JP2021072157A - Recycling method for lithium ion battery - Google Patents
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 238000011109 contamination Methods 0.000 claims abstract description 16
- 238000010828 elution Methods 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 1
- 230000005611 electricity Effects 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 150000002739 metals Chemical class 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000011084 recovery Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000011888 foil Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Secondary Cells (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
本発明は、使用済みのリチウムイオン電池のリサイクル方法に関し、特には、熱処理せずに使用済みのリチウムイオン電池から各種有価金属を分離、回収することができるリサイクル方法に関する。なお、本明細書において、リチウムイオン電池の最小構成単位をセル（単電池）と称し、セルを複数使用して、直列接続又は並列接続して容量等を調整したものをモジュール（組電池）と称し、さらに、モジュールを複数組み合わせて蓄電システムを構成したものをパックと称する。そして、セル電圧とは、セルを放電時にセルに負荷される電圧を意味する。 The present invention relates to a method for recycling a used lithium-ion battery, and more particularly to a recycling method capable of separating and recovering various valuable metals from a used lithium-ion battery without heat treatment. In the present specification, the minimum structural unit of a lithium-ion battery is referred to as a cell (cell battery), and a module (combined battery) is a battery in which a plurality of cells are used and connected in series or in parallel to adjust the capacity and the like. Further, a pack is a combination of a plurality of modules to form a power storage system. The cell voltage means the voltage applied to the cell when the cell is discharged.
リチウムイオン電池は、エネルギー密度などの性能が優れていることから、電気自動車用などとして広く研究開発が行われている。リチウムイオン電池には、正極活物質としてマンガン酸リチウム（ＬｉＭｎＯ４）、コバルト酸リチウム（ＬｉＣｏＯ２）、ニッケル酸リチウム（ＬｉＮｉＯ２）、鉄リン酸リチウム（ＬｉＦｅＰＯ４）などが含まれており、また、正極集電体として、アルミ箔、負極集電体として、Ｃｕ箔などが含まれている。したがって、使用済みのリチウムイオン電池からこれらの電池素材を適切に分離して、Ｃｕ、Ｃｏ、Ｎｉなどの各種有価金属を回収することが求められている。 Lithium-ion batteries are widely researched and developed for electric vehicles because of their excellent performance such as energy density. The lithium ion battery contains lithium manganate (LiMnO 4 ), lithium cobalt oxide (LiCoO 2 ), lithium nickel oxide (LiNiO 2 ), lithium iron phosphate (LiFePO 4 ), and the like as positive electrode active materials. , Aluminum foil is included as the positive electrode current collector, and Cu foil is included as the negative electrode current collector. Therefore, it is required to appropriately separate these battery materials from the used lithium-ion battery and recover various valuable metals such as Cu, Co, and Ni.
使用済みのリチウムイオン電池から電池素材を回収する方法として、電池を水に浸漬して残留する電気の放電を行った後、焙焼してセパレータや電解液などの有機物質を分解燃焼させた後、その焙焼物を粉砕、篩分けし、その中に含まれる各種の有価金属を分離回収することが行われている（例えば、特許文献１〜３）。また、放電後に、電池ケースに穴を空けて電解液を除去した後、電池ケースを切断して、中から正極、負極、セパレータを機械的に取り出して、電極集電体を構成する銅箔やアルミ箔、また電極活物質を化学的に分離することが行われている（例えば、特許文献４〜５）。 As a method of recovering the battery material from a used lithium-ion battery, the battery is immersed in water to discharge the remaining electricity, and then roasted to decompose and burn organic substances such as separators and electrolytes. , The roasted product is crushed and sieved, and various valuable metals contained therein are separated and recovered (for example, Patent Documents 1 to 3). Further, after discharging, a hole is made in the battery case to remove the electrolytic solution, and then the battery case is cut, and the positive electrode, the negative electrode, and the separator are mechanically taken out from the inside to form a copper foil or a copper foil constituting the electrode current collector. The aluminum foil and the electrode active material are chemically separated (for example, Patent Documents 4 to 5).
使用済みの電池には電気が残留しているため、安全にリサイクルを進めるためには、上記の通り、導電性を有する液体に浸漬して完全放電したり、放電器を用いて残留する電気を放電したりして、電気的危険性を除去することが行われている。しかしながら、リチウムイオン電池は特性上、放電によりある程度電圧を下げても、復電現象によって電圧が回復することがあり、その結果、電池セルの解体作業時に火花が発生することがあった。万が一、その火花によって有機溶媒に引火した場合には、火災や爆発など大規模な災害が懸念されるという問題があった。 Since electricity remains in the used battery, in order to proceed with recycling safely, as described above, it is immersed in a conductive liquid to completely discharge it, or the remaining electricity is discharged using a discharger. Electric discharge is removed to eliminate electrical hazards. However, due to the characteristics of lithium-ion batteries, even if the voltage is lowered to some extent by discharging, the voltage may recover due to the power recovery phenomenon, and as a result, sparks may occur during the dismantling work of the battery cells. In the unlikely event that the spark ignites the organic solvent, there is a problem that there is a concern about a large-scale disaster such as a fire or an explosion.
一方、上記復電現象を抑えるために、水に浸漬するなどして０Ｖ付近まで完全放電に近い形での放電手法を用いることが考えられる。しかし、この場合、負極集電体の銅が溶出してしまい、取り出した正極にコンタミネーションが生じるという問題があった。
このようなことから、本発明は、上記問題を解消することを目的とするものであって、使用済みリチウムイオン電池解体時に残留する電気によって火花が発生することなく、且つ、銅による正極へのコンタミネーションを抑制することができる、リチウムイオン電池のリサイクル方法を提供することを課題とする。
On the other hand, in order to suppress the above-mentioned power recovery phenomenon, it is conceivable to use a discharge method in a form close to complete discharge up to around 0 V by immersing in water. However, in this case, there is a problem that the copper of the negative electrode current collector elutes and contamination occurs in the taken out positive electrode.
Therefore, the present invention aims to solve the above-mentioned problems, and the electricity remaining at the time of disassembling the used lithium-ion battery does not generate sparks, and copper is used for the positive electrode. An object of the present invention is to provide a method for recycling a lithium ion battery that can suppress contamination.
上記の課題を解決するために、本発明者らは鋭意研究を行った結果、放電工程と解体工程とが分かれていると、その間に復電現象が起こることから、放電させながら火花の発生しない電圧まで低下させた時点で解体作業を開始し、また、銅の溶出によるコンタミネーションが軽微な時点で解体作業を終了させることにより、安全にリチウムイオン電池の解体作業が可能となると共に、正極への銅によるコンタミネーションを抑制することができるとの知見が得られた。 As a result of diligent research to solve the above problems, if the discharge process and the dismantling process are separated, a power recovery phenomenon occurs between them, so that sparks do not occur while discharging. By starting the dismantling work when the voltage is lowered to the voltage and ending the dismantling work when the contamination due to copper elution is slight, the lithium ion battery can be safely disassembled and the positive electrode is reached. It was found that the contamination by copper can be suppressed.
本発明者らは、この知見に基づき、以下の発明を提供する。
１）使用済みリチウムイオン電池を放電、解体して電池素材を分離、回収する方法であって、放電を実施して火花が発生しないセル電圧以下となった段階で解体作業を開始し、銅の溶出による汚染がない或いは汚染が軽微な段階で解体作業を終了することを特徴とするリチウムイオン電池のリサイクル方法。
２）抵抗を用いて放電しセル電圧が２．４Ｖ以下となってから、リチウムイオン電池の解体作業を開始することを特徴とする上記１）記載のリチウムイオン電池のリサイクル方法。
３）固定抵抗（１Ω）による放電を実施した場合にセル電圧が０．６Ｖ以下となってから３０分以内にリチウムイオン電池の解体作業を終了することを特徴とする上記１）又は２）に記載のリチウムイオン電池のリサイクル方法。
４）０．０１〜１００Ωの抵抗を用いて放電することを特徴とする上記１）〜３）のいずれか一に記載のリチウムイオン電池のリサイクル方法。
５）正極中への銅の溶出量が１０ｐｐｍ以下であることを特徴とする上記１）〜４）のいずれか一に記載のリチウムイオン電池のリサイクル方法。
Based on this finding, the present inventors provide the following inventions.
1) This is a method of discharging and disassembling a used lithium-ion battery to separate and recover the battery material. When the battery voltage is below the cell voltage at which sparks do not occur after discharging, the dismantling work is started and the copper is used. A method for recycling a lithium-ion battery, characterized in that the dismantling work is completed at a stage where there is no contamination due to elution or the contamination is minor.
2) The method for recycling a lithium ion battery according to 1) above, wherein the dismantling work of the lithium ion battery is started after discharging using a resistor and the cell voltage becomes 2.4 V or less.
3) The above 1) or 2) is characterized in that the dismantling work of the lithium ion battery is completed within 30 minutes after the cell voltage becomes 0.6 V or less when the discharge is performed by the fixed resistance (1 Ω). The method for recycling a lithium-ion battery described.
4) The method for recycling a lithium ion battery according to any one of 1) to 3) above, which comprises discharging using a resistor of 0.01 to 100Ω.
5) The method for recycling a lithium ion battery according to any one of 1) to 4) above, wherein the amount of copper eluted into the positive electrode is 10 ppm or less.
本発明によれば、安全にリチウムイオン電池を解体することができるとともに、銅による正極へのコンタミネーションを低減することができるという優れた効果を有する。また、回収された金属は、汚染が少ないことから直接、他の製品の製造に利用することができるという優れた効果を有する。さらに本発明によれば、熱処理を行わずに電池の解体作業を行うため、コンパクトな処理設備とすることができ、低コストで電池素材を回収することができるという優れた効果を有する。 According to the present invention, the lithium ion battery can be safely disassembled, and the contamination of copper to the positive electrode can be reduced, which is an excellent effect. In addition, the recovered metal has an excellent effect that it can be directly used for manufacturing other products because it is less contaminated. Further, according to the present invention, since the battery is disassembled without heat treatment, it is possible to obtain a compact processing facility and have an excellent effect that the battery material can be recovered at low cost.
本発明のリチウムイオン電池のリサイクル方法は、使用済みの電池を、熱処理せずに電池を機械的に解体することができることを特徴とする。そして、使用済みのリチウムイオン電池を解体後は、各種電池素材を適宜、分離、回収することができる。リチウムイオン電池は通常、正極として、Ａｌ箔材の両面にＣｏ、Ｎｉ、Ｍｎなどが含まれる正極材が塗布されたものが使用され、負極として、Ｃｕ箔材の両面にＣ（グラファイト）が塗布されたものが使用される。したがって、正極材から、高価なＭｎ、Ｃｏ、Ｎｉなどを分離回収することができる。 The method for recycling a lithium-ion battery of the present invention is characterized in that a used battery can be mechanically disassembled without heat treatment. Then, after disassembling the used lithium-ion battery, various battery materials can be appropriately separated and recovered. Lithium-ion batteries are usually used as a positive electrode in which a positive electrode material containing Co, Ni, Mn, etc. is coated on both sides of an Al foil material, and as a negative electrode, C (graphite) is coated on both sides of a Cu foil material. The one that has been used is used. Therefore, expensive Mn, Co, Ni and the like can be separated and recovered from the positive electrode material.
一般に使用済みのリチウムイオン電池は機能破壊を目的として熱処理を施し、素材のリサイクルを念頭においていない場合には、焼却後に埋め立てや路盤材などに用いられ、一方、素材をリサイクルする場合は、熱処理後、粉砕などを行った後、濃縮工程（化学的手法、物理的手法）を経て、各種素材の選別、分離回収が行われる。しかし、いずれの場合も、大規模な焼却設備が必要であり、また、焙焼物を粉砕などするため複雑で高コストな処理となる。これに対して、本発明のリサイクル方法は、このような熱処理は行わずに、電池素材を回収するため、コンパクトな設備とすることができ、低コストで、有価金属を回収することができるというメリットがある。 Generally, used lithium-ion batteries are heat-treated for the purpose of destroying their functions. If the material is not recycled, it is used for landfill or roadbed material after incineration. On the other hand, if the material is recycled, it is after heat treatment. After performing crushing and the like, various materials are sorted and separated and recovered through a concentration step (chemical method, physical method). However, in either case, a large-scale incineration facility is required, and the roasted product is crushed, which is a complicated and costly process. On the other hand, in the recycling method of the present invention, since the battery material is recovered without performing such heat treatment, the equipment can be made compact and the valuable metal can be recovered at low cost. There are merits.
ここで、使用済みのリチウムイオン電池を解体する場合、予め電池に残留する電気を放電する必要がある。放電が十分でないと、電池の解体作業時に火花が発生して、電池に含まれる有機溶媒に引火して、火災や爆発などのおそれがあるためである。一方、完全に放電させた場合には、負極集電体を構成する銅が溶出して、正極活物質を構成するＮｉ、Ｃｏなどの有価金属を汚染してしまい、直接他の製品の製造に利用できない。 Here, when disassembling a used lithium-ion battery, it is necessary to discharge the electricity remaining in the battery in advance. This is because if the discharge is insufficient, sparks are generated during the dismantling work of the battery, and the organic solvent contained in the battery is ignited, which may cause a fire or an explosion. On the other hand, when the battery is completely discharged, the copper constituting the negative electrode current collector elutes and contaminates valuable metals such as Ni and Co constituting the positive electrode active material, which is directly used for manufacturing other products. Not available.
図１に、放電工程から解体工程（洗浄、開封処理）までの使用済み電池の電圧変化を示す。固定抵抗（１Ω）による放電を実施した場合、銅の溶出がないセル電圧０．６Ｖで放電を中断すると、復電現象によって、セル電圧１．１Ｖ以上に上昇し、電池を解体（短絡）すると、火花（スパーク）が発生するということがあった。 FIG. 1 shows the voltage change of the used battery from the discharge process to the disassembly process (cleaning, opening process). When discharging with a fixed resistor (1Ω), if the discharging is interrupted at a cell voltage of 0.6V without copper elution, the cell voltage rises to 1.1V or more due to the power recovery phenomenon, and the battery is disassembled (short-circuited). , Sparks were sometimes generated.
このように、電池解体時における火花の発生と銅の溶出を考慮した最適な放電には、トレードオフの関係がある。この点、充放電器を活用することで、電圧１．１Ｖ以下、０．６Ｖ以上にセル電圧を制御することも考えられるが、一般的に組電池として使用するリチウムイオン電池において、一つ一つのセルに対して電圧を制御しながら解体を進めることは、高コストとなるため、現実性がない。 As described above, there is a trade-off relationship between the generation of sparks at the time of battery dismantling and the optimum discharge considering the elution of copper. In this regard, it is conceivable to control the cell voltage to a voltage of 1.1 V or less and 0.6 V or more by utilizing a charger / discharger, but in a lithium ion battery generally used as an assembled battery, each one is used. It is not realistic to proceed with dismantling while controlling the voltage for one cell because it is expensive.
本発明者らは、試行錯誤の末、放電工程と解体工程とが分かれていることで、その間に復電現象が起こることから、使用済みの電池を放電させながら解体すれば、復電現象を生じさせることがないことを閃いた。
これに基づき本発明は、放電を実施して火花が発生しない電圧以下となった段階で解体作業を開始し、銅の溶出による汚染がない或いは汚染が軽微な段階で解体作業を終了することを特徴とするものである。なお、放電を続けながら解体と分別とを実施するが、分別過程で導通部が離れ、放電状態が解かれることになるが、このときは火花が発生することはないため、特に問題はない。
After trial and error, the present inventors separate the discharge process and the disassembly process, and a power recovery phenomenon occurs between them. Therefore, if the used battery is disassembled while being discharged, the power recovery phenomenon can be caused. I flashed that it wouldn't happen.
Based on this, the present invention starts the dismantling work when the voltage becomes lower than the voltage at which sparks are not generated by performing electric discharge, and ends the dismantling work when there is no contamination due to elution of copper or the contamination is slight. It is a feature. Disassembly and separation are carried out while continuing the discharge, but the conductive part is separated during the separation process and the discharge state is released, but at this time, sparks do not occur, so there is no particular problem.
図２に、放電工程中に解体工程（洗浄、開封処理）を実施したときの使用済み電池の電圧変化を示す。固定抵抗（１Ω）による放電を実施しながら、セル電圧が２．４Ｖ以下となってから解体作業を開始する。放電状態を解除した後に解体すると、セル電圧が１．１Ｖ以上で火花が発生するが、放電しながら解体した場合は、セル電圧が２．４Ｖ以下でも火花が発生しないことがある。好ましくはセル電圧が２．０Ｖ以下、より好ましくは１．５Ｖ以下、さらに好ましくは、１．２Ｖ以下の時点で解体作業を開始する。なお、温度、湿度、電池の状態によって火花が発生するセル電圧が若干異なることから、事前に火花の発生するセル電圧を確認することが好ましい。 FIG. 2 shows the voltage change of the used battery when the disassembling step (cleaning, opening process) is performed during the discharging step. While discharging with a fixed resistor (1Ω), the dismantling work is started after the cell voltage becomes 2.4V or less. When disassembled after releasing the discharged state, sparks are generated when the cell voltage is 1.1 V or more, but when disassembled while discharging, sparks may not be generated even when the cell voltage is 2.4 V or less. The dismantling work is preferably started when the cell voltage is 2.0 V or less, more preferably 1.5 V or less, and even more preferably 1.2 V or less. Since the cell voltage at which sparks are generated differs slightly depending on the temperature, humidity, and battery condition, it is preferable to confirm the cell voltage at which sparks are generated in advance.
表１に、固定抵抗（１Ω）による放電を実施した場合の、セル電圧０．６Ｖ以下の放電時間に対する正極中のＣｕ品位を示す。表１のとおり、放電時間が１５分でＣｕ濃度が６ｗｔｐｐｍであり、２０分で８ｗｔｐｐｍであり、３０分で９ｗｔｐｐｍであり、３５分で１２ｗｔｐｐｍである。なお、使用済みのリチウムイオン電池をセル電圧０．６Ｖ以下（固定抵抗は１Ωとする）にせずに解体し、回収した正極を分析すると６ｗｔｐｐｍ程度のＣｕが含まれていた。この結果から、固定抵抗（１Ω）による放電を実施した場合に、セル電圧が０．６Ｖとなる前に解体作業を終了させることが好ましいが、０．６Ｖとなってから３０分以内であれば、銅の溶出量が１０ｗｔｐｐｍ以下と少なく銅による汚染は軽微であり、許容されるものである。 Table 1 shows the Cu grade in the positive electrode for a discharge time of a cell voltage of 0.6 V or less when discharging with a fixed resistance (1 Ω) is performed. As shown in Table 1, the discharge time is 15 minutes, the Cu concentration is 6 wtppm, 20 minutes is 8 wtppm, 30 minutes is 9 wtppm, and 35 minutes is 12 wtppm. When the used lithium-ion battery was disassembled without reducing the cell voltage to 0.6 V or less (fixed resistance is 1 Ω) and the recovered positive electrode was analyzed, Cu of about 6 wtppm was contained. From this result, when discharging with a fixed resistor (1Ω), it is preferable to finish the dismantling work before the cell voltage reaches 0.6V, but if it is within 30 minutes after reaching 0.6V. The elution amount of copper is as small as 10 wtppm or less, and the contamination by copper is slight and is acceptable.
図２では、１Ωの固定抵抗器を用いて放電を行っているが、抵抗値が低いほど、銅が溶出するまでの時間が短く（図２のグラフの傾きが大きい）、抵抗値が高いほど、銅が溶出するまでの時間が長い（図２のグラフの傾きが小さい）。したがって、すぐに解体する場合には、低抵抗のものを用いて放電し、一方、数日後、あるいは１週間後に解体を予定している場合には、高抵抗のものを用いて放電することができる。このように、解体作業時間あるいは解体作業予定日等を考慮して、抵抗値を決めることが望ましい。好ましくは０．０１〜１００Ωの抵抗を用いることができる。 In FIG. 2, discharge is performed using a 1Ω fixed resistor. The lower the resistance value, the shorter the time until copper elutes (the slope of the graph in FIG. 2 is larger), and the higher the resistance value. , It takes a long time for copper to elute (the slope of the graph in FIG. 2 is small). Therefore, if you want to disassemble immediately, you can discharge using a low resistance one, while if you plan to disassemble after a few days or a week, you can discharge using a high resistance one. it can. In this way, it is desirable to determine the resistance value in consideration of the dismantling work time, the scheduled dismantling work date, and the like. Preferably, a resistor of 0.01 to 100 Ω can be used.
本開示では、固定抵抗器を用いて放電を行っているが、例えば、ＳＵＳ線（番線）やニクロム線など素材自体が適度な抵抗を有しているものを活用してもよく、さらには、電球などを用いることもできる。このように固定抵抗を始め、多種多様な部材を用いて放電することが可能であり、その中から適度な抵抗を有すものを選択することができる。 In the present disclosure, discharge is performed using a fixed resistor, but for example, a material such as a SUS wire (numbered wire) or a nichrome wire having an appropriate resistance may be utilized, and further, a material having an appropriate resistance may be used. A light bulb or the like can also be used. In this way, it is possible to discharge using a wide variety of members including fixed resistance, and one having an appropriate resistance can be selected from among them.
以上の方法を用いて、使用済みのリチウムイオン電池を安全に解体することができ、その後は、従来技術を用いて、各種の電池素材を分離、回収することができる。通常、リチウムイオン電池は、Ａｌ素材、あるいは、Ｆｅ、ＳＵＳ素材のケースの中に、Ａｌ箔材の両面に正極材（Ｃｏ、Ｎｉ、Ｍｎなどが含まれる）が塗布された正極と、Ｃｕ箔材の両面に負極材（Ｃ）が塗布された負極と、ＰＰ（ポリプロピレン）やＰＥ（ポリエチレン）からなるセパレータが設置されている。 The used lithium-ion battery can be safely disassembled by using the above method, and then various battery materials can be separated and recovered by using the prior art. Usually, a lithium ion battery has a positive electrode in which positive electrode materials (including Co, Ni, Mn, etc.) are coated on both sides of the Al foil material in a case made of Al material or Fe, SUS material, and a Cu foil. A negative electrode coated with a negative electrode material (C) on both sides of the material and a separator made of PP (polypropylene) or PE (polyethylene) are installed.
回収した正極は、水素吸蔵合金などの製品の原料として、あるいは、製錬原料とすることができる。正極をフラックス（ＣａＯなど）と共に溶解すると、Ａｌが還元剤となって、リチウムと複合酸化物を形成しているＣｏ、Ｎｉ、Ｍｎを金属（メタル）として、還元することができる。このとき、Ａｌが過剰に含まれているため、メタル中にＡｌが取り込まれるが、水素吸蔵合金にはＡｌを含む組成のものが存在することから、Ａｌが含まれていても特に問題はない。このように製品とする場合には、不純物となり得るＣｕを低減する本発明が特に有効である。精錬原料とする場合には、酸溶解、精製（溶媒抽出など）によって、高価なＣｏ、Ｎｉ、Ｍｎを各々、分離回収することができる。一方、回収した負極は、Ｃｕ精錬原料とすることができ、ＰＰやＰＥは、プラスチックリサイクルへと分離することができる。また、ケース素材であるＡｌはＡｌ二次合金として、ＦｅやＳＵＳは鉄屑（鉄鋼原料）として、それぞれ分離、回収することができる。 The recovered positive electrode can be used as a raw material for products such as hydrogen storage alloys or as a raw material for smelting. When the positive electrode is dissolved together with a flux (CaO or the like), Al can be used as a reducing agent, and Co, Ni, and Mn forming a composite oxide with lithium can be reduced as a metal. At this time, since Al is excessively contained, Al is incorporated into the metal, but since some hydrogen storage alloys have a composition containing Al, there is no particular problem even if Al is contained. .. In the case of producing a product in this way, the present invention that reduces Cu that can be an impurity is particularly effective. When used as a refining raw material, expensive Co, Ni, and Mn can be separated and recovered by acid dissolution and purification (solvent extraction, etc.). On the other hand, the recovered negative electrode can be used as a Cu refining raw material, and PP and PE can be separated into plastic recycling. Further, Al, which is a case material, can be separated and recovered as an Al secondary alloy, and Fe and SUS can be separated and recovered as iron scrap (steel raw material).
次に、本発明の実施例等について説明する。なお、以下の実施例は、あくまで代表的な例を示しているもので、本発明はこれらの実施例に制限される必要はなく、明細書の記載される技術思想の範囲で解釈されるべきものである。 Next, examples and the like of the present invention will be described. It should be noted that the following examples are merely representative examples, and the present invention need not be limited to these examples and should be interpreted within the scope of the technical idea described in the specification. It is a thing.
（実施例１）
使用済みのリチウムイオンの電池パックをモジュールへと解体した後、モジュールを粗放電した（セル電圧０．６Ｖ／セル以上、固定抵抗１Ω）。次に、このモジュールを解体して、使用済み電池セルとし、電池セルを放電しながら、セル電圧が２．４Ｖ以下（固定抵抗１Ω）となってから電池セルを解体（開封）して、セル電圧が０．６Ｖ以下となってから３０分以内に正極、負極、セパレータ、ケース、蓋、端子の各種電池素材を分離した。その後、上記の手法によって、各種電池素材から有価金属等を回収した。このとき、正極中のＣｕの品位は６ｗｔｐｐｍであった。
(Example 1)
After disassembling the used lithium-ion battery pack into a module, the module was extensively discharged (cell voltage 0.6 V / cell or more, fixed resistance 1 Ω). Next, this module is disassembled to make a used battery cell, and while discharging the battery cell, the battery cell is disassembled (opened) after the cell voltage becomes 2.4 V or less (fixed resistance 1 Ω). Within 30 minutes after the voltage became 0.6 V or less, various battery materials for the positive electrode, the negative electrode, the separator, the case, the lid, and the terminal were separated. Then, valuable metals and the like were recovered from various battery materials by the above method. At this time, the grade of Cu in the positive electrode was 6 wtppm.
（実施例２）
使用済みのリチウムイオンの電池パックをモジュールへと解体した後、モジュールを粗放電した（セル電圧０．６Ｖ／セル以上、固定抵抗１Ω）。次に、このモジュールを解体して、使用済み電池セルとし、電池セルを放電しながら、セル電圧が１．６Ｖ以下（ＳＵＳ線使用）となってから、電池セルを解体（開封）して、セル電圧が０．６Ｖ以下となってから３０分以内に正極、負極、セパレータ、ケース、蓋、端子の各種電池素材を分離した。その後、上記の手法によって、各種電池素材から有価金属等を回収した。このとき、正極中のＣｕの品位は１０ｗｔｐｐｍ未満であった。
(Example 2)
After disassembling the used lithium-ion battery pack into a module, the module was extensively discharged (cell voltage 0.6 V / cell or more, fixed resistance 1 Ω). Next, this module is disassembled to make a used battery cell, and while discharging the battery cell, the cell voltage becomes 1.6 V or less (using a SUS line), and then the battery cell is disassembled (opened). Within 30 minutes after the cell voltage became 0.6 V or less, various battery materials for the positive electrode, the negative electrode, the separator, the case, the lid, and the terminal were separated. Then, valuable metals and the like were recovered from various battery materials by the above method. At this time, the grade of Cu in the positive electrode was less than 10 wtppm.
本発明は、安全にリチウムイオン電池を解体することができるとともに、銅による正極へのコンタミネーションを低減することができる。そして、回収された金属は、汚染が少ないことから直接、他の製品の製造に利用することができる。本発明のリサイクル方法は、電気自動車、定地（住宅、ビル、太陽電池、風力発電）用蓄電池（システム）、非常用蓄電池（ＵＰＳや可搬バッテリーなど）、建設機械車両（産業用車両）、フォークリフト、電動車いす、などに用いられる大型のバッテリーや、携帯電話用や単三電池型などの小型のバッテリーに、用いられているリチウムイオン電池から、有価金属を回収するのに有用である。
INDUSTRIAL APPLICABILITY According to the present invention, the lithium ion battery can be safely disassembled, and contamination of the positive electrode by copper can be reduced. The recovered metal can be directly used for manufacturing other products because it is less contaminated. The recycling method of the present invention includes electric vehicles, storage batteries (systems) for fixed land (houses, buildings, solar cells, wind power generation), emergency storage batteries (UPS, portable batteries, etc.), construction machinery vehicles (industrial vehicles), It is useful for recovering valuable metals from lithium-ion batteries used in large batteries used in forklifts, electric wheelchairs, etc., and small batteries used in mobile phones, AA batteries, etc.
Claims (5)
The method for recycling a lithium ion battery according to any one of claims 1 to 4, wherein the amount of copper eluted into the positive electrode is 10 ppm or less.
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