JP2015219948A - Method for recovering valuables from lithium ion secondary battery - Google Patents
Method for recovering valuables from lithium ion secondary battery Download PDFInfo
- Publication number
- JP2015219948A JP2015219948A JP2014100081A JP2014100081A JP2015219948A JP 2015219948 A JP2015219948 A JP 2015219948A JP 2014100081 A JP2014100081 A JP 2014100081A JP 2014100081 A JP2014100081 A JP 2014100081A JP 2015219948 A JP2015219948 A JP 2015219948A
- Authority
- JP
- Japan
- Prior art keywords
- lithium ion
- ion secondary
- secondary battery
- magnetic force
- gauss
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 82
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 69
- 230000005291 magnetic effect Effects 0.000 claims abstract description 103
- 239000000463 material Substances 0.000 claims abstract description 92
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 59
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 59
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000002889 diamagnetic material Substances 0.000 claims abstract description 7
- 239000000696 magnetic material Substances 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 239000002907 paramagnetic material Substances 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 238000007885 magnetic separation Methods 0.000 abstract description 2
- 230000005298 paramagnetic effect Effects 0.000 abstract description 2
- 239000012634 fragment Substances 0.000 abstract 2
- 238000000926 separation method Methods 0.000 description 25
- 239000011888 foil Substances 0.000 description 23
- 239000011889 copper foil Substances 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000012141 concentrate Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000003302 ferromagnetic material Substances 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000006148 magnetic separator Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000150258 Prospect Hill orthohantavirus Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000218 poly(hydroxyvalerate) Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010187 selection method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
Description
本発明は、リチウムイオン二次電池からの有価物回収方法に関するもので、特に、アルミニウム、銅などの有価物を簡易かつ効率的にリチウムイオン二次電池から回収する方法に関するものである。
なお、この明細書及び特許請求の範囲において、リチウムイオン二次電池とは、リチウムイオン二次電池の製造工程で発生する不良品や使用済みで廃棄される携帯電話、ＰＣ、家電用の小型リチウムイオン二次電池、車載用や産業用の大型のリチウムイオン二次電池、及びその他のリチウムを構成要素として含む電池を包含する概念である。
The present invention relates to a method for recovering valuable materials from a lithium ion secondary battery, and more particularly to a method for easily and efficiently recovering valuable materials such as aluminum and copper from a lithium ion secondary battery.
In this specification and claims, a lithium ion secondary battery means a defective product generated in the manufacturing process of a lithium ion secondary battery, a small lithium for mobile phones, PCs, and home appliances that are used and discarded. It is a concept including an ion secondary battery, a large-sized lithium ion secondary battery for in-vehicle use or industrial use, and a battery containing other lithium as a constituent element.
リチウムイオン二次電池は、アルミニウム箔にリチウム、コバルト、ニッケルなどを塗布した正極、銅箔に黒鉛などを塗布した負極、そして電解液、セパレーターなどから構成されている。このようにリチウムイオン二次電池には、リチウム、コバルト、ニッケル、アルミニウム、銅などの有価物が含まれているため、廃棄等されたリチウムイオン二次電池から、これらの有用物質を回収することは、資源の乏しいわが国にとって非常に重要である。 A lithium ion secondary battery is composed of a positive electrode in which lithium, cobalt, nickel or the like is applied to an aluminum foil, a negative electrode in which graphite or the like is applied to a copper foil, an electrolyte, a separator, or the like. As described above, since lithium ion secondary batteries contain valuable materials such as lithium, cobalt, nickel, aluminum, and copper, these useful substances must be recovered from discarded lithium ion secondary batteries. Is very important for our poor country.
リチウムイオン二次電池からの有価物回収方法に関しては、特許文献１に、使用済みリチウム二次電池を焙焼し、次に破砕した後、破砕物を篩分けして篩下を回収する、主にコバルトの回収を目的とした回収方法が提案されている。
しかし、この提案技術にあっては、アルミニウム、銅などの他の有価物を効率よく回収できるものではなかった。
With regard to a method for recovering valuable materials from lithium ion secondary batteries, Patent Document 1 discloses a method in which used lithium secondary batteries are roasted and then crushed, and then crushed materials are sieved to collect the sieving. In addition, a recovery method for recovering cobalt has been proposed.
However, this proposed technique cannot efficiently recover other valuable materials such as aluminum and copper.
また、特許文献２には、アルミニウム製ケースに内蔵された使用済みリチウム電池を該アルミニウム製ケースとともに焙焼し、得られた焙焼物を破砕し、磁選して磁性物と非磁性物に分別し、さらに渦電流を発生させた非磁性物に磁石からの磁界を印加して、該非磁性物を該磁石から反撥させることにより、主としてアルミニウムからなる破砕粉と、主として銅からなる破砕粉とに分別して回収する方法が提案されている。
しかしながら、この渦電流を用いた選別方法にあっては、渦電流を発生させた非磁性物を磁石から反撥させて分離する際、非磁性物の形状の影響を受け易く、ともに空気の抵抗を受けることで煩雑な運動を呈する箔形状である正極集電体としてのアルミニウム箔と負極集電体としての銅箔とを、必ずしも精度良く分離できるものではなかった。
Patent Document 2 discloses that a used lithium battery built in an aluminum case is roasted together with the aluminum case, and the obtained roasted material is crushed and magnetically separated to be separated into a magnetic material and a non-magnetic material. Further, by applying a magnetic field from a magnet to a non-magnetic material that has generated eddy current and repelling the non-magnetic material from the magnet, it is separated into crushed powder mainly made of aluminum and crushed powder mainly made of copper. A separate collection method has been proposed.
However, in this sorting method using eddy currents, when repelling and separating the non-magnetic material that generated the eddy current from the magnet, it is easily affected by the shape of the non-magnetic material. The aluminum foil as the positive electrode current collector and the copper foil as the negative electrode current collector, each of which has a foil shape that exhibits complicated movements when received, cannot always be accurately separated.
更に、特許文献３には、正極集電体としてのアルミニウムを有する正極と負極集電体としての銅を有する負極とを有するリチウムイオン二次電池を、２５０℃〜５５０℃の温度で加熱して加熱物を得る加熱工程と、前記加熱物中の前記正極と前記負極とを選別する選別工程と、前記選別工程により選別された前記正極及び前記負極をそれぞれ破砕し、正極破砕物及び負極破砕物をそれぞれ得る破砕工程と、前記正極破砕物を篩分けして、前記アルミニウムを回収する第１の篩選別工程と、前記負極破砕物を篩分けして、前記銅を回収する第２の篩選別工程とを含むリチウムイオン二次電池からの有価物の回収方法が提案されている。
しかし、この提案技術では、正極と負極との選別工程を考慮した場合、その前工程である加熱工程においては、正極と負極との選別が容易となる電池セルの状態で加熱することが望ましく、電池セルの集合体である電池モジュール、更には電池モジュールの集合体である電池パックの場合には、それらを解体した後に加熱することが必要となり、また、正極と負極との選別工程は主に手作業となることから、かならずしも簡易かつ効率的に有価物を回収できる方法ではなかった。
Further, in Patent Document 3, a lithium ion secondary battery having a positive electrode having aluminum as a positive electrode current collector and a negative electrode having copper as a negative electrode current collector is heated at a temperature of 250 ° C. to 550 ° C. A heating step for obtaining a heated product, a sorting step for sorting the positive electrode and the negative electrode in the heated product, and crushing the positive electrode and the negative electrode sorted by the sorting step, respectively, Respectively, a first sieving step of sieving the crushed positive electrode to recover the aluminum, and a second sieving to recover the copper by sieving the crushed negative electrode A method for recovering valuable materials from a lithium ion secondary battery including a process has been proposed.
However, in this proposed technique, when considering the selection process of the positive electrode and the negative electrode, in the heating process that is the previous process, it is desirable to heat in the state of the battery cell that facilitates the selection of the positive electrode and the negative electrode, In the case of a battery module that is an assembly of battery cells, and further, a battery pack that is an assembly of battery modules, it is necessary to heat them after disassembling them. Since it is a manual operation, it has not always been a simple and efficient method for recovering valuable materials.
本発明は、上述した背景技術が有する種々の課題に鑑み成されたものであって、その目的は、リチウムイオン二次電池から、アルミニウム、銅などの有価物を簡単かつ効率的に回収することができる、リチウムイオン二次電池からの有価物回収方法を提案することにある。 The present invention has been made in view of the various problems of the background art described above, and its purpose is to easily and efficiently recover valuable materials such as aluminum and copper from a lithium ion secondary battery. It is to propose a method for recovering valuable materials from a lithium ion secondary battery.
上記した課題を解決するため、本発明は、次の〔１〕〜〔６〕に記載のリチウムイオン二次電池からの有価物回収方法とした。
〔１〕リチウムイオン二次電池を３００℃以上の温度で加熱し、次に破砕した後、得られた破砕物に対して８０００ガウス以上の高磁力選別を行い、常磁性体であるアルミニウムを磁着物として、反磁性体である銅を非磁着物として回収することを特徴とする、リチウムイオン二次電池からの有価物回収方法。
〔２〕上記破砕物に対する８０００ガウス以上の高磁力選別に先だって、破砕物を篩分け分級し、１．０〜１０．０ｍｍの破砕物に対して、上記８０００ガウス以上の高磁力選別を行うことを特徴とする、〔１〕に記載のリチウムイオン二次電池からの有価物回収方法。
〔３〕上記破砕物に対する８０００ガウス以上の高磁力選別に先だって、破砕物に対して３０００ガウス以下の低磁力選別を行い、破砕物中から強磁性体である鉄系金属を分離し、該鉄系金属が分離された破砕物に対して、上記８０００ガウス以上の高磁力選別を行うことを特徴とする、〔１〕又は〔２〕に記載のリチウムイオン二次電池からの有価物回収方法。
〔４〕上記破砕物に対する８０００ガウス以上の高磁力選別に先だって、上記破砕、分級、低磁力選別を複数回繰り返して行うことを特徴とする、〔３〕に記載のリチウムイオン二次電池からの有価物回収方法。
〔５〕上記８０００ガウス以上の高磁力選別が、高磁気・高勾配磁界を有する分離装置を用いて行われることを特徴とする、〔１〕〜〔４〕のいずれかに記載のリチウムイオン二次電池からの有価物回収方法。
〔６〕上記８０００ガウス以上の高磁力選別が、表面に所要の高磁気・高勾配磁界を有するマグネットドラムと、該マグネットドラムに掛架されたベルトコンベアと、該ベルトコンベア上に上記破砕物を供給するフィーダとを備えてなる装置を用いて行われることを特徴とする、〔１〕〜〔５〕のいずれかに記載のリチウムイオン二次電池からの有価物回収方法。
In order to solve the above-described problems, the present invention is a method for recovering valuable materials from lithium ion secondary batteries according to the following [1] to [6].
[1] A lithium ion secondary battery is heated at a temperature of 300 ° C. or higher and then crushed, and the resulting crushed material is subjected to high magnetic force sorting of 8000 gauss or more to magnetize aluminum as a paramagnetic material. A method for recovering a valuable material from a lithium ion secondary battery, wherein copper, which is a diamagnetic material, is recovered as a non-magnetic material as a kimono.
[2] Prior to high magnetic force selection of 8000 gauss or more for the crushed material, the crushed material is sieved and classified, and high magnetic force selection of 8000 gauss or more is performed on the crushed material of 1.0 to 10.0 mm. The method for recovering valuable materials from the lithium ion secondary battery according to [1].
[3] Prior to high magnetic force selection of 8000 gauss or more for the crushed material, low magnetic force selection of 3000 gauss or less is performed on the crushed material, and iron-based metal as a ferromagnetic material is separated from the crushed material. The method for recovering a valuable material from a lithium ion secondary battery according to [1] or [2], wherein the high magnetic force sorting of 8000 Gauss or more is performed on the crushed material from which the system metal is separated.
[4] The lithium ion secondary battery according to [3], wherein the crushing, classification, and low magnetic force sorting are repeated a plurality of times prior to high magnetic force sorting of 8000 Gauss or more with respect to the crushed material. Valuables collection method.
[5] The lithium ion secondary battery according to any one of [1] to [4], wherein the high magnetic force selection of 8000 gauss or more is performed using a separation device having a high magnetic field and a high gradient magnetic field. How to recover valuable materials from secondary batteries.
[6] The high magnetic force sorting of 8000 gauss or more is performed by a magnet drum having a required high magnetic / high gradient magnetic field on the surface, a belt conveyor hung on the magnet drum, and the crushed material on the belt conveyor. The method for recovering a valuable material from a lithium ion secondary battery according to any one of [1] to [5], wherein the method is performed using an apparatus including a feeder to be supplied.
上記した本発明に係るリチウムイオン二次電池からの有価物回収方法によれば、リチウムイオン二次電池の形態、即ち電池セル、電池モジュール、そして電池パックを区別することなく処理することが可能となる。また、リチウムイオン二次電池から有価物、特に、アルミニウム、銅を簡易かつ効率的に回収することができる。 According to the valuable material recovery method from the lithium ion secondary battery according to the present invention described above, it is possible to process the lithium ion secondary battery without distinguishing the form of the battery, that is, the battery cell, the battery module, and the battery pack. Become. Further, valuable materials, particularly aluminum and copper, can be easily and efficiently recovered from the lithium ion secondary battery.
以下、上記した本発明に係るリチウムイオン二次電池からの有価物回収方法の実施の形態を、詳細に説明する。 Hereinafter, an embodiment of a method for recovering valuable materials from a lithium ion secondary battery according to the present invention will be described in detail.
リチウムイオン二次電池は、アルミニウム箔にリチウム、コバルト、ニッケルなどを塗布した正極、銅箔に黒鉛などを塗布した負極、電解液、セパレーターなどから構成されている。そして、上記正極と負極との間を、電解液中においてリチウムイオンが移動することで、電池としての役割を果たす。 A lithium ion secondary battery is composed of a positive electrode in which lithium, cobalt, nickel or the like is applied to an aluminum foil, a negative electrode in which graphite or the like is applied to a copper foil, an electrolyte, a separator, or the like. The lithium ion moves between the positive electrode and the negative electrode in the electrolytic solution, thereby serving as a battery.
リチウムイオン二次電池は、上記したように正極、負極、電解液、セパレーターなどで構成されているが、その形状は使用目的により異なる。特に電気自動車（ＥＶ）、プラグインハイブリッド車（ＰＨＶ）などの車載用に使用されるリチウムイオン二次電池は、ラミネート型、円筒型、角型などと数種類の電池セルがあり、また電池セルの集合体である電池モジュール、更には電池モジュールの集合体である電池パックも、電池メーカーや自動車メーカーによりその形状、大きさが大きく異なる。そのため、リチウムイオン二次電池からの有価物回収を行うにあたっては、これらの電池セル、電池モジュール、そして電池パックを、区別することなく処理することが可能な方法を確立する必要がある。 As described above, the lithium ion secondary battery is composed of a positive electrode, a negative electrode, an electrolytic solution, a separator, and the like, but the shape varies depending on the purpose of use. In particular, lithium ion secondary batteries used in vehicles such as electric vehicles (EV) and plug-in hybrid vehicles (PHV) have several types of battery cells such as laminate type, cylindrical type, and square type. The shape and size of battery modules that are aggregates and battery packs that are aggregates of battery modules vary greatly depending on the battery manufacturer and automobile manufacturer. Therefore, when recovering valuable materials from a lithium ion secondary battery, it is necessary to establish a method capable of processing these battery cells, battery modules, and battery packs without distinction.
本発明に係るリチウムイオン二次電池からの有価物回収方法は、ＰＣ、携帯電話などに使用される小型リチウムイオン二次電池の他に、上記したＥＶ、ＰＨＶなどの車載用に使用される大型リチウムイオン二次電池について、電池パック或いは電池モジュールごと、３００℃以上の温度で先ず加熱し、次に破砕した後、得られた破砕物に対して８０００ガウス以上の高磁力選別を行い、常磁性体であるアルミニウムを磁着物として、反磁性体である銅を非磁着物として回収するものである。即ち、加熱工程、破砕工程、そして高磁力選別工程を少なくとも含み、必要に応じて更に他の工程を含むものである。
以下、上記した各工程について、詳述する。
The valuable material recovery method from the lithium ion secondary battery according to the present invention is not limited to the small lithium ion secondary battery used for PCs, mobile phones, etc., but is also used for large vehicles used for in-vehicle use such as EVs and PHVs. For lithium ion secondary batteries, each battery pack or battery module is first heated at a temperature of 300 ° C. or higher and then crushed, and the resulting crushed material is subjected to high magnetic force selection of 8000 gauss or more to obtain paramagnetic properties. Aluminum, which is a body, is recovered as a magnetic product, and copper, which is a diamagnetic material, is recovered as a non-magnetic material. That is, it includes at least a heating step, a crushing step, and a high magnetic force selection step, and further includes other steps as necessary.
Hereinafter, each process described above will be described in detail.
−加熱工程−
加熱工程としては、リチウムイオン二次電池を、電池セル、電池モジュール、そして電池パックを区別することなく、３００℃以上の温度で加熱することができれば、その加熱手段、加熱雰囲気などに特に制限はなく、目的に応じて適宜選択することができる。
リチウムイオン二次電池を、３００℃以上の温度で加熱することで、該電池中に含まれる電解液などの有害物質の除去及び無害化、そして、セパレーターなどの可燃物の除去を実施する。なお、加熱温度が５５０℃を超えると、正極集電体としてのアルミニウム箔及び負極集電体としての銅箔の少なくとも一部が酸化されて脆い酸化アルミニウム、酸化銅になる虞があるため、窒素ガス、アルゴンガス、ＣＯ、ＣＯ2などのガスを通風させて、非酸化雰囲気、還元性雰囲気下において加熱を行うことが好ましい。かかる観点及び経済性の観点から、前記加熱温度は、４００〜６００℃とすることが好ましく、かかる温度条件の下で加熱処理されたリチウムイオン二次電池は、正極集電体としてのアルミニウム箔、負極集電体としての銅箔が、ともに溶融することなく箔形状を維持したまま、後工程に移行されることとなる。
-Heating process-
As a heating process, if the lithium ion secondary battery can be heated at a temperature of 300 ° C. or higher without distinguishing battery cells, battery modules, and battery packs, there are no particular restrictions on the heating means, heating atmosphere, etc. And can be appropriately selected according to the purpose.
By heating the lithium ion secondary battery at a temperature of 300 ° C. or higher, harmful substances such as an electrolyte contained in the battery are removed and detoxified, and combustibles such as a separator are removed. If the heating temperature exceeds 550 ° C., at least part of the aluminum foil as the positive electrode current collector and the copper foil as the negative electrode current collector may be oxidized to become brittle aluminum oxide or copper oxide. It is preferable to perform heating in a non-oxidizing atmosphere and a reducing atmosphere by passing a gas such as gas, argon gas, CO, or CO 2 . From this viewpoint and economical viewpoint, the heating temperature is preferably 400 to 600 ° C., and the lithium ion secondary battery heat-treated under such a temperature condition includes an aluminum foil as a positive electrode current collector, The copper foil as the negative electrode current collector is transferred to the subsequent step while maintaining the foil shape without melting together.
ここで、上記加熱温度とは、加熱時のリチウムイオン二次電池周辺の気体の温度をいい、例えば、加熱時の加熱炉内においてリチウムイオン二次電池が置かれた付近の気体の温度をいう。また前記加熱の時間としては、特に制限はないが、リチウムイオン二次電池の形状や大きさに応じて適宜選択し、０．５時間〜６時間の範囲内で行うことが好ましく、１時間〜４時間の範囲内で行うことがより好ましい。 Here, the heating temperature refers to the temperature of the gas around the lithium ion secondary battery during heating, for example, the temperature of the gas in the vicinity where the lithium ion secondary battery is placed in the heating furnace during heating. . The heating time is not particularly limited, but is appropriately selected according to the shape and size of the lithium ion secondary battery, and is preferably performed within a range of 0.5 to 6 hours. It is more preferable to carry out within the range of 4 hours.
上記リチウムイオン二次電池の加熱は、炉を用いて行うことができ、炉としては、特に制限はないが、ロータリーキルン炉、流動床炉、トンネル炉、マッフル等のバッチ式炉、キュウポラ炉、ストーカー炉などを用いることができる。 The lithium ion secondary battery can be heated using a furnace, and the furnace is not particularly limited. However, a rotary kiln furnace, a fluidized bed furnace, a tunnel furnace, a muffled batch furnace, a cupola furnace, a stalker, etc. A furnace or the like can be used.
−破砕工程−
リチウムイオン二次電池からアルミニウム、銅などの有価物を効率的に回収するためには、構成する部品、元素の単体分離が必要であり、この単体分離を促進することを目的に、加熱したリチウムイオン二次電池の破砕を行う。
この破砕工程は、上記したように単体分離を促進することを目的とするものであることから、効率的に構成する部品、元素の単体分離を図るために、少なくとも破砕工程を実施することとし、必要に応じて、多段階の破砕を行うとともに、その間に分級、低磁力選別等の単体分離した成分の分離を行い、後工程である高磁力選別工程に適した破砕物とする。
この単体分離を目的とした破砕工程として、２段階で破砕を行うとともに、その間に分級工程及び低磁力選別工程を実施する形態について、以下に説明する。
-Shredding process-
In order to efficiently recover valuable materials such as aluminum and copper from lithium ion secondary batteries, it is necessary to separate the constituent parts and elements, and heated lithium for the purpose of promoting this separation. Crush the ion secondary battery.
Since this crushing process is intended to promote simple substance separation as described above, at least the crushing process is to be carried out in order to achieve simple separation of the components and elements that constitute efficiently. If necessary, multi-stage crushing is performed, and in the meantime, single separated components such as classification and low magnetic force separation are separated to obtain a crushed material suitable for a high magnetic force sorting step which is a subsequent process.
As a crushing process for the purpose of this simple substance separation, a mode in which crushing is performed in two stages and a classification process and a low magnetic force selection process are performed between them will be described below.
ａ．一次破砕工程
この一次破砕工程は、強固なリチウムイオン二次電池の筺体を破壊するとともに、正極集電体としてのアルミニウム箔や負極集電体としての銅箔に塗布されているコバルト、ニッケルなどの極材成分を剥がすことを目的として実施される。この一次破砕の目的を達成できるものであれば、その破砕手法、破砕粒径は問わないが、例えば、攪拌効果を持つ剪断式の破砕設備を用いて、目標平均破砕粒径１０．０〜２０．０ｍｍで行うことができる。この加熱後の破砕では、リチウムイオン二次電池をそのまま直接破砕するのではなく、３００℃以上の加熱により脆くなり、かつ重量が減っているリチウムイオン二次電池を破砕するものであるため、破砕の負担が軽減されている。また加熱物はその殆どが金属であり、破砕が困難な炭素、有機物がほとんどなくなっており、また部品は熱膨張により物理的に剥離・分解されているために、この面でも破砕の負担が軽減される。
a. Primary crushing process This primary crushing process destroys a strong lithium-ion secondary battery housing, and is applied to aluminum foil as a positive electrode current collector or copper foil applied to a copper foil as a negative electrode current collector. It is carried out for the purpose of peeling off the polar material components. As long as the purpose of the primary crushing can be achieved, the crushing technique and the crushing particle diameter are not limited. For example, the target average crushing particle diameter is 10.0 to 20 using a shearing crushing equipment having a stirring effect. 0.0 mm. In this crushing after heating, the lithium ion secondary battery is not directly crushed as it is, but it crushes a lithium ion secondary battery that becomes brittle and decreases in weight when heated at 300 ° C. or higher. The burden of is reduced. Most of the heated products are metal, carbon and organic materials that are difficult to crush are almost gone, and the parts are physically peeled and decomposed by thermal expansion. Is done.
ｂ．一次分級工程
上記一次破砕工程により、正極集電体としてのアルミニウム箔や負極集電体としての銅箔から剥がされた極材成分であるコバルト、ニッケルなどの粉体物を分離することを目的に、分級を行う。この分級は、本発明者等の検証では、ＪＩＳ Ｚ ８８０１規格に基づいた目開き１．０ｍｍの篩を用いて破砕物を分級することで、篩下にアルミニウム箔や銅箔から剥がされた極材成分が、篩上にその他の破砕物が分離することが判明している。ここで、回収される篩下の極材成分には、コバルト、ニッケル、リチウムを含む粉体物となり、これらの粉体物は、公知の精錬プロセスによって、それぞれ濃縮した状態で回収することができる。
b. Primary classification process For the purpose of separating powder materials such as cobalt and nickel, which are electrode material components peeled off from the aluminum foil as the positive electrode current collector and the copper foil as the negative electrode current collector, by the primary crushing process. Classify. In the classification by the present inventors, this classification is performed by classifying crushed materials using a sieve having an opening of 1.0 mm based on JIS Z 8801 standard, so that the pole peeled off from the aluminum foil or copper foil under the sieve. It has been found that the material component separates other crushed material on the sieve. Here, the recovered pole material component is a powder containing cobalt, nickel, and lithium, and these powder can be recovered in a concentrated state by a known refining process. .
ｃ．一次選別工程
上記分級工程で得た１．０ｍｍの篩上産物から、リチウムイオン二次電池の構成物質である筺体や鉄系部品等の強磁性体である鉄系金属の破砕物を磁力選別により分離を行う。ここでは主にリチウムイオン二次電池の強磁性体、即ち鉄系や磁性のあるＳＵＳ製の部品及び筐体の破砕物の分離を目的としており、３０００ガウス以下、好ましくは１００〜１５００ガウスの低磁力の磁力選別で、その分離が可能である。この低磁力選別を行う装置としては、例えば、選別面を磁束密度３００ガウスに調節した吊下げ式磁力選別設備を用いて行うことができる。
なお、現在、市場に流通している大型のリチウムイオン二次電池の多くは、筐体や部品に鉄やＳＵＳ等の磁性素材を多く使用しているが、アルミニウム等の磁性を持たない筺体で構成されるリチウムイオン二次電池も存在し、今後このようなリチウムイオン二次電池も普及して行くことが予想される。これら非磁性体筺体や部品の破砕物の分離は、上記した低磁力を用いた磁力選別の代わりに、風力やエアーテーブル等の比重選別装置を用いることや、磁力選別設備と組み合わせることで対応が可能であるため、処理対象に応じて、この選別工程を実施する。
c. Primary screening process From the 1.0 mm sieve product obtained in the classification process, the ferrous metal crushed material, which is a ferromagnetic material such as a casing or iron-based component, which is a constituent material of a lithium ion secondary battery, is magnetically sorted. Perform separation. The purpose here is mainly for separation of ferromagnetic materials of lithium ion secondary batteries, that is, iron-based or magnetic SUS parts and casing crushed materials, which are as low as 3000 gauss or less, preferably as low as 100 to 1500 gauss. Separation is possible by magnetic separation of magnetic force. As an apparatus for performing this low magnetic force sorting, for example, it is possible to use a suspended magnetic sorting facility whose sorting surface is adjusted to a magnetic flux density of 300 gauss.
Currently, many large-sized lithium ion secondary batteries on the market use a lot of magnetic materials such as iron and SUS for casings and parts. There are lithium ion secondary batteries that are configured, and it is expected that such lithium ion secondary batteries will become widespread in the future. Separation of crushed materials of these non-magnetic bodies and parts can be handled by using a specific gravity sorting device such as a wind or air table instead of the above-mentioned magnetic sorting using low magnetic force, or by combining with magnetic sorting equipment. Since this is possible, this sorting step is performed according to the processing target.
ｄ．二次破砕工程
上記低磁力を用いた選別工程により分離した非磁着物、即ち、主にアルミニウム箔と銅箔の破砕物を、後工程である本発明の最大の特徴部分である高磁力を用いたアルミニウムと銅との選別工程での分離効率を向上させることを目的に、再度破砕処理を施す。この二次破砕工程における破砕方式は、上記した一次破砕工程と同様に、その破砕方式を問わないが、アルミニウム箔や銅箔に塗布されているコバルト、ニッケルなどの極材成分をより効率良く剥がすため、またアルミニウム箔、銅箔自体をも細かく破砕するために、原料が撹拌され擦られる効果を持つ高速回転式の剪断式破砕手法を選択することが好ましい。かかる効果的な破砕手法を備える破砕装置としては、例えば、破砕室内に設置された回転破砕刃が、該破砕刃の真下にある交換可能なスクリーンを通過する寸法になるまで破砕原料を再循環しながら破砕処理を行う、剪断式破砕機を挙げることができる。
d. Secondary crushing process Non-magnetized material separated by the sorting process using the low magnetic force, that is, mainly the crushed material of aluminum foil and copper foil, uses the high magnetic force which is the greatest characteristic part of the present invention which is the subsequent process. The crushing process is performed again for the purpose of improving the separation efficiency in the sorting process of aluminum and copper. The crushing method in this secondary crushing step is not limited to the crushing method, as in the above-described primary crushing step, but more effectively strips the polar material components such as cobalt and nickel applied to the aluminum foil and copper foil. Therefore, in order to finely crush the aluminum foil and the copper foil itself, it is preferable to select a high-speed rotary shearing crushing method having an effect that the raw material is stirred and rubbed. As a crushing apparatus equipped with such an effective crushing method, for example, the crushing raw material is recirculated until the rotary crushing blade installed in the crushing chamber reaches a size that passes through a replaceable screen directly below the crushing blade. A shearing type crusher that performs crushing treatment can be given.
この二次破砕工程における破砕粒径は、上記した単体分離の目的が達成でき、かつ、後の高磁力を用いた選別工程におけるアルミニウム、銅の選別の容易性および収率性を考慮し、適宜決定されることとなるが、本発明者等の検証では、平均破砕粒径を１０ｍｍ以下とすることが好ましく、３．０〜７．０ｍｍの範囲内とすることがより好ましいことが判明している。 The crushing particle size in this secondary crushing process can be achieved as appropriate in consideration of the ease of the separation of aluminum and copper and the yield in the subsequent cleaving process using high magnetic force. Although it will be determined, in the verification by the present inventors, it has been found that the average crushed particle size is preferably 10 mm or less, and more preferably within the range of 3.0 to 7.0 mm. Yes.
ｅ．二次分級工程
上記二次破砕工程を経た破砕物に対し、後工程の高磁力を用いた選別に適した粒度帯のものとするために、分級を実施する。本発明者等の検証では、ＪＩＳ Ｚ ８８０１規格に基づいた篩いを用い、１０．０ｍｍを超える破砕物と、１．０〜１０．０ｍｍの破砕物と、１．０ｍｍに満たない破砕物とに篩分けすることが、有価物の選別、特にアルミニウム、銅、コバルトなどの選別に適していることが判明している。これは、１０ｍｍを超える破砕物は、アルミニウム箔と銅箔との単体分離が不十分であり、アルミニウム箔に包まれる形で銅箔が混在しており、高磁力選別でも、これらを分離・回収することが困難である。この１０ｍｍを超える破砕物に関しては、再度破砕工程に戻すことにより、アルミニウムと銅の回収率を向上させることが可能である。１．０〜１０．０ｍｍの中間物に対しては、アルミニウムと銅とを高磁力選別により効率的に分離・回収することができ、１．０ｍｍに満たない破砕物中には、コバルト、ニッケルなどの極材成分が濃縮されている。
e. Secondary classification step For the crushed material that has undergone the secondary crushing step, classification is carried out in order to obtain a particle size suitable for sorting using high magnetic force in the subsequent step. In verification by the present inventors, a sieve based on the JIS Z 8801 standard was used, and a crushed material exceeding 10.0 mm, a crushed material of 1.0 to 10.0 mm, and a crushed material less than 1.0 mm. It has been found that sieving is suitable for sorting valuable materials, particularly for sorting aluminum, copper, cobalt and the like. This is because crushed material exceeding 10 mm is insufficiently separated into aluminum foil and copper foil, and copper foil is mixed in the form of being wrapped in aluminum foil. Difficult to do. About the crushed material exceeding 10 mm, it is possible to improve the recovery rate of aluminum and copper by returning to the crushing process again. For intermediates of 1.0 to 10.0 mm, aluminum and copper can be efficiently separated and recovered by high magnetic sorting, and in crushed materials less than 1.0 mm, cobalt and nickel The extreme ingredients such as are concentrated.
ｆ．二次選別工程
上記分級工程で分級した１．０〜１０．０ｍｍの破砕物に対し、後の高磁力選別に用いる装置の保全を目的として、先の低磁力を用いた一次選別工程にて分離できなかった残存する強磁性体である鉄系金属の分離を行う。この二次選別に用いる装置としては、上記一次選別と同様に、３０００ガウス以下、好ましくは３００〜１５００ガウスの低磁力の磁力選別で分離が可能である。この低磁力選別を行う装置としては、例えば、ドラムの表面磁束密度が１０００ガウス程度としてあるドラム式磁力選別設備を用いて行うことができる。
また、当工程は、上記したように後工程の設備保全を目的として行うものであるため、磁着物である鉄系金属の形状が塊状である場合には、箔形状のアルミニウム、銅から、例えば風力やエアーテーブルのような形状選別技術と組み合わせることで、より効果的な分離が可能となるため、その組み合わせの選別方法を採用することは好ましい。
f. Secondary sorting step The crushed material of 1.0-10.0 mm classified in the above classification step is separated in the primary sorting step using the previous low magnetic force for the purpose of maintaining the equipment used for the subsequent high magnetic force sorting. Separation of the iron-based metal which is the remaining ferromagnetic material that could not be performed. The apparatus used for the secondary sorting can be separated by magnetic sorting with a low magnetic force of 3000 gauss or less, preferably 300 to 1500 gauss, as in the primary sorting. As an apparatus for performing this low magnetic force sorting, for example, a drum type magnetic sorting device having a drum surface magnetic flux density of about 1000 gauss can be used.
Moreover, since this process is performed for the purpose of equipment maintenance in the subsequent process as described above, when the shape of the iron-based metal that is a magnetic deposit is a lump, from foil-shaped aluminum, copper, for example, Since a more effective separation becomes possible by combining with a shape selection technique such as wind power or an air table, it is preferable to employ a combination selection method.
上記した一次破砕工程（ａ）〜二次選別工程（ｆ）までの一連の工程は、加熱処理されたリチウムイオン二次電池に対し、構成する部品、元素の単体分離を図るとともに、後工程である高磁力選別工程に適した破砕物とすることを目的として成された破砕工程の一例として記載したものであり、何らこれらの一連の工程に限定されるものではない。例えば、処理対象であるリチウムイオン二次電池、また破砕設備によっては、上記した多段階の破砕を行うことなく、１段の破砕工程で良い場合があり、また分級工程も、コバルトなどの極材成分が濃縮されている１．０ｍｍに満たない破砕物と、それ以上との分級のみを行えば良い場合がある。更に、使用する高磁力選別機によっては、事前の強磁性体である鉄系金属の選別工程が不要となる場合もある。 The series of steps from the primary crushing step (a) to the secondary sorting step (f) described above is intended to separate constituent components and elements from the heat-treated lithium ion secondary battery, and in a subsequent step. It is described as an example of a crushing process for the purpose of obtaining a crushed material suitable for a certain high magnetic force sorting process, and is not limited to a series of these processes. For example, depending on the lithium ion secondary battery to be treated and the crushing equipment, a single crushing process may be used without performing the multistage crushing described above, and the classification process may also be an extreme material such as cobalt. In some cases, it is only necessary to classify the crushed material having a concentration of less than 1.0 mm and the crushed material. Furthermore, depending on the high magnetic force sorter to be used, there is a case where a sorting step of a ferrous metal that is a prior ferromagnetic material becomes unnecessary.
−高磁力選別工程−
上記加熱工程、破砕工程、必要に応じて多段階の破砕を行うとともに、その間に分級、選別等の単体分離した成分の分離工程を実施した破砕物、具体的には、強磁性金属が取り除かれ、１．０〜１０．０ｍｍに分級されたリチウムイオン二次電池の破砕物に対し、８０００ガウス以上、好ましくは１００００ガウス以上の高磁力選別を行い、常磁性体であるアルミニウムを磁着物として、反磁性体である銅を非磁着物として回収する。
-High magnetic force sorting process-
The above-mentioned heating process, crushing process, and multistage crushing as necessary, while the crushed material, specifically the ferromagnetic metal, is removed during the separation process of the separated components such as classification and sorting. The crushed material of the lithium ion secondary battery classified into 1.0 to 10.0 mm is subjected to high magnetic force selection of 8000 gauss or more, preferably 10000 gauss or more, and aluminum as a paramagnetic material is used as a magnetized product. Copper, which is a diamagnetic material, is recovered as a non-magnetic product.
この高磁力選別工程において使用する高磁力選別機の模式図を、図１に示す。
この高磁力選別機は、高磁力、高勾配磁気、詳しくは、２０，０００ガウス（理論磁束密度最高値）もの強力な磁場が局所的に存在するマグネットドラムと、該マグネットドラムに掛架されたベルトコンベアと、該ベルトコンベア上に分離対象物を供給するフィーダとを有する分離装置であり、フィーダにより供給された分離対象物をベルトコンベアにより搬送し、マグネットドラム上を通過させ、磁着物と非磁着物の分離を行う装置である。
本発明にかかる有価物回収方法おいては、図１に示したように、アルミニウムと銅とが混在する破砕物をベルトコンベアにより搬送させ、そして、常磁性体であるアルミニウムはマグネットドラムの磁場により磁着され、マグネットドラムの磁場の影響がなくなるまでベルトコンベア上にはり付いた状態で流れ、その磁場の影響が無くなった位置で自重により落下する。一方、反磁性体である銅は、マグネットドラムの磁場に対する反撥力と回転するベルトコンベアによる慣性力により、早い時期においてベルトコンベアから落下し、明確にアルミニウムとは選別される。
A schematic diagram of a high magnetic force sorter used in this high magnetic force sorting step is shown in FIG.
This high magnetic force sorter is a high magnetic force, high gradient magnetic field, more specifically, a magnet drum having a strong magnetic field of 20,000 gauss (maximum theoretical magnetic flux density) locally, and is suspended on the magnet drum. A separation device having a belt conveyor and a feeder for supplying a separation object on the belt conveyor. The separation object supplied by the feeder is conveyed by the belt conveyor and passed on a magnetic drum so that the magnetic material and It is an apparatus for separating magnetic deposits.
In the valuable material recovery method according to the present invention, as shown in FIG. 1, a crushed material in which aluminum and copper are mixed is conveyed by a belt conveyor, and aluminum which is a paramagnetic material is caused by a magnetic field of a magnet drum. It is magnetically attached and flows on the belt conveyor until it is no longer affected by the magnetic field of the magnetic drum, and falls by its own weight at a position where the influence of the magnetic field is eliminated. On the other hand, copper, which is a diamagnetic material, falls from the belt conveyor at an early stage due to the repulsive force against the magnetic field of the magnet drum and the inertial force of the rotating belt conveyor, and is clearly separated from aluminum.
この高磁力を用いた磁力選別によれば、『形状』、『密度』、『粒度』等の複数の因子に影響されながら分離を行う比重選別や、少なくとも『形状』と『元素としての特性』に影響を受ける先に先行技術として挙げた渦電流を利用した選別方法とは異なり、アルミニウムと銅との磁性の違い、即ち、『元素としての特性』のみによってその選別が成されるものとなる。そのために、これまで解決が困難であった箔と言う『形状』の因子の不確定さの影響を受けていた渦電流を利用した選別と比較し、この高磁力選別は、磁着物としてアルミニウムを、非磁着物として銅を、高効率で分離し、それぞれを濃縮することが可能となる。 According to the magnetic selection using this high magnetic force, the specific gravity selection that performs separation while being influenced by multiple factors such as “shape”, “density”, “grain size”, and at least “shape” and “element characteristics” Unlike the sorting method using eddy currents, which was previously mentioned as a prior art, the sorting is made only by the difference in magnetism between aluminum and copper, that is, “elemental characteristics”. . For this reason, compared with sorting using eddy currents, which has been affected by the uncertainty of the “shape” factor called foil, which has been difficult to solve up to now, this high magnetic force sorting uses aluminum as a magnetic deposit. It becomes possible to separate copper as non-magnetic deposits with high efficiency and concentrate each of them.
ここで、８０００ガウス以上の高磁力を用いるとしたのは、いずれも弱磁性体であるアルミニウムと銅に、磁性の違いに基づいたマグネットドラムに対する吸着力の差異を明確に発現させるためであり、この場合、反磁性体である銅はマグネットドラムに吸着せず、常磁性体であるアルミニウムは微弱ではあるがマグネットドラムに吸着するものとなる。かかる観点から、磁力選別するにあたって１００００ガウス以上の高磁力を用いることはより好ましい。 Here, the reason why a high magnetic force of 8000 gauss or more is used is to clearly express the difference in attractive force with respect to the magnet drum based on the difference in magnetism between aluminum and copper, which are both weak magnetic materials, In this case, copper, which is a diamagnetic material, is not attracted to the magnet drum, and aluminum, which is a paramagnetic material, is weak but is attracted to the magnet drum. From this point of view, it is more preferable to use a high magnetic force of 10,000 gauss or more for magnetic selection.
本発明者等の検証では、上記した高磁力を用いた選別によって、アルミニウムと銅とを、それぞれ７０％以上の品位と回収率で濃縮、分離回収することができることが判明している。
なお、銅濃縮物中のアルミニウムを更に調査したところ、ラミネート型セル特有のアルミニウム圧着部材が多く混在していた。これは部材重量が高磁力選別機の磁界の影響よりも、重力の影響が大きいために混在してしまったと推察される。これらの圧着部材は、例えばエアーテーブルのような比重選別設備により分離可能であるため、上記した高磁力選別工程の前或いは後工程として、エアーテーブルを用いた比重選別を行うことにより、更なる品位の向上を図ることができる。
In the verification by the present inventors, it has been found that aluminum and copper can be concentrated, separated and recovered at a quality and recovery rate of 70% or more, respectively, by the above-described screening using high magnetic force.
In addition, when the aluminum in the copper concentrate was further investigated, many aluminum crimping members peculiar to the laminate type cell were mixed. This is presumed that the weight of the member is mixed because the influence of gravity is larger than the influence of the magnetic field of the high magnetic separator. Since these crimping members can be separated by specific gravity sorting equipment such as an air table, for example, by performing specific gravity sorting using an air table before or after the above high magnetic force sorting process, further quality is achieved. Can be improved.
リチウムイオン二次電池であるラミネート型電池セルの集合体からなる車載用電池モジュールに対し、本発明に係る有価物回収方法に従い、銅とアルミニウムの分離を行った。 Copper and aluminum were separated from an in-vehicle battery module made of an assembly of laminated battery cells, which are lithium ion secondary batteries, according to the valuable material recovery method according to the present invention.
先ず、車載用モジュールを４００〜６００℃の熱風を発生させることが可能な熱風式加熱炉を用い、３時間の加熱処理を施した。この際、アルミニウムの酸化を防止するためにＮ2ガスにより炉内を置換して実施した。
この加熱処置を施した電池モジュールを、攪拌効果を持ち、且つ、強固な筐体を破砕可能な剪断式破砕装置により破砕し、得られた破砕物に対してＪＩＳ Ｚ ８８０１規格に基づいた目開き１．０ｍｍの篩により分級した。
First, the in-vehicle module was subjected to heat treatment for 3 hours using a hot air heating furnace capable of generating 400 to 600 ° C. hot air. At this time, in order to prevent oxidation of aluminum, the inside of the furnace was replaced with N 2 gas.
The battery module subjected to the heat treatment is crushed by a shearing crushing device having a stirring effect and capable of crushing a strong casing, and the resulting crushed material is based on the JIS Z 8801 standard. Classification was performed with a 1.0 mm sieve.
先の分級工程により得られた１．０ｍｍを超える篩上産物に対し、磁束密度３００Ｇの吊下げ式磁力選別設備を用いて磁着成分である筐体破砕物と鉄系部品の除去を行った。 With respect to the sieved product exceeding 1.0 mm obtained in the previous classification process, the crushed case and iron-based parts, which are magnetic components, were removed using a suspension type magnetic separator having a magnetic flux density of 300 G. .
リチウムイオン二次電池を破砕することで得られた銅箔とアルミニウム箔の単体分離状況、再破砕の最適粒度を調査することを目的に、先の工程により得られた非磁着成分のサンプルを採取、分級処理を行い、それぞれの粒度帯で高磁力選別（図１に示した理論磁束密度最高値が２０，０００ガウスの高磁気・高勾配磁界を有する分離装置使用）を実施した。
得られた濃縮物中の銅とアルミニウムを分析し、比率でまとめたものを表１に示す。
Table 1 shows the results of analyzing copper and aluminum in the resulting concentrate and summarizing them by ratio.
表１から、粒度が大きい程、各濃縮物の品位が悪化していることが分かる。また、各分離物の重量比率をみると、分離効率の悪い条件ほど、アルミニウム濃縮物の重量比が上昇していることが分かる。これは、分離効率の悪い条件下では、銅箔がアルミニウム濃縮物側に混入していること示している。この現象と各濃縮物の外観から、粒度の大きい条件下では、アルミニウム箔と銅箔の単体分離が不十分であり、アルミニウム箔に包まれる形で銅箔が混入していると考えられる。
２．０〜３．０ｍｍに関しては、粒子が細かくなってしまったため、正極材成分であるコバルトやニッケル等が箔に付着し、磁力を帯びてしまい、アルミニウム濃縮物側に移動してしまったと推察される。これは、分級精度を向上させることにより、解決は可能である。
上記のことから、リチウムイオン二次電池の破砕物中のから銅箔とアルミニウム箔を効率良く分離するためには、単体分離が十分に行われるまで破砕を行う必要があり、その粒度は１０．０ｍｍ以下、望ましくは３．０〜７．０ｍｍの範囲になるように設定する必要がある。同時に、粒度帯が小さくなると正極材成分の磁性物が箔に付着してしまうため、粉砕・分級手法を十分に制御する必要がある。
From Table 1, it can be seen that the greater the particle size, the worse the quality of each concentrate. Moreover, when the weight ratio of each isolate | separation thing is seen, it turns out that the weight ratio of an aluminum concentrate is increasing, so that the conditions where separation efficiency is bad. This indicates that the copper foil is mixed on the aluminum concentrate side under the condition of poor separation efficiency. From this phenomenon and the appearance of each concentrate, it is considered that the single separation of the aluminum foil and the copper foil is insufficient under conditions with a large particle size, and the copper foil is mixed in a form wrapped in the aluminum foil.
About 2.0-3.0mm, since the particles became fine, it was speculated that the positive electrode material components such as cobalt and nickel adhered to the foil, became magnetic, and moved to the aluminum concentrate side. Is done. This can be solved by improving the classification accuracy.
From the above, in order to efficiently separate the copper foil and the aluminum foil from the crushed material of the lithium ion secondary battery, it is necessary to crush until the single separation is sufficiently performed. It is necessary to set it to be in the range of 0 mm or less, desirably 3.0 to 7.0 mm. At the same time, since the magnetic material of the positive electrode material component adheres to the foil when the particle size band becomes small, it is necessary to sufficiently control the pulverization / classification method.
上記〔００３４〕段の低磁力選別で残された非磁着物は、先の調査内容を考慮し、平均粒度が３．０〜７．０ｍｍの範囲になるよう、高速回転式の剪断式破砕装置により二次破砕処理を施した後、ＪＩＳ Ｚ ８８０１規格に基づいた目開き１．０ｍｍと１０．０ｍｍの篩により分級した。 The non-magnetized material left by the low magnetic force sorting in the above [0034] stage is a high-speed rotary shearing crusher so that the average particle size is in the range of 3.0 to 7.0 mm in consideration of the contents of the previous investigation. Then, after the secondary crushing treatment, classification was performed with a sieve having an opening of 1.0 mm and 10.0 mm based on JIS Z 8801 standard.
分級した１０．０ｍｍを超える篩上産物は、１．０ｍｍと１０．０ｍｍの篩中間物と同程度の粒度帯になるまで再度破砕処理を行い、改めて分級を行い、１．０ｍｍ以下の極材成分と、その他再破砕物を得た。
再破砕物は先に得た１．０ｍｍと１０．０ｍｍの篩中間物と混ぜ、次工程の低磁力選別により、磁着物を更に分離した。
分離した非磁着物は、高磁力選別（図１に示した理論磁束密度最高値が２０，０００ガウスの高磁気・高勾配磁界を有する分離装置使用）により、アルミニウム箔と銅箔の分離を行った。
The classified product on the sieve exceeding 10.0 mm is crushed again until it has a particle size band similar to the intermediate size of 1.0 mm and 10.0 mm, classified again, and the pole material of 1.0 mm or less Ingredients and other re-crushed materials were obtained.
The re-crushed material was mixed with the previously obtained 1.0 mm and 10.0 mm sieve intermediates, and the magnetic deposits were further separated by low-magnetization sorting in the next step.
The separated non-magnetized material is separated into aluminum foil and copper foil by high magnetic force sorting (using a separator having a high magnetic and high gradient magnetic field with a maximum theoretical magnetic flux density of 20,000 gauss shown in FIG. 1). It was.
得られた分離物の銅、アルミニウムの分析値を表２に、それぞれのマテリアルバランスを表３に記載する。
表２、表３から、アルミニウムと銅を、それぞれ７０％以上の品位と回収率で濃縮、分離することができることが分かる。 From Tables 2 and 3, it can be seen that aluminum and copper can be concentrated and separated with a quality and recovery rate of 70% or more, respectively.
本発明に係る技術は、リチウムイオン二次電池の形態、即ち電池セル、電池モジュール、そして電池パックを区別することなく実施可能な方法であり、今後市場の拡大が見込まれる車載用や産業用の大型リチウムイオン二次電池からの有価物回収方法として好適に利用することができる。 The technology according to the present invention is a method that can be implemented without distinguishing the form of a lithium ion secondary battery, that is, a battery cell, a battery module, and a battery pack. It can be suitably used as a valuable material recovery method from a large-sized lithium ion secondary battery.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014100081A JP6469362B2 (en) | 2014-05-14 | 2014-05-14 | Method for recovering valuable materials from lithium ion secondary batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014100081A JP6469362B2 (en) | 2014-05-14 | 2014-05-14 | Method for recovering valuable materials from lithium ion secondary batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2015219948A true JP2015219948A (en) | 2015-12-07 |
| JP6469362B2 JP6469362B2 (en) | 2019-02-13 |
Family
ID=54779192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014100081A Active JP6469362B2 (en) | 2014-05-14 | 2014-05-14 | Method for recovering valuable materials from lithium ion secondary batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6469362B2 (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6198027B1 (en) * | 2017-01-24 | 2017-09-20 | 三菱マテリアル株式会社 | How to recover valuable materials from used lithium ion batteries |
| JP2017174517A (en) * | 2016-03-18 | 2017-09-28 | 三菱マテリアル株式会社 | Method for collecting valuable substance from used lithium ion battery |
| CN107492695A (en) * | 2017-07-17 | 2017-12-19 | 中航锂电（洛阳）有限公司 | The separation method of positive/negative plate in a kind of lithium ion battery removal process |
| JP2018026279A (en) * | 2016-08-10 | 2018-02-15 | 太平洋セメント株式会社 | Method for recovery of valuables from wasted lithium ion battery, and method for preparing data base |
| CN107946686A (en) * | 2017-11-09 | 2018-04-20 | 合肥国轩高科动力能源有限公司 | Waste lithium ion battery recovery method |
| JP2018159477A (en) * | 2017-03-22 | 2018-10-11 | 太平洋セメント株式会社 | Treatment method of waste lithium-ion battery |
| JP2020061297A (en) * | 2018-10-11 | 2020-04-16 | Ｄｏｗａエコシステム株式会社 | Method of recovering valuable material from lithium ion secondary battery |
| JP2020069406A (en) * | 2018-10-29 | 2020-05-07 | 太平洋セメント株式会社 | Processing device and processing method of metal-containing waste |
| WO2021157483A1 (en) * | 2020-02-06 | 2021-08-12 | Ｄｏｗａエコシステム株式会社 | Separation method for valuable resources |
| JP2021133346A (en) * | 2020-02-28 | 2021-09-13 | 太平洋セメント株式会社 | Chromium reduction method for mix metal |
| CN114006066A (en) * | 2020-12-22 | 2022-02-01 | 深圳清研装备科技有限公司 | Method for separating and recovering anode and cathode mixed powder of waste ternary lithium ion battery |
| US11482737B2 (en) | 2020-01-03 | 2022-10-25 | Dowa Eco-System Co., Ltd. | Method for recovering valuable material from lithium ion secondary battery |
| JP7316411B1 (en) | 2022-04-19 | 2023-07-27 | 松田産業株式会社 | Method for collecting valuables from lithium ion secondary battery |
| WO2024090313A1 (en) * | 2022-10-25 | 2024-05-02 | Ｄｏｗａエコシステム株式会社 | Method for recovering valuable materials from lithium ion secondary batteries |
| US12107244B2 (en) | 2020-01-03 | 2024-10-01 | Dowa Eco-System Co., Ltd. | Method for recovering valuable material from lithium ion secondary battery |
| JP7571367B2 (en) | 2022-10-25 | 2024-10-23 | Ｄｏｗａエコシステム株式会社 | Method for recovering valuable materials from lithium-ion secondary batteries |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0741874A (en) * | 1993-07-26 | 1995-02-10 | Setsuichi Kasai | Method for recovering metal slag of waste |
| JPH1074539A (en) * | 1996-09-02 | 1998-03-17 | Nikko Kinzoku Kk | Method for recovering reusable material from used lithium battery |
| JPH11242967A (en) * | 1997-12-25 | 1999-09-07 | Nippon Mining & Metals Co Ltd | Method of recovering valuable material from used lithium battery |
| JPH11253889A (en) * | 1998-03-09 | 1999-09-21 | Dowa Mining Co Ltd | Method and device for recovering metal from solid waste |
| JP2001058138A (en) * | 1999-08-23 | 2001-03-06 | Nippon Mining & Metals Co Ltd | Treatment method for recycling waste of office automation equipment |
| JP2001179221A (en) * | 1999-12-22 | 2001-07-03 | Dowa Mining Co Ltd | Method and apparatus for segregated recovery of communication device and recovery substrate part |
| JP2001232340A (en) * | 2000-02-22 | 2001-08-28 | Ishikawajima Harima Heavy Ind Co Ltd | Method and device for treating dry distillation residue of shredder dust |
| JP2002194448A (en) * | 2000-12-28 | 2002-07-10 | Nippon Mining & Metals Co Ltd | Method for recovering metal from electronic or electric parts with resin |
| WO2007099714A1 (en) * | 2006-03-03 | 2007-09-07 | Ehime University | Method of recovering metal and high-gradient magnetic separator |
| JP2012079630A (en) * | 2010-10-05 | 2012-04-19 | Dowa Eco-System Co Ltd | Recovery method of valuables from lithium ion secondary battery and recovered material having valuables |
| JP2013004299A (en) * | 2011-06-16 | 2013-01-07 | Mitsubishi Materials Corp | Recycling method of lithium ion secondary battery |
| JP2013080595A (en) * | 2011-10-03 | 2013-05-02 | Dowa Eco-System Co Ltd | Method for recovering valuable from lithium ion secondary battery |
-
2014
- 2014-05-14 JP JP2014100081A patent/JP6469362B2/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0741874A (en) * | 1993-07-26 | 1995-02-10 | Setsuichi Kasai | Method for recovering metal slag of waste |
| JPH1074539A (en) * | 1996-09-02 | 1998-03-17 | Nikko Kinzoku Kk | Method for recovering reusable material from used lithium battery |
| JPH11242967A (en) * | 1997-12-25 | 1999-09-07 | Nippon Mining & Metals Co Ltd | Method of recovering valuable material from used lithium battery |
| JPH11253889A (en) * | 1998-03-09 | 1999-09-21 | Dowa Mining Co Ltd | Method and device for recovering metal from solid waste |
| JP2001058138A (en) * | 1999-08-23 | 2001-03-06 | Nippon Mining & Metals Co Ltd | Treatment method for recycling waste of office automation equipment |
| JP2001179221A (en) * | 1999-12-22 | 2001-07-03 | Dowa Mining Co Ltd | Method and apparatus for segregated recovery of communication device and recovery substrate part |
| JP2001232340A (en) * | 2000-02-22 | 2001-08-28 | Ishikawajima Harima Heavy Ind Co Ltd | Method and device for treating dry distillation residue of shredder dust |
| JP2002194448A (en) * | 2000-12-28 | 2002-07-10 | Nippon Mining & Metals Co Ltd | Method for recovering metal from electronic or electric parts with resin |
| WO2007099714A1 (en) * | 2006-03-03 | 2007-09-07 | Ehime University | Method of recovering metal and high-gradient magnetic separator |
| JP2012079630A (en) * | 2010-10-05 | 2012-04-19 | Dowa Eco-System Co Ltd | Recovery method of valuables from lithium ion secondary battery and recovered material having valuables |
| JP2013004299A (en) * | 2011-06-16 | 2013-01-07 | Mitsubishi Materials Corp | Recycling method of lithium ion secondary battery |
| JP2013080595A (en) * | 2011-10-03 | 2013-05-02 | Dowa Eco-System Co Ltd | Method for recovering valuable from lithium ion secondary battery |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017174517A (en) * | 2016-03-18 | 2017-09-28 | 三菱マテリアル株式会社 | Method for collecting valuable substance from used lithium ion battery |
| JP2018026279A (en) * | 2016-08-10 | 2018-02-15 | 太平洋セメント株式会社 | Method for recovery of valuables from wasted lithium ion battery, and method for preparing data base |
| US11088406B2 (en) | 2017-01-24 | 2021-08-10 | Mitsubishi Materials Corporation | Method for recovering valuable material from used lithium-ion battery |
| WO2018139445A1 (en) | 2017-01-24 | 2018-08-02 | 三菱マテリアル株式会社 | Method for recovering valuable material from used lithium-ion battery |
| JP2018120716A (en) * | 2017-01-24 | 2018-08-02 | 三菱マテリアル株式会社 | Method for recovering valuables from used lithium ion batteries |
| CN110199429A (en) * | 2017-01-24 | 2019-09-03 | 三菱综合材料株式会社 | From the method for the lithium ion battery recycling valuable material used |
| KR20190110543A (en) | 2017-01-24 | 2019-09-30 | 미쓰비시 마테리알 가부시키가이샤 | Valuables collection method from used lithium ion battery |
| JP6198027B1 (en) * | 2017-01-24 | 2017-09-20 | 三菱マテリアル株式会社 | How to recover valuable materials from used lithium ion batteries |
| JP7017860B2 (en) | 2017-03-22 | 2022-02-09 | 太平洋セメント株式会社 | How to dispose of waste lithium-ion batteries |
| JP2018159477A (en) * | 2017-03-22 | 2018-10-11 | 太平洋セメント株式会社 | Treatment method of waste lithium-ion battery |
| CN107492695A (en) * | 2017-07-17 | 2017-12-19 | 中航锂电（洛阳）有限公司 | The separation method of positive/negative plate in a kind of lithium ion battery removal process |
| CN107946686A (en) * | 2017-11-09 | 2018-04-20 | 合肥国轩高科动力能源有限公司 | Waste lithium ion battery recovery method |
| JP2020061297A (en) * | 2018-10-11 | 2020-04-16 | Ｄｏｗａエコシステム株式会社 | Method of recovering valuable material from lithium ion secondary battery |
| JP2020069406A (en) * | 2018-10-29 | 2020-05-07 | 太平洋セメント株式会社 | Processing device and processing method of metal-containing waste |
| US11482737B2 (en) | 2020-01-03 | 2022-10-25 | Dowa Eco-System Co., Ltd. | Method for recovering valuable material from lithium ion secondary battery |
| US12107244B2 (en) | 2020-01-03 | 2024-10-01 | Dowa Eco-System Co., Ltd. | Method for recovering valuable material from lithium ion secondary battery |
| JP2021123760A (en) * | 2020-02-06 | 2021-08-30 | Ｄｏｗａエコシステム株式会社 | Valuable material sorting method |
| WO2021157483A1 (en) * | 2020-02-06 | 2021-08-12 | Ｄｏｗａエコシステム株式会社 | Separation method for valuable resources |
| JP2021133346A (en) * | 2020-02-28 | 2021-09-13 | 太平洋セメント株式会社 | Chromium reduction method for mix metal |
| CN114006066A (en) * | 2020-12-22 | 2022-02-01 | 深圳清研装备科技有限公司 | Method for separating and recovering anode and cathode mixed powder of waste ternary lithium ion battery |
| CN114006066B (en) * | 2020-12-22 | 2024-03-15 | 深圳清研锂业科技有限公司 | Method for separating and recycling mixed powder of positive and negative electrodes of waste ternary lithium ion battery |
| JP7316411B1 (en) | 2022-04-19 | 2023-07-27 | 松田産業株式会社 | Method for collecting valuables from lithium ion secondary battery |
| WO2023204230A1 (en) * | 2022-04-19 | 2023-10-26 | 松田産業株式会社 | Method for recovering valuable materials from lithium-ion secondary battery |
| JP2023158921A (en) * | 2022-04-19 | 2023-10-31 | 松田産業株式会社 | Method for recovering valuable materials from lithium-ion secondary battery |
| WO2024090313A1 (en) * | 2022-10-25 | 2024-05-02 | Ｄｏｗａエコシステム株式会社 | Method for recovering valuable materials from lithium ion secondary batteries |
| JP7571367B2 (en) | 2022-10-25 | 2024-10-23 | Ｄｏｗａエコシステム株式会社 | Method for recovering valuable materials from lithium-ion secondary batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6469362B2 (en) | 2019-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6469362B2 (en) | Method for recovering valuable materials from lithium ion secondary batteries | |
| JP6378502B2 (en) | Method for recovering valuable materials from lithium ion secondary batteries | |
| CN110199429B (en) | Method for recovering valuable substances from used lithium ion battery | |
| JP6859598B2 (en) | How to recover valuables from used lithium-ion batteries | |
| KR101883100B1 (en) | Method of recovering valuable metals from wasted batteries and system for the same | |
| JP6268130B2 (en) | Method for recovering valuable materials from lithium-ion batteries | |
| JP6748274B2 (en) | How to recover valuables from lithium-ion secondary batteries | |
| Hu et al. | High-intensity magnetic separation for recovery of LiFePO4 and graphite from spent lithium-ion batteries | |
| JP3079287B2 (en) | How to recover valuable resources from used lithium batteries | |
| WO2013051305A1 (en) | Method for recovering valuable materials from lithium ion secondary cells | |
| EP4101550A1 (en) | Separation method for valuable resources | |
| JP6676124B1 (en) | Method of recovering valuable resources from lithium ion secondary batteries | |
| WO2020179692A1 (en) | Treatment system and treatment method for waste lithium ion batteries | |
| WO2021177200A1 (en) | Method for concentrating valuable metal contained in lithium ion secondary battery | |
| JP2021141060A (en) | Method for concentrating valuable metal included in lithium-ion secondary battery | |
| EP4215291A1 (en) | Method for recovering valuable materials from lithium ion secondary battery | |
| JP7268382B2 (en) | How to dispose of used lithium-ion batteries | |
| JP6994418B2 (en) | Disposal device and treatment method for waste lithium-ion batteries | |
| EP4212258A1 (en) | Valuable matter recovery method | |
| JP7413847B2 (en) | Method for recovering valuable metals from waste batteries | |
| JPH08287967A (en) | Method of recovering cobalt, copper, and lithium from used lithium secondary battery | |
| WO2023204230A1 (en) | Method for recovering valuable materials from lithium-ion secondary battery | |
| JP7355713B2 (en) | Pretreatment method for recovering valuable elements from secondary batteries and method for recovering valuable elements from secondary batteries | |
| EP4215288A1 (en) | Method for recovering valuable substance | |
| AU2023241377A1 (en) | Battery recycling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170317 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180131 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180220 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20180423 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180606 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20181009 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20181025 |
|
| 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: 20190108 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20190116 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6469362 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 |