JP2022036638A - 非水電解液二次電池の処理方法 - Google Patents
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 16
- 238000003672 processing method Methods 0.000 title abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 110
- 239000011888 foil Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 238000002844 melting Methods 0.000 claims abstract description 39
- 230000008018 melting Effects 0.000 claims abstract description 39
- 239000011149 active material Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 239000007769 metal material Substances 0.000 claims abstract description 15
- 239000000155 melt Substances 0.000 claims abstract description 14
- 239000002905 metal composite material Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000002893 slag Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 31
- 239000008151 electrolyte solution Substances 0.000 claims description 27
- 239000011230 binding agent Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- 238000006722 reduction reaction Methods 0.000 abstract description 6
- 239000003832 thermite Substances 0.000 description 32
- 239000007774 positive electrode material Substances 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 7
- -1 lithium nickel cobalt aluminum Chemical compound 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- XVUMPDDKXKGPMS-UHFFFAOYSA-N lithium;trifluoromethylsulfonylazanide Chemical compound [Li+].[NH-]S(=O)(=O)C(F)(F)F XVUMPDDKXKGPMS-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0038—Obtaining aluminium by other processes
- C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0084—Obtaining aluminium melting and handling molten aluminium
- C22B21/0092—Remelting scrap, skimmings or any secondary source aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/02—Obtaining aluminium with reducing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
Description
以下、図面を参照して本発明の実施形態について詳細に説明する。
取出工程S10では、セル容器12を開封して取り出した捲回型の電極体を巻き戻すことにより、シート状の正極を得る。シート状の正極は、加熱工程S11および溶融工程S12に供される。なお、取出工程S10では、非水電解液二次電池10を放電させる放電工程、放電させた非水電解液二次電池10のセル容器12内を洗浄液で洗浄するセル内洗浄工程等を行っても良い。
加熱工程S11は、取出工程S10で得られたシート状の正極に対し加熱処理を行う。加熱処理がされた正極は次工程である溶融工程S12に供される。加熱処理により、溶融工程S12におけるテルミット反応が促進され、正極を溶融し活物質を還元することが可能となる。
溶融工程S12は、加熱処理により加熱された正極を溶融する。溶融工程S12について、正極活物質としてLiNixCoyMnzO2を用いた場合を例に説明する。溶融工程S12では、正極に含まれるAl箔が還元剤となり、以下のような反応が生じる。反応の結果、金属複合酸化物を構成する金属を含む金属材料として、Ni、CoおよびMnを含有する合金(NixCoyMnz)が得られる。
LiNixCoyMnzO2+Al → 1/2Li2O+NixCoyMnz+1/2Al2O3
分離工程S13では、溶融物を冷却することにより金属複合酸化物を構成する金属を含む金属材料とスラグとを分離する。
本実施形態に係る非水電解液二次電池の処理方法では、溶融工程S12の前に加熱工程S11を有することにより、溶融工程S12において自発的な酸化還元反応(テルミット反応)が進むので、低コストで正極の還元反応を促進させることができる。
以下に、本発明の効果を確認するために行った実験について説明する。
捲回型の電極体と非水電解液とがセル容器12に収容された使用済みの非水電解液二次電池を用意した。用意した非水電解液二次電池に含まれる正極と非水電解液の構成は以下の通りである。
活物質(LiNi1/6Co2/3Mn1/6O2) 72~73質量%
バインダー(PVDF) 3~4質量%
導電材 4質量%
非水電解液 非水溶媒(DMC:EMC:PC) 質量比28:27:28
電解質(LiPF6) 1M
「〇」:正極の一部が溶融し、金属材料が得られ、テルミット反応が起きた。
「×」:金属材料が得られず、テルミット反応が起きなかった。
加熱工程S11を行わなかったシート状の正極を比較例1とした。加熱温度を変えたこと以外は実施例1~4と同じ条件として加熱処理を行った正極を比較例2とした。比較例1~2について、実施例1~4と同じ方法および基準で評価した。
S11 加熱工程
S12 溶融工程
S13 分離工程
Claims (4)
- Alを含む箔と、金属複合酸化物としての活物質とを有する正極を備える非水電解液二次電池の処理方法であって、
前記正極を加熱する加熱処理を行う加熱工程と、
前記箔と前記活物質との反応熱により前記正極を溶融して溶融物を得る溶融工程と、
前記溶融物を、前記金属複合酸化物を構成する金属を含む金属材料とスラグとに分離する分離工程と
を有する非水電解液二次電池の処理方法。 - 前記加熱処理は、前記箔が粉体化しない温度で加熱を行う請求項1に記載の非水電解液二次電池の処理方法。
- 前記正極はバインダーを含み、
前記加熱処理は、前記バインダーを分解する温度で加熱を行う請求項1または2に記載の非水電解液二次電池の処理方法。 - 前記加熱処理は、400℃以上650℃以下で加熱を行う請求項3に記載の非水電解液二次電池の処理方法。
Priority Applications (4)
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JP2020140948A JP2022036638A (ja) | 2020-08-24 | 2020-08-24 | 非水電解液二次電池の処理方法 |
CN202180051262.9A CN115917835A (zh) | 2020-08-24 | 2021-07-28 | 非水电解液二次电池的正极的处理方法 |
PCT/JP2021/027851 WO2022044667A1 (ja) | 2020-08-24 | 2021-07-28 | 非水電解液二次電池の正極の処理方法 |
US18/021,380 US20240039067A1 (en) | 2020-08-24 | 2021-07-28 | Treatment method for positive electrode of non-aqueous electrolyte secondary battery |
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WO (1) | WO2022044667A1 (ja) |
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JP5434934B2 (ja) * | 2011-02-18 | 2014-03-05 | 住友金属鉱山株式会社 | 有価金属回収方法 |
JP5657730B2 (ja) * | 2013-03-29 | 2015-01-21 | Jx日鉱日石金属株式会社 | リチウムイオン電池からの有価物の回収方法 |
JP6818202B2 (ja) * | 2017-05-08 | 2021-01-20 | 日本重化学工業株式会社 | リチウムイオン電池の処理方法 |
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2020
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2021
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