate Substances 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 230000005294 ferromagnetic effect Effects 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000012545 processing Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000003302 ferromagnetic material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 13
- BGPVFRJUHWVFKM-UHFFFAOYSA-N N1=C2C=CC=CC2=[N+]([O-])C1(CC1)CCC21N=C1C=CC=CC1=[N+]2[O-] Chemical compound N1=C2C=CC=CC2=[N+]([O-])C1(CC1)CCC21N=C1C=CC=CC1=[N+]2[O-] BGPVFRJUHWVFKM-UHFFFAOYSA-N 0.000 description 11
- 239000003621 irrigation water Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 229910001172 neodymium magnet Inorganic materials 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910000828 alnico Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 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
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
Abstract
Description
本発明は、リチウムイオン二次電池、リチウムイオンポリマー二次電池等のリチウムイオン二次電池に使用されるセパレータ基材の製造方法に関するものである。 The present invention relates to a method for producing a separator base material used in lithium ion secondary batteries such as lithium ion secondary batteries and lithium ion polymer secondary batteries.
近年のデジタルカメラ、携帯電話、携帯情報端末等の携帯電子機器の普及とその高性能化に伴い、高いエネルギー密度を有する二次電池として、有機電解液（非水電解液）を使用するリチウムイオン二次電池が注目されてきた。リチウムイオン二次電池中には、正極と負極を分離する目的でセパレータが使用されている。 Lithium ions that use organic electrolyte (non-aqueous electrolyte) as a secondary battery with high energy density as portable electronic devices such as digital cameras, mobile phones, and personal digital assistants become more popular and have higher performance in recent years. Secondary batteries have attracted attention. In the lithium ion secondary battery, a separator is used for the purpose of separating the positive electrode and the negative electrode.
セパレータ中に金属異物が存在すると、正極と負極との間の絶縁性が不十分となって、内部短絡を引き起こし、リチウムイオン二次電池の充放電機能が発揮されない可能性があることから、セパレータ製造工程においては、セパレータ中への金属異物の混入を抑制するための対策が求められている。 If there is a metal foreign substance in the separator, the insulation between the positive electrode and the negative electrode becomes insufficient, causing an internal short circuit, and the charge / discharge function of the lithium ion secondary battery may not be exhibited. In the manufacturing process, there is a demand for measures for suppressing the mixing of metallic foreign matters into the separator.
現行のリチウムイオン二次電池のセパレータとしては、ポリエチレン等のポリオレフィン系多孔性フィルムが一般に使用されている。このようなセパレータには、電池内部の温度が１３０℃近傍になった場合、溶融して微多孔を塞ぐことでリチウムイオンの移動を妨げ、電流を遮断させるシャットダウン機能があるが、何らかの状況によりさらに温度が上昇した場合、ポリオレフィン系多孔性フィルム自体が溶融収縮して短絡を起こし、電池の熱暴走、発火に繋がる可能性が示唆されている。 As separators for current lithium ion secondary batteries, polyolefin-based porous films such as polyethylene are generally used. Such a separator has a shutdown function that prevents the movement of lithium ions by melting and plugging micropores when the temperature inside the battery is close to 130 ° C., and shuts off the current. It has been suggested that when the temperature rises, the polyolefin-based porous film itself melts and contracts to cause a short circuit, which may lead to thermal runaway and ignition of the battery.
そのため、２００℃近くの温度でも溶融及び収縮が起こらない耐熱性セパレータの開発が進められており、再生セルロース繊維や、合成樹脂短繊維を含有してなる不織布をセパレータ基材として使用することが提案されている（例えば、特許文献１〜３参照）。 Therefore, development of a heat-resistant separator that does not melt and shrink even at temperatures close to 200 ° C. is underway, and it is proposed to use recycled cellulose fibers and nonwoven fabrics containing synthetic resin short fibers as the separator base material. (For example, see Patent Documents 1 to 3).
再生セルロース繊維や合成樹脂短繊維を含有してなる不織布を生産する方法の一つとして、湿式抄紙法が挙げられる。湿式抄紙法を用いてリチウムイオン二次電池用セパレータ基材を製造する場合には、抄紙で使用する用水中に金属異物が存在していると、セパレータ基材内へ混入し、電池の内部短絡を引き起こす要因となるため、用水中の金属異物除去が製造における課題となっている。 As one of methods for producing a nonwoven fabric containing regenerated cellulose fibers or synthetic resin short fibers, a wet papermaking method can be mentioned. When manufacturing separator substrates for lithium ion secondary batteries using the wet papermaking method, if there are metallic foreign objects in the water used for papermaking, they will enter the separator substrate and cause internal short circuit of the battery. Therefore, the removal of metallic foreign matters in the irrigation water is a problem in manufacturing.
用水中の金属異物除去方法として、磁石を用いる方法が一般的に用いられているが、長時間使用していると、磁石表面に付着した金属異物が水流によって再度用水内に戻されるため、除去した金属異物は定期的に回収、廃棄する必要がある。磁石に吸着した金属異物は、磁力によって磁石表面に強く引き寄せられているため、回収には多くの工数が必要となるという問題がある。 A method using a magnet is generally used as a method for removing metallic foreign matter in water. However, if used for a long time, the metallic foreign matter attached to the surface of the magnet is returned to the working water again by the water flow. It is necessary to collect and dispose of the metal foreign matter regularly. Since the metal foreign matter adsorbed on the magnet is strongly attracted to the magnet surface by the magnetic force, there is a problem that many man-hours are required for recovery.
本発明は、リチウムイオン二次電池に用いられるセパレータ基材の製造において、セパレータ基材中への金属異物の混入を抑制することを目的としたものである。 The object of the present invention is to suppress the mixing of metal foreign matter into the separator base material in the manufacture of the separator base material used in the lithium ion secondary battery.
本発明者らは、この課題を解決するために鋭意検討を行った結果、強磁性体の金網と永久磁石とを有する処理装置で処理した抄紙用水を用いた湿式抄紙法によって、セパレータ基材中への金属異物の混入を抑制できることを見出し、本発明に至ったものである。 As a result of diligent studies to solve this problem, the inventors of the present invention have found that the separator base material can be obtained by a wet papermaking method using a papermaking water treated with a processing apparatus having a ferromagnetic wire mesh and a permanent magnet. The present inventors have found that metal foreign matter can be prevented from being mixed into the present invention, and have reached the present invention.
即ち、本発明は、湿式抄紙法によるリチウムイオン二次電池用セパレータ基材の製造において、抄紙用水として強磁性体の金網と永久磁石とを有する処理装置で処理した水を使用することを特徴とするリチウムイオン二次電池用セパレータ基材製造方法である。 That is, the present invention is characterized in that, in the production of a separator base material for a lithium ion secondary battery by a wet papermaking method, water treated with a processing apparatus having a ferromagnetic wire mesh and a permanent magnet is used as papermaking water. This is a separator base material manufacturing method for a lithium ion secondary battery.
また、強磁性体の金網の材質が亜鉛引鉄、あるいはフェライト系ステンレスであるとより好ましい。 Further, it is more preferable that the material of the ferromagnetic wire mesh is galvanized iron or ferritic stainless steel.
また、強磁性体の金網の目開きが２ｍｍ以下であるとより好ましい。 Moreover, it is more preferable that the opening of the ferromagnetic metal mesh is 2 mm or less.
本発明の製造方法によって製造されたリチウムイオン二次電池用セパレータ基材は、金属異物の含有量が抑制されており、リチウムイオン二次電池の内部短絡不良率を下げることが可能となる。また、本発明で使用している強磁性体の金網と永久磁石とを有する処理装置は、抄紙用水中の金属異物の除去性能が高い。さらに用水中から除去した金属異物を容易に回収、廃棄することができるため、除去した金属異物が再度用水中に混入することを抑制することができる。 In the separator base material for a lithium ion secondary battery manufactured by the manufacturing method of the present invention, the content of metal foreign matter is suppressed, and the internal short circuit defect rate of the lithium ion secondary battery can be lowered. Further, the processing apparatus having a ferromagnetic wire mesh and a permanent magnet used in the present invention has a high ability to remove metallic foreign matters in papermaking water. Furthermore, since the metal foreign matter removed from the irrigation water can be easily collected and discarded, it is possible to prevent the removed metal foreign matter from being mixed into the irrigation water again.
本発明のリチウムイオン二次電池用セパレータ基材製造方法について説明する。本発明のリチウムイオン二次電池用セパレータ基材は、湿式抄紙法を用いて繊維ウェブを形成し、その繊維ウェブを接着・溶融・絡合させる方法によって製造された不織布から構成される。湿式抄紙法は、繊維を水中に分散して均質な抄紙スラリーとし、この抄紙スラリーを円網、長網、短網、傾斜式等のワイヤーの少なくとも１つを有する抄紙機を用いて繊維ウェブを形成する方法である。 The separator base material manufacturing method for lithium ion secondary batteries of the present invention will be described. The separator substrate for a lithium ion secondary battery of the present invention is composed of a nonwoven fabric produced by a method in which a fiber web is formed using a wet papermaking method and the fiber web is bonded, melted and entangled. In the wet papermaking method, fibers are dispersed in water to form a homogeneous papermaking slurry, and this papermaking slurry is made into a fiber web using a papermaking machine having at least one of a wire such as a circular net, a long net, a short net, and an inclined type. It is a method of forming.
本発明のリチウムイオン二次電池用セパレータ基材製造方法においては、湿式抄紙法で使用される抄紙用水として、強磁性体の金網と永久磁石とを有する処理装置で処理された水を使用する。抄紙用水は、繊維の分散、抄紙スラリーの希釈、抄紙機ワイヤー、ブランケットの洗浄水等の湿式抄紙法による抄紙工程で使用される水を指す。 In the separator base material manufacturing method for a lithium ion secondary battery of the present invention, water processed by a processing apparatus having a ferromagnetic wire mesh and a permanent magnet is used as the papermaking water used in the wet papermaking method. Papermaking water refers to water used in the papermaking process by a wet papermaking method such as fiber dispersion, papermaking slurry dilution, papermaking machine wire, blanket washing water.
本発明のリチウムイオン二次電池用セパレータ基材製造方法においては、全ての抄紙用水に強磁性体の金網と永久磁石とを有する処理装置で処理された水を使用することが好ましいが、処理装置を用いない水を併用することもできる。 In the separator base material manufacturing method for a lithium ion secondary battery of the present invention, it is preferable to use water treated with a processing device having a ferromagnetic wire mesh and a permanent magnet for all papermaking water. Water without using can also be used in combination.
本発明における抄紙用水処理装置の概略図を図１に示す。給水口１から装置内に入った抄紙用水は、強磁性体の金網３によって濾過される。永久磁石４は強磁性体の金網３と接触している。濾過された抄紙用水は出水口５から装置外に出される。 A schematic diagram of a papermaking water treatment apparatus in the present invention is shown in FIG. The papermaking water that enters the apparatus through the water supply port 1 is filtered by the ferromagnetic wire mesh 3. The permanent magnet 4 is in contact with the ferromagnetic wire mesh 3. The filtered papermaking water is discharged from the water outlet 5 to the outside of the apparatus.
強磁性体の金網３は、用水流に対して略直角に接する面を有している。それ以外の形状は特に制限されず、円柱状、円筒篭状、多角柱状、多角錘篭状、平板状等の形状を取ることができる。 The ferromagnetic wire mesh 3 has a surface that is in contact with the water flow at a substantially right angle. Other shapes are not particularly limited, and may be a columnar shape, a cylindrical bowl shape, a polygonal column shape, a polygonal pyramid shape, a flat plate shape, or the like.
永久磁石４は強磁性体の金網３と接触しており、強磁性体の金網３、または処理装置本体２に固定されている。永久磁石４が強磁性体の金網３に固定されている場合、着脱可能な状態で固定されている。永久磁石４の個数は、金網３が１個に対して１個、または複数個であり、特に制限されない。永久磁石４は、用水流に対して略平行、略直交のどちらの方向に置かれても良い。永久磁石４を強磁性体の金網３から見て下流側に置いた場合には、用水中から除去した金属異物をより容易に回収することができるため好ましい。 The permanent magnet 4 is in contact with the ferromagnetic wire mesh 3 and is fixed to the ferromagnetic wire mesh 3 or the processing apparatus main body 2. When the permanent magnet 4 is fixed to the ferromagnetic wire mesh 3, it is fixed in a detachable state. The number of permanent magnets 4 is not particularly limited, and is one or a plurality of wire meshes 3. The permanent magnet 4 may be placed in either a direction substantially parallel or substantially orthogonal to the water flow. It is preferable to place the permanent magnet 4 on the downstream side when viewed from the ferromagnetic metal mesh 3 because the metal foreign matter removed from the irrigation water can be collected more easily.
永久磁石としては、アルニコ磁石、フェライト磁石、ネオジム磁石等の磁石が使用可能であるが、これらに制限されるものではない。 As permanent magnets, magnets such as alnico magnets, ferrite magnets and neodymium magnets can be used, but are not limited thereto.
本発明における抄紙用水処理装置は、抄紙用水配管に対して一段で、または複数段で使用される。複数段で使用した場合には、抄紙用水中の金属異物の除去性能が高くなるため好ましい。 The papermaking water treatment apparatus in the present invention is used in one stage or in a plurality of stages with respect to the papermaking water pipe. When used in a plurality of stages, it is preferable because the metal foreign matter removal performance in the papermaking water is enhanced.
強磁性体の金網の材質としては、鉄、亜鉛引鉄、フェライト系ステンレス、ニッケル等が挙げられる。亜鉛引鉄、フェライト系ステンレスは耐腐食性が高く、強磁性体の金網の材質として使用した場合、金網自体の腐食による抄紙用水中での金属異物発生が抑制されるため、特に好ましい。 Examples of the material of the ferromagnetic wire mesh include iron, zinc-drawn iron, ferritic stainless steel, and nickel. Zinc-coated iron and ferritic stainless steel are particularly preferred because they have high corrosion resistance and, when used as a ferromagnetic wire mesh material, metal foreign matter generation in papermaking water due to corrosion of the wire mesh itself is suppressed.
金網は、織金網、クリンプ金網、溶接金網、パンチングメタル等、一般に用いられている方法で製造したものが使用できる。金網の目開きは２００μｍから２ｍｍが好ましく、５００μｍから２ｍｍがさらに好ましい。金網の目開きが２ｍｍを超えると、永久磁石との接触により磁化された場合でも微小な金属異物の通過割合が増加するので好ましくない。一方、金網の目開きが２００μｍ未満になると、微小な金属異物の除去効率は良好になるが、砂等の金属異物以外の異物による目詰まりを誘発しやすくなるため好ましくない。 As the wire mesh, those manufactured by a generally used method such as a woven wire mesh, a crimp wire mesh, a welded wire mesh, and a punching metal can be used. The mesh opening of the wire mesh is preferably 200 μm to 2 mm, and more preferably 500 μm to 2 mm. If the mesh opening of the wire mesh exceeds 2 mm, the passage rate of minute metallic foreign matter increases even when magnetized by contact with a permanent magnet. On the other hand, if the mesh opening of the wire mesh is less than 200 μm, the removal efficiency of minute metallic foreign matters is improved, but it is not preferable because clogging by foreign matters other than metallic foreign matters such as sand is easily induced.
本発明で使用される抄紙用水処理装置においては、強磁性体の金網と永久磁石とを接触させて金網を磁化させる。その金網をスクリーンとして使用することによって、抄紙用水中の金属異物のうち磁性を有するものが磁化された金網に引きつけられ、金網に付着して用水中から除去される。強磁性体の金網と永久磁石とを接触させることによって金網全体が磁化されるため、永久磁石を単独で使用する場合に比べて用水との接触面積が大きくなり、金属異物の除去能力を向上させることができる。 In the papermaking water treatment apparatus used in the present invention, a ferromagnetic metal mesh and a permanent magnet are brought into contact with each other to magnetize the metal mesh. By using the wire mesh as a screen, metal foreign matter in the papermaking water is attracted to the magnetized wire mesh and attached to the wire mesh and removed from the water. Since the entire wire mesh is magnetized by bringing the ferromagnetic wire mesh into contact with the permanent magnet, the contact area with the water becomes larger than when the permanent magnet is used alone, and the ability to remove metallic foreign matter is improved. be able to.
金網から永久磁石を離すと、金網に付着している金属異物が金網から離れるため、磁石を単独で使用した場合に比べて、金属異物の回収、廃棄を容易に行うことができる。 When the permanent magnet is separated from the wire mesh, the metal foreign matter adhering to the wire mesh is separated from the wire mesh. Therefore, the metal foreign matter can be easily collected and discarded as compared with the case where the magnet is used alone.
本発明におけるリチウムイオン二次電池用セパレータ基材を構成する繊維については、セルロース系繊維、合成樹脂繊維、無機繊維など湿式抄紙法で繊維ウェブを形成できる繊維であれば適宜使用することができる。繊維は１種類を単独で使用しても、２種類以上の繊維を組み合わせて使用しても良い。 As the fiber constituting the separator base material for a lithium ion secondary battery in the present invention, any fiber that can form a fiber web by a wet papermaking method, such as cellulosic fiber, synthetic resin fiber, and inorganic fiber, can be used as appropriate. One type of fiber may be used alone, or two or more types of fibers may be used in combination.
繊維ウェブから不織布を形成する方法としては、水流交絡法、ニードルパンチ法、サーマルボンド法等、一般に用いられている方法を適宜使用することができる。 As a method for forming a nonwoven fabric from a fiber web, a generally used method such as a hydroentanglement method, a needle punch method, a thermal bond method, or the like can be appropriately used.
以下、本発明を実施例によりさらに詳細に説明するが、本発明は本実施例に限定されるものではない。なお以下に示す部、並びに％はいずれも質量基準である。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a present Example. The parts and% shown below are based on mass.
（実施例１）
繊度０．０６ｄｔｅｘ（平均繊維径２．４μｍ）、繊維長３ｍｍの配向結晶化させたポリエチレンテレフタレート（ＰＥＴ）系短繊維４０部と、繊度０．１ｄｔｅｘ（平均繊維径３．０μｍ）、繊維長１ｍｍの配向結晶化させたＰＥＴ系短繊維１０部と、繊度０．２ｄｔｅｘ（平均繊維径４．３μｍ）、繊維長３ｍｍの未延伸ＰＥＴ系熱融着性短繊維５０部とを一緒に混合し、パルパーにより水中で離解させ、アジテーターによる攪拌のもと、濃度１％の均一な抄造用スラリーを調製した。この抄造用スラリーを、円網抄紙機を用いた湿式抄紙法によって繊維ウェブに抄き上げた。抄造用スラリーの調製時、及び繊維ウェブの抄き上げ時には、図１に示した処理装置で処理した抄紙用水を使用した。金網３は鉄製、目開き５ｍｍのものを使用し、永久磁石４はネオジム磁石棒〔商品名：ＰＣＭＢ−１５ カネテック製〕を３本使用した。永久磁石４は金網３に脱着可能な状態で固定した。
Example 1
40 parts of polyethylene terephthalate (PET) short fibers having a fineness of 0.06 dtex (average fiber diameter of 2.4 μm) and a fiber length of 3 mm, a fineness of 0.1 dtex (average fiber diameter of 3.0 μm), and a fiber length of 1 mm 10 parts of oriented PET crystal short fibers and 50 parts of unstretched PET heat-sealable short fibers having a fineness of 0.2 dtex (average fiber diameter 4.3 μm) and a fiber length of 3 mm are mixed together, A uniform papermaking slurry having a concentration of 1% was prepared by disaggregating in water with a pulper and stirring with an agitator. This papermaking slurry was made into a fiber web by a wet papermaking method using a circular paper machine. At the time of preparing the papermaking slurry and at the time of making up the fiber web, the papermaking water treated with the processing apparatus shown in FIG. 1 was used. The wire mesh 3 is made of iron and has an opening of 5 mm, and the permanent magnet 4 is made of three neodymium magnet rods (trade name: PCMB-15, manufactured by Kanetech). The permanent magnet 4 was fixed to the wire mesh 3 in a detachable state.
得られた繊維ウェブは、温度１２０℃のシリンダードライヤーによってＰＥＴ系熱融着性短繊維を接着させて強度を発現させ、坪量１０．５ｇ／ｍ２、幅５０ｃｍの不織布とした。さらに、この不織布を金属ロール−金属ロールからなる１ニップの熱カレンダーを使用して、ロール温度１８５℃、線圧８０ｋＮ／ｍ、搬送速度２０ｍ／分の条件で加熱処理を実施して、坪量１０．５ｇ／ｍ２、厚さ１７μｍのリチウムイオン二次電池用セパレータ基材を作製した。 The obtained fiber web was bonded to PET heat-fusible short fibers with a cylinder dryer at a temperature of 120 ° C. to develop strength, and was a nonwoven fabric having a basis weight of 10.5 g / m 2 and a width of 50 cm. Furthermore, this nonwoven fabric was subjected to heat treatment under the conditions of a roll temperature of 185 ° C., a linear pressure of 80 kN / m, and a conveyance speed of 20 m / min, using a 1-nip heat calender consisting of a metal roll and a metal roll. A separator substrate for a lithium ion secondary battery having a thickness of 10.5 g / m 2 and a thickness of 17 μm was produced.
（実施例２）
金網３の材質を亜鉛引鉄とした以外は、実施例１と同様にしてリチウムイオン二次電池用セパレータ基材を作製した。
(Example 2)
A separator substrate for a lithium ion secondary battery was produced in the same manner as in Example 1 except that the material of the wire mesh 3 was zinc-drawn iron.
（実施例３）
金網３の材質をフェライト系ステンレス（ＳＵＳ４３０）とした以外は、実施例１と同様にしてリチウムイオン二次電池用セパレータ基材を作製した。
(Example 3)
A separator base material for a lithium ion secondary battery was produced in the same manner as in Example 1 except that the material of the wire mesh 3 was changed to ferritic stainless steel (SUS430).
（実施例４）
金網３の目開きを１ｍｍとした以外は、実施例１と同様にしてリチウムイオン二次電池用セパレータ基材を作製した。
Example 4
A separator substrate for a lithium ion secondary battery was produced in the same manner as in Example 1 except that the opening of the wire mesh 3 was 1 mm.
（実施例５）
金網３の材質を亜鉛引鉄、目開きを１ｍｍとした以外は、実施例１と同様にしてリチウムイオン二次電池用セパレータ基材を作製した。
(Example 5)
A separator substrate for a lithium ion secondary battery was produced in the same manner as in Example 1 except that the material of the wire mesh 3 was zinc-drawn iron and the mesh opening was 1 mm.
（実施例６）
金網３の材質をフェライト系ステンレス（ＳＵＳ４３０）、目開きを１ｍｍとした以外は、実施例１と同様にしてリチウムイオン二次電池用セパレータ基材を作製した。
(Example 6)
A separator substrate for a lithium ion secondary battery was produced in the same manner as in Example 1 except that the material of the wire mesh 3 was ferritic stainless steel (SUS430) and the mesh opening was 1 mm.
（比較例１）
図１に示した処理装置から、金網３及び永久磁石４を取り除いた以外は、実施例１と同様にしてリチウムイオン二次電池用セパレータ基材を作製した。
(Comparative Example 1)
A separator substrate for a lithium ion secondary battery was produced in the same manner as in Example 1 except that the wire mesh 3 and the permanent magnet 4 were removed from the processing apparatus shown in FIG.
（比較例２）
図１に示した処理装置から、金網３を取り除いた以外は、実施例１と同様にしてリチウムイオン二次電池用セパレータ基材を作製した。永久磁石４は、処理装置本体２内側の抄紙用水が通過する部分に脱着可能な状態で固定した。
(Comparative Example 2)
A separator substrate for a lithium ion secondary battery was produced in the same manner as in Example 1 except that the wire mesh 3 was removed from the processing apparatus shown in FIG. The permanent magnet 4 was fixed in a removable state to a portion through which the papermaking water passes inside the processing apparatus main body 2.
（比較例３）
図１に示した処理装置から、永久磁石４を取り除いた以外は、実施例１と同様にしてリチウムイオン二次電池用セパレータ基材を作製した。
(Comparative Example 3)
A separator substrate for a lithium ion secondary battery was produced in the same manner as in Example 1 except that the permanent magnet 4 was removed from the processing apparatus shown in FIG.
（比較例４）
金網３の材質をオーステナイト系ステンレス（ＳＵＳ３０４）とした以外は、実施例１と同様にしてリチウムイオン二次電池用セパレータ基材を作製した。
(Comparative Example 4)
A separator substrate for a lithium ion secondary battery was produced in the same manner as in Example 1 except that the material of the wire mesh 3 was austenitic stainless steel (SUS304).
＜評価＞
実施例１〜６及び比較例１〜４で使用した抄紙用水処理装置と、実施例及び比較例で作製したリチウムイオン二次電池用セパレータ基材を、下記の評価に供した。評価結果を表１に示す。
<Evaluation>
The papermaking water treatment apparatus used in Examples 1 to 6 and Comparative Examples 1 to 4 and the separator base material for lithium ion secondary batteries prepared in Examples and Comparative Examples were subjected to the following evaluation. The evaluation results are shown in Table 1.
［金属異物回収・廃棄性］
使用後の抄紙用水処理装置を分解し、永久磁石及び金網で用水中から除去された金属異物の回収・廃棄性を評価した。評価基準は以下の指標に従った。
◎：用水中から除去された金属異物のほぼ全てを容易に回収・廃棄できる
○：用水中から除去された金属異物の一部は回収できないが、大半を回収・廃棄できる
△：用水中から除去された金属異物の多くを回収・廃棄できない
×：用水中から除去された金属異物の回収・廃棄が困難である
××：処理装置中に金属異物が存在せず、用水中から除去できていない
[Metal foreign matter collection and disposal]
The paper processing water treatment device after use was disassembled, and the recovery and disposal of the metal foreign matter removed from the water with permanent magnets and wire mesh was evaluated. The evaluation criteria followed the following indicators.
◎: Almost all of the metal foreign matter removed from the irrigation water can be easily recovered and discarded ○: Some of the metal foreign matter removed from the irrigation water cannot be recovered, but most can be recovered and discarded △: Removed from the irrigation water Many of the foreign metal particles cannot be recovered / discarded ×: The recovery / disposal of the foreign metal particles removed from the irrigation water is difficult XX: No foreign metal particles are present in the treatment equipment and they cannot be removed from the irrigation water
［鉄反応数評価］
リチウムイオン二次電池用セパレータ基材から５００ｍｍ×５００ｍｍの試験片を採取し、その試験片に５％塩酸水溶液を均一に噴霧した。続いて、５％フェロシアン化カリウム水溶液を試験片に均一に噴霧し、そのまま１時間放置して自然乾燥させた。リチウムイオン二次電池用セパレータ基材内に鉄分が存在する場合には、塩酸で溶解して鉄イオンが発生し、その鉄イオンがフェロシアン化カリウムによってプルシアンブルー発色を呈する。その発色数を目視によって計測し、試験片１ｍ２あたりの個数として評価した。
[Evaluation of number of iron reactions]
A test piece of 500 mm × 500 mm was taken from the separator base material for a lithium ion secondary battery, and a 5% hydrochloric acid aqueous solution was uniformly sprayed on the test piece. Subsequently, a 5% potassium ferrocyanide aqueous solution was uniformly sprayed on the test piece and left to stand for 1 hour to dry naturally. When iron is present in the separator base material for a lithium ion secondary battery, it dissolves with hydrochloric acid to generate iron ions, and the iron ions exhibit Prussian blue coloration due to potassium ferrocyanide. The number of developed colors was visually measured and evaluated as the number per 1 m 2 of the test piece.
＜リチウムイオン二次電池用セパレータの作製＞
板状ベーマイト（平均粒径：１μｍ、アスペクト比：１０）１０００ｇ、水８００ｇ、イソプロピルアルコール２００ｇ、ポリビニルブチラール３７５ｇを容器に入れ、攪拌機（商品名：スリーワンモーター、新東化学社製）で１時間攪拌して分散させ、均一なスラリーとした。このスラリー中に、実施例１〜６、比較例１〜４で作製したセパレータ基材をそれぞれ通し、引き上げ塗布によりスラリーを塗布した後、所定の間隔を有するギャップの間を通し、乾燥して、両面に多孔膜（厚さ：３μｍ）を有するリチウムイオン二次電池用セパレータを得た。
<Preparation of separator for lithium ion secondary battery>
1000 g of plate boehmite (average particle size: 1 μm, aspect ratio: 10), 800 g of water, 200 g of isopropyl alcohol, and 375 g of polyvinyl butyral are placed in a container and stirred for 1 hour with a stirrer (trade name: Three-One Motor, Shinto Chemical Co., Ltd.). And dispersed into a uniform slurry. In this slurry, the separator base materials prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were respectively passed, and after applying the slurry by pulling application, the gap was passed through a gap having a predetermined interval and dried. A separator for a lithium ion secondary battery having a porous film (thickness: 3 μm) on both surfaces was obtained.
＜リチウムイオン二次電池正極の作製＞
正極活物質であるコバルト酸リチウム７５部、導電助剤であるアセチレンブラック１５部、及びバインダーであるポリフッ化ビニリデン（ＰＶｄＦ）５部をＮ−メチル−２−ピロリドン（ＮＭＰ）中に均一に混合して、正極剤ペーストを作製した。この正極剤ペーストを厚さ２２μｍのアルミニウム箔上に塗工し、乾燥、カレンダー処理を行って、厚さ９７μｍのリチウムイオン二次電池正極を作製した。
<Preparation of lithium ion secondary battery positive electrode>
Uniformly mix 75 parts of lithium cobaltate as the positive electrode active material, 15 parts of acetylene black as the conductive additive, and 5 parts of polyvinylidene fluoride (PVdF) as the binder into N-methyl-2-pyrrolidone (NMP). Thus, a positive electrode paste was prepared. This positive electrode paste was applied onto an aluminum foil having a thickness of 22 μm, dried and calendered to produce a lithium ion secondary battery positive electrode having a thickness of 97 μm.
＜リチウムイオン二次電池負極の作製＞
負極活物質である黒鉛９５部と、バインダーであるＰＶｄＦ５部とを、ＮＭＰを溶剤として均一になるように混合して、負極剤ペーストを作製した。この負極剤ペーストを厚さ２４μｍの銅箔上に塗工し、乾燥、カレンダー処理を行って厚さ９２μｍのリチウムイオン二次電池負極を作製した。
<Preparation of negative electrode for lithium ion secondary battery>
A negative electrode agent paste was prepared by mixing 95 parts of graphite as a negative electrode active material and 5 parts of PVdF as a binder so as to be uniform using NMP as a solvent. This negative electrode agent paste was applied onto a 24 μm thick copper foil, dried and calendered to produce a 92 μm thick lithium ion secondary battery negative electrode.
＜リチウムイオン二次電池の作製＞
実施例及び比較例で作製したセパレータ基材を用いて作製したセパレータを介して、正極と負極とを重ね合わせ、ラミネートフィルム外装材内に装填し、電解質として１ｍｏｌ／ＬのＬｉＢＦ４を溶解させたエチレンカーボネート／ジエチルカーボネート（体積比１／１）溶液を注入し、真空封止を行ってリチウムイオン二次電池を作製した。
<Production of lithium ion secondary battery>
The positive electrode and the negative electrode were overlapped with each other through the separator prepared using the separator base material prepared in Examples and Comparative Examples, and loaded in a laminate film exterior material, and 1 mol / L LiBF 4 was dissolved as an electrolyte. An ethylene carbonate / diethyl carbonate (volume ratio 1/1) solution was injected and vacuum sealed to produce a lithium ion secondary battery.
［セパレータ機能評価］
作製したリチウムイオン二次電池について、１Ｃでの定電流充電（４．１Ｖまで）と４．１Ｖでの定電圧充電とを行ってから、１Ｃで３．０Ｖまでの定電流放電を行った。定電流充電−定電圧充電−定電流放電のサイクルを１０回繰り返し、実施例及び比較例で作製したセパレータ基材から作製したセパレータが、セパレータとして機能しているかどうかを評価した。評価基準は以下の指標に従った。
○：１０回の充放電サイクルが問題なく終了した
×：充放電サイクルが１０回に達する前に、充電が行えなくなった
[Separator function evaluation]
The produced lithium ion secondary battery was subjected to constant current charging at 1C (up to 4.1V) and constant voltage charging at 4.1V, and then constant current discharging up to 3.0V at 1C. The cycle of constant current charge-constant voltage charge-constant current discharge was repeated 10 times, and it was evaluated whether or not the separator produced from the separator base material produced in Examples and Comparative Examples was functioning as a separator. The evaluation criteria followed the following indicators.
○: 10 charging / discharging cycles ended without problems ×: Charging could not be performed before the charging / discharging cycle reached 10 times
実施例１〜６は、比較例１〜４に比べて鉄反応数が少ない。強磁性体の金網と永久磁石とを有する処理装置で処理した抄紙用水を使用して作製されたリチウムイオン二次電池用セパレータ基材中においては、そのような処理装置で処理されていない抄紙用水を使用して作製されたセパレータ基材に比べて、金属異物の混入が抑制されていることを示している。 Examples 1-6 have few iron reaction numbers compared with Comparative Examples 1-4. In the separator base material for a lithium ion secondary battery produced using a papermaking water treated by a treatment device having a ferromagnetic wire mesh and a permanent magnet, the papermaking water is not treated by such a treatment device. It is shown that mixing of metal foreign matters is suppressed as compared with a separator base material produced using
実施例２〜３、または実施例５〜６は、実施例１に比べて鉄反応数が少ない。強磁性体の金網の材質が亜鉛引鉄、あるいはフェライト系ステンレスであることによって、金網自体の腐食による抄紙用水中での金属異物発生が抑制されていることを示している。 Examples 2-3 and Examples 5-6 have fewer iron reactions than Example 1. It is shown that the formation of metallic foreign matter in the papermaking water due to the corrosion of the wire mesh itself is suppressed by the fact that the material of the ferromagnetic wire mesh is galvanized iron or ferritic stainless steel.
実施例４〜６は実施例１に比べて鉄反応数が少ない。強磁性体の金網の目開きが２ｍｍ以下であることによって、本発明の抄紙用水処理装置による金属異物の除去性能が向上していることを示している。 Examples 4-6 have few iron reaction numbers compared with Example 1. FIG. When the opening of the metal mesh of the ferromagnetic material is 2 mm or less, it is shown that the metal foreign matter removing performance of the papermaking water treatment device of the present invention is improved.
実施例１〜６は、比較例１〜４に比べて金属異物回収・廃棄性が良好であった。強磁性体の金網と永久磁石とを有する処理装置を使用することによって、抄紙用水から回収された金属異物の回収・廃棄が容易になることを示している。 Examples 1-6 were good in metal foreign material collection | recovery and discardability compared with Comparative Examples 1-4. This shows that the use of a processing apparatus having a ferromagnetic wire mesh and a permanent magnet facilitates the recovery and disposal of metallic foreign matter recovered from papermaking water.
実施例１〜６は、比較例１〜４に比べてセパレータ機能が良好であった。比較例１〜４では、セパレータ基材中の金属異物の存在によって、リチウムイオン二次電池中で内部短絡が生じており、セパレータがその機能を発揮していないのに対して、実施例１〜６では、セパレータ基材中の金属異物混入が抑制されており、電池の内部短絡が抑えられていることを示している。 In Examples 1 to 6, the separator function was better than Comparative Examples 1 to 4. In Comparative Examples 1 to 4, an internal short circuit occurs in the lithium ion secondary battery due to the presence of the metal foreign matter in the separator base material, whereas the separator does not perform its function. No. 6 shows that metal foreign matter mixing in the separator substrate is suppressed, and internal short circuit of the battery is suppressed.
１ 抄紙用水給水口
２ 抄紙用水処理装置本体
３ 強磁性体金網
４ 永久磁石
５ 抄紙用水出水口
1 Papermaking water supply port 2 Papermaking water treatment device body 3 Ferromagnetic wire mesh 4 Permanent magnet 5 Papermaking water outlet
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015065097A (en) * | 2013-09-26 | 2015-04-09 | 日本ゼオン株式会社 | Method for manufacturing slurry for porous film, and slurry for porous film |
| JP2017112102A (en) * | 2015-12-10 | 2017-06-22 | 株式会社半導体エネルギー研究所 | Power storage device, method of producing power storage device, and electronic device |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015065097A (en) * | 2013-09-26 | 2015-04-09 | 日本ゼオン株式会社 | Method for manufacturing slurry for porous film, and slurry for porous film |
| JP2017112102A (en) * | 2015-12-10 | 2017-06-22 | 株式会社半導体エネルギー研究所 | Power storage device, method of producing power storage device, and electronic device |
| CN107017430A (en) * | 2015-12-10 | 2017-08-04 | 株式会社半导体能源研究所 | Electrical storage device, the manufacture method of electrical storage device and electronic equipment |
| CN107017430B (en) * | 2015-12-10 | 2021-10-26 | 株式会社半导体能源研究所 | Power storage device, method for manufacturing power storage device, and electronic apparatus |
| US11264648B2 (en) | 2015-12-10 | 2022-03-01 | Semiconductor Laboratory Energy Co., Ltd. | Power storage device, method for manufacturing power storage device, and electronic device |
| US11942602B2 (en) | 2015-12-10 | 2024-03-26 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device, method for manufacturing power storage device, and electronic device |
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