JP7220340B1 - METHOD FOR RECOVERING METAL FROM LITHIUM-ION BATTERY - Google Patents
METHOD FOR RECOVERING METAL FROM LITHIUM-ION BATTERY Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 78
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 238000002386 leaching Methods 0.000 claims abstract description 65
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 55
- 239000011572 manganese Substances 0.000 claims abstract description 51
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 37
- 239000007774 positive electrode material Substances 0.000 claims abstract description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 35
- 239000002893 slag Substances 0.000 claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 28
- 239000010439 graphite Substances 0.000 claims abstract description 27
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 27
- 238000005259 measurement Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002739 metals Chemical class 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims description 35
- 239000012298 atmosphere Substances 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 14
- 229910002441 CoNi Inorganic materials 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 4
- 239000006182 cathode active material Substances 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- -1 nickel-cobalt-aluminum Chemical compound 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 229910010093 LiAlO Inorganic materials 0.000 description 1
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 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
- 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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- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
【課題】溶媒抽出前の浸出工程において、リチウムイオン電池の電池滓から効率的で容易に金属（リチウム、マンガン）を回収する方法を提供する。【解決手段】本発明の方法は、正極活物質としてリチウム（Ｌｉ）、コバルト（Ｃｏ）及びニッケル（Ｎｉ）を含み、負極活物質として黒鉛（Ｃ）を含むリチウムイオン電池から金属を回収する方法であって、（ａ）Ｘ線回折（ＸＲＤ）測定において、回折角度１８．７°のピーク強度Ａと２６．５°のピーク強度Ｂとの比（Ａ／Ｂ）が０～０．１５の範囲にある、リチウムイオン電池の電池滓を準備する工程と、（ｂ１）電池滓を水中に分散させ、３０～８０℃の浸出液中に２～２４時間かけてリチウムを浸出させる工程、及び（ｂ２）電池滓を１～３質量％の濃度の硫酸水溶液中に分散させ、３０～８０℃の浸出液中に０．５～２４時間かけてリチウムとマンガンを浸出させる工程のいずれかを含む。【選択図】図１A method for efficiently and easily recovering metals (lithium, manganese) from battery slag of lithium ion batteries in a leaching step prior to solvent extraction is provided. A method of recovering metals from a lithium ion battery containing lithium (Li), cobalt (Co) and nickel (Ni) as positive electrode active materials and graphite (C) as a negative electrode active material. (a) In X-ray diffraction (XRD) measurement, the ratio (A/B) of the peak intensity A at a diffraction angle of 18.7° and the peak intensity B at 26.5° is 0 to 0.15 (b1) dispersing the battery slag in water and leaching lithium in a leaching solution at 30 to 80° C. for 2 to 24 hours; and (b2). ) dispersing the battery slag in an aqueous sulfuric acid solution having a concentration of 1 to 3% by mass, and leaching lithium and manganese in the leaching solution at 30 to 80° C. for 0.5 to 24 hours. [Selection drawing] Fig. 1
Description
本発明は、リチウムイオン電池からの金属回収方法に関し、具体的には、リチウムイオン電池の電池滓から金属を回収する方法に関し、より具体的には、リチウムイオン電池の電池滓からリチウム、マンガンを回収する方法に関する。 TECHNICAL FIELD The present invention relates to a method for recovering metals from lithium ion batteries, and more specifically to a method for recovering metals from battery slag of lithium ion batteries, and more specifically to a method for recovering lithium and manganese from battery slag of lithium ion batteries. Regarding the method of collection.
リチウムイオン電池は、各種の電子デバイスをはじめとして多くの産業分野で使用されており、マンガン、ニッケルおよびコバルトを含有するリチウム金属複合酸化物を正極材として用いるものが一般的に知られている。近年、その使用量の増加および使用範囲の拡大に伴い、電池の製品寿命や製造過程で不良により廃棄される量が増大している状況にある。かかる状況の下では、大量に廃棄されるリチウムイオン電池から、ニッケルおよびコバルト等の高価な元素を再利用するべく比較的低コストで容易に回収することが望まれる。 Lithium ion batteries are used in many industrial fields, including various electronic devices, and generally known are those that use a lithium metal composite oxide containing manganese, nickel and cobalt as a positive electrode material. In recent years, with the increase in the amount used and the expansion of the range of use, the amount of waste due to defects in the product life and manufacturing process of batteries is increasing. Under such circumstances, it is desirable to recover expensive elements such as nickel and cobalt from large quantities of discarded lithium-ion batteries for reuse at relatively low cost and easily.
有価金属の回収のためにリチウムイオン電池を処理するには、従来からある一般的な方法として、例えば、はじめにリチウムイオン電池を必要に応じて焙焼、粉砕および篩選別等の各工程を経て得られた粉状ないし粒状のリチウムイオン電池滓を準備する。その電池滓を酸浸出し、そこに含まれ得るリチウム、ニッケル、コバルト、マンガン、鉄、銅、アルミニウム等を溶液中に溶解させて浸出液を得る。その浸出液に対して溶媒抽出法を実施して、各金属元素を順次に分離させる。その際、まず鉄およびアルミニウムを回収し、続いてマンガンおよび銅、そしてコバルト、その後にニッケルを回収して、最後に水相にリチウムを残して回収する。 In order to process lithium-ion batteries for the recovery of valuable metals, for example, as a conventional general method, lithium-ion batteries are first obtained through processes such as roasting, pulverization, and sifting as required. Prepare powdered or granular lithium ion battery slag. The battery slag is acid-leached, and lithium, nickel, cobalt, manganese, iron, copper, aluminum, etc. that may be contained therein are dissolved in the solution to obtain a leachate. A solvent extraction method is performed on the leachate to sequentially separate each metal element. In doing so, iron and aluminum are recovered first, followed by manganese and copper, then cobalt, then nickel, and finally lithium, remaining in the aqueous phase.
従来の方法では、上述したように溶媒抽出後にリチウムを回収するのが一般的であるが、溶媒抽出前の浸出工程でリチウムが回収可能となる方法例として、例えば下記の特許文献１、２がある。特許文献１は、リチウムが含まれる電池廃棄物の熱処理方法及びリチウム回収方法を開示する。文献１の熱処理方法では、電池廃棄物を配置した熱処理炉内で、酸素と、窒素、二酸化炭素及び水蒸気からなる群から選択される少なくとも一種とを含む雰囲気ガスを流して、炉内酸素分圧を調整しながら、電池廃棄物を加熱する。文献１のリチウム回収方法では、熱処理工程後の電池廃棄物から得られる電池粉末中のリチウムを、弱酸性溶液、水又はアルカリ性溶液のいずれかで浸出させるリチウム浸出工程を含む。 In conventional methods, lithium is generally recovered after solvent extraction as described above. Examples of methods that enable lithium to be recovered in a leaching step before solvent extraction are disclosed in Patent Documents 1 and 2 below. be. Patent Document 1 discloses a heat treatment method for battery waste containing lithium and a lithium recovery method. In the heat treatment method of Document 1, an atmosphere gas containing oxygen and at least one selected from the group consisting of nitrogen, carbon dioxide, and water vapor is flowed in a heat treatment furnace in which battery waste is placed, and the partial pressure of oxygen in the furnace is increased. Heat the battery waste while adjusting the . The lithium recovery method of Document 1 includes a lithium leaching step of leaching lithium in battery powder obtained from battery waste after the heat treatment step with either a weakly acidic solution, water, or an alkaline solution.
特許文献２は、リチウムイオン電池廃棄物を焙焼して得られた電池滓からリチウムを回収する方法を開示する。その回収方法では、アルミン酸リチウムを含有する電池滓を、酸性溶液中に浸出させる浸出工程と、浸出工程で得られる浸出後液のｐＨを上昇させて中和するとともに固液分離して、リチウム溶解液を得る中和工程とを含む。 Patent Document 2 discloses a method for recovering lithium from battery slag obtained by roasting lithium ion battery waste. In the recovery method, the battery slag containing lithium aluminate is leached into an acidic solution, and the pH of the post-leaching solution obtained in the leaching step is raised to neutralize and solid-liquid separate to separate lithium. and a neutralization step to obtain a lysate.
特許文献１、２は、いずれも溶媒抽出前の浸出工程でリチウムが回収可能となる方法であるが、リチウムイオン電池の負極活物質の種類に関する情報は何も開示しておらず、かつ溶媒抽出前の浸出工程でのマンガンの回収については何ら言及していない。 Both Patent Documents 1 and 2 are methods in which lithium can be recovered in a leaching step before solvent extraction, but do not disclose any information about the type of negative electrode active material for lithium ion batteries, and solvent extraction No mention is made of manganese recovery in the previous leaching step.
特許文献１では、リチウムイオン電池滓の組成が分析／明示されておらずその組成が不明確であり、実施例ではリチウムの回収（浸出）率が５０～６０％程度（段落「００４８」）に留まっている。 In Patent Document 1, the composition of the lithium-ion battery slag is not analyzed/specified, and the composition is unclear. Staying.
特許文献２では、リチウムイオン電池滓中のアルミン酸リチウムの存在の有無を確認するためにＸ線回折法（ＸＲＤ）による分析結果が示されているが（段落「００２５」、図２）、他の組成とリチウムの回収率との関係等は開示されていない。 In Patent Document 2, an analysis result by X-ray diffraction method (XRD) is shown to confirm the presence or absence of lithium aluminate in lithium ion battery slag (paragraph “0025”, FIG. 2). The relationship between the composition of and the recovery rate of lithium is not disclosed.
本発明は、上記した従来技術の事情に鑑みて成されたものであって、その目的は、溶媒抽出前の浸出工程において、リチウムイオン電池の電池滓から効率的で容易に金属（リチウム、マンガン）を回収する方法を提供することである。 The present invention has been made in view of the circumstances of the prior art described above, and its object is to efficiently and easily remove metals (lithium, manganese, ) is to provide a method for recovering the
本発明の一態様は、正極活物質としてリチウム（Ｌｉ）、コバルト（Ｃｏ）及びニッケル（Ｎｉ）を含み、負極活物質として黒鉛（Ｃ）を含むリチウムイオン電池から金属を回収する方法であって、（ａ）Ｘ線回折（ＸＲＤ）測定において、回折角度１８．７°のピーク強度Ａと２６．５°のピーク強度Ｂとの比（Ａ／Ｂ）が０～０．１５の範囲にある、リチウムイオン電池の電池滓を準備する工程と、（ｂ）電池滓を水中に分散させ、３０～８０℃の浸出液中に２～２４時間かけてリチウムを浸出させる工程と、を含む方法を提供する。 One aspect of the present invention is a method for recovering metal from a lithium ion battery containing lithium (Li), cobalt (Co), and nickel (Ni) as a positive electrode active material and graphite (C) as a negative electrode active material, , (a) in X-ray diffraction (XRD) measurement, the ratio (A / B) of the peak intensity A at a diffraction angle of 18.7 ° and the peak intensity B at 26.5 ° is in the range of 0 to 0.15 and (b) dispersing the battery slag in water and leaching lithium in a leaching solution at 30-80° C. for 2-24 hours. do.
本発明の他の一態様は、正極活物質としてリチウム（Ｌｉ）、コバルト（Ｃｏ）及びニッケル（Ｎｉ）を含み、負極活物質として黒鉛（Ｃ）を含むリチウムイオン電池から金属を回収する方法であって、（ａ）Ｘ線回折（ＸＲＤ）測定において、回折角度１８．７°のピーク強度Ａと２６．５°のピーク強度Ｂとの比（Ａ／Ｂ）が０～０．１５の範囲にある、リチウムイオン電池の電池滓を準備する工程と、（ｂ）電池滓を１～３質量％の濃度の硫酸水溶液中に分散させ、３０～８０℃の浸出液中に０．５～２４時間かけてリチウムとマンガンを浸出させる工程と、を含む方法を提供する。 Another aspect of the present invention is a method for recovering metal from a lithium ion battery containing lithium (Li), cobalt (Co) and nickel (Ni) as positive electrode active materials and graphite (C) as negative electrode active materials. (a) In X-ray diffraction (XRD) measurement, the ratio (A / B) of the peak intensity A at a diffraction angle of 18.7 ° and the peak intensity B at 26.5 ° is in the range of 0 to 0.15 (b) dispersing the battery residue in an aqueous solution of sulfuric acid with a concentration of 1 to 3% by mass and placing it in a leachate at 30 to 80° C. for 0.5 to 24 hours. and leaching the lithium and manganese by applying.
本発明の他の各態様では、電池滓は、（ｉ）Ｘ線回折（ＸＲＤ）測定において、ＣｏＮｉに起因するピークを有し、あるいはＬｉ２ＣＯ３とＣｏ３Ｏ４の一方または双方に起因するピークを有し、（ｉｉ）１０～３５質量％の黒鉛（Ｃ）を含み、あるいは正極活物質はマンガン（Ｍｎ）を含む。 In other aspects of the invention, the battery slag (i) has peaks attributed to CoNi in X-ray diffraction (XRD) measurements , or attributed to one or both of Li2CO3 and Co3O4 . and (ii) contains 10 to 35% by mass of graphite (C), or the positive electrode active material contains manganese (Mn).
本発明の他の一態様では、リチウムイオン電池の電池滓を準備する工程（ａ）は、（ａ１）リチウムイオン電池を加熱炉内の大気中で５００～６００℃の温度で０．３～１０時間保持する熱処理工程と、（ａ２）熱処理後のリチウムイオン電池を粉砕して粉砕物を得る粉砕工程と、（ａ３）粉砕物を篩分けして粉状のリチウムイオン電池滓を得る篩分け工程と、を含む。 In another aspect of the present invention, the step (a) of preparing battery slag for a lithium ion battery includes (a1) heating the lithium ion battery to 0.3 to 10°C at a temperature of 500 to 600°C in the air in a heating furnace. (a2) a pulverizing step of pulverizing the heat-treated lithium ion battery to obtain a pulverized product; and (a3) a sieving step of sieving the pulverized product to obtain a powdery lithium ion battery residue. and including.
本発明の他の一態様では、熱処理工程（ａ１）は、加熱炉内を大気に代えて、酸素濃度が１～２１体積％の不活性ガスまたは過熱水蒸気の雰囲気、及び酸素濃度が１～３体積％の不活性ガスまたは過熱水蒸気の雰囲気のいずれかの状態にして加熱することを含む。 In another aspect of the present invention, the heat treatment step (a1) includes replacing the atmosphere in the heating furnace with an inert gas or superheated steam atmosphere having an oxygen concentration of 1 to 21% by volume and an oxygen concentration of 1 to 3. It includes heating in an atmosphere of either vol % inert gas or superheated steam.
本発明によれば、リチウムイオン電池の電池滓から溶媒抽出前の浸出工程でリチウム／マンガンを効率的で容易に分離／回収することが可能となる。 According to the present invention, it is possible to efficiently and easily separate/recover lithium/manganese from battery residue of a lithium ion battery in a leaching step prior to solvent extraction.
図面や表を参照しながら本発明の実施の形態を説明する。図１は、本発明の一実施形態のリチウムイオン電池から金属を回収する方法の工程を示す図である。最初に図１を参照しながら本発明の回収方法の概要（フロー）を説明する。 Embodiments of the present invention will be described with reference to drawings and tables. FIG. 1 is a diagram showing steps of a method for recovering metals from a lithium-ion battery according to one embodiment of the present invention. First, an overview (flow) of the recovery method of the present invention will be described with reference to FIG.
工程Ｓ１では、リチウムイオン電池の電池滓（以下、リチウムイオン電池滓、あるいは単に電池宰とも呼ぶ。）を準備する。原料となるリチウムイオン電池は、正極活物質としてリチウム（Ｌｉ）、コバルト（Ｃｏ）及びニッケル（Ｎｉ）を含み、負極活物質として黒鉛（Ｃ）を含む。また正極活物質はマンガン（Ｍｎ）を含むことができる。黒鉛（Ｃ）は、電池滓に１０～３５質量％含むことができる。電池滓は、Ｘ線回折（ＸＲＤ）測定において、回折角度１８．７°のピーク強度Ａと２６．５°のピーク強度Ｂとの比（Ａ／Ｂ）が０～０．１５の範囲にあるものを準備する。詳細は後述するが、このピーク強度比（Ａ／Ｂ）に着目するのは、リチウムイオン電池の正極活物質の結晶構造の崩壊によるリチウム（Ｌｉ）の取出（浸出）やすさの目安（指標）となるからである。さらに、電池滓は、Ｘ線回折（ＸＲＤ）測定において、ＣｏＮｉに起因するピーク、あるいはＬｉ２ＣＯ３とＣｏ３Ｏ４の一方または双方に起因するピークを有するという特徴がある。 In step S1, a battery slag of a lithium ion battery (hereinafter also referred to as lithium ion battery slag or simply battery slag) is prepared. A lithium-ion battery as a raw material contains lithium (Li), cobalt (Co), and nickel (Ni) as positive electrode active materials, and graphite (C) as a negative electrode active material. Also, the positive electrode active material may contain manganese (Mn). Graphite (C) can be contained in the battery slag in an amount of 10 to 35% by mass. In X-ray diffraction (XRD) measurement, the battery residue has a ratio (A/B) of peak intensity A at a diffraction angle of 18.7° and peak intensity B at 26.5° in the range of 0 to 0.15. prepare things Details will be described later, but the focus is on this peak intensity ratio (A / B), which is a measure (index) of how easily lithium (Li) is extracted (leached) due to the collapse of the crystal structure of the positive electrode active material of the lithium ion battery. This is because Furthermore, the battery slag is characterized by having peaks attributed to CoNi, or peaks attributed to one or both of Li 2 CO 3 and Co 3 O 4 in X-ray diffraction (XRD) measurements.
工程Ｓ２では、工程Ｓ１で得られた電池滓を水中に分散させ、３０～８０℃の浸出液中に２～２４時間かけてリチウムを浸出させる。この水（温水）を用いた浸出では、Ｃｏ、Ｎｉ及びＭｎの浸出をほぼ完全に抑制しつつＬｉのみを浸出させることができる。電池滓の水スラリー中の含有量は、５０～１５０ｇ／Ｌ、好ましくは８０～１２０ｇ／Ｌ程度が良い。含有量が少ないと処理（浸出）量が低くなりすぎ処理効率が悪く、逆に高すぎるとスラリーの攪拌が十出来なくなり反応の均一性が低くなってしまうからである。 In step S2, the battery residue obtained in step S1 is dispersed in water, and lithium is leached in a leaching solution at 30 to 80° C. for 2 to 24 hours. In the leaching using this water (warm water), only Li can be leached while leaching of Co, Ni and Mn is almost completely suppressed. The content of the battery residue in the water slurry is 50 to 150 g/L, preferably 80 to 120 g/L. If the content is too low, the treatment (leaching) amount will be too low, resulting in poor treatment efficiency.
工程Ｓ３では、工程Ｓ１で得られた電池滓を１～５質量％の濃度の硫酸水溶液中に分散させ、３０～８０℃の浸出液中に０．５～２４時間かけてＬｉとＭｎを浸出させる。工程Ｓ３は工程Ｓ２に代えて、または並行して行うことができる。この希硫酸水溶液を用いた浸出では、ＣｏとＮｉの浸出を低く抑えつつＬｉとＭｎを浸出させることができる。電池滓の硫酸水溶液スラリー中の含有量は、水の場合と同様な理由で、５０～１５０ｇ／Ｌ、好ましくは８０～１２０ｇ／Ｌ程度が良い。 In step S3, the battery slag obtained in step S1 is dispersed in an aqueous sulfuric acid solution having a concentration of 1 to 5% by mass, and Li and Mn are leached out in a leaching solution at 30 to 80°C for 0.5 to 24 hours. . Step S3 can be performed in place of or in parallel with step S2. In the leaching using this dilute sulfuric acid aqueous solution, Li and Mn can be leached while suppressing the leaching of Co and Ni. The content of the battery residue in the sulfuric acid aqueous solution slurry is 50 to 150 g/L, preferably 80 to 120 g/L, for the same reason as in the case of water.
希硫酸の濃度は、０より大きく８質量％以下であり、好ましくは１～３質量％である。硫酸濃度が濃すぎると、ＣｏとＮｉの希硫酸への浸出量が多くなりすぎて、Ｌｉとの分離が悪くなるためである。浸出時間は、０．２５～２４時間であり、好ましくは０．２５～２時間であり、より好ましくは０．２５～１時間である。浸出温度は、常温～１００℃が良く、好ましくは３０℃～８０℃、より好ましくは６０℃～８０℃である。希硫酸を用いた場合、希硫酸濃度、浸出温度、浸出時間がＬｉとＣｏおよびＮｉの回収（浸出）率に影響を与えるため、これらを電池滓の組成やピーク強度比（Ａ／Ｂ）によって、適宜調整する事が好ましい。 The concentration of dilute sulfuric acid is greater than 0 and 8% by mass or less, preferably 1 to 3% by mass. This is because if the concentration of sulfuric acid is too high, the amounts of Co and Ni leached into dilute sulfuric acid are too large, and the separation from Li becomes poor. The leaching time is 0.25-24 hours, preferably 0.25-2 hours, more preferably 0.25-1 hour. The leaching temperature is preferably room temperature to 100°C, preferably 30°C to 80°C, more preferably 60°C to 80°C. When dilute sulfuric acid is used, the dilute sulfuric acid concentration, leaching temperature, and leaching time affect the recovery (leaching) rate of Li, Co, and Ni. is preferably adjusted as appropriate.
電池滓を希硫酸に浸出させると、浸出初期にＬｉ、ＭｎとＣｏおよびＮｉが浸出され、時間経過に従ってＣｏおよびＮｉの回収（浸出）率が低下する傾向が見られる。また、温度が高いほど、ＣｏおよびＮｉの浸出率の低下が速くなる傾向があり、Ｌｉ、Ｍｎの回収（浸出）は低下する傾向があるが、大きく低下することはない。希硫酸による浸出が進むにつれて、浸出液のｐＨは高くなる。浸出開始直後に、Ｌｉ、ＭｎとＣｏおよびＮｉの浸出が始まり、ｐＨも上昇し始めると考えられる。ｐＨの上昇に伴ってＣｏおよびＮｉは沈殿するものと考えられ、この沈殿によってＣｏおよびＮｉの見かけの回収（浸出）率が小さくなる。この反応は、温度が高いと早く進むため、温度が高いほどＬｉ、ＭｎとＣｏおよびＮｉの分離に要する時間は短くなる。Ｍｎは、浸出時間が２時間以内の場合は、Ｌｉと同じ浸出率を示す。反応時間が長くなると、Ｍｎの回収（浸出）率は低下する傾向が見られる。 When the battery slag is leached with dilute sulfuric acid, Li, Mn, Co and Ni are leached out in the initial stage of leaching, and the recovery (leaching) rate of Co and Ni tends to decrease over time. Also, the higher the temperature, the faster the rate of Co and Ni leaching tends to decrease, and the recovery (leaching) of Li and Mn tends to decrease, but does not decrease significantly. As the leaching with dilute sulfuric acid progresses, the pH of the leaching solution increases. Immediately after the start of leaching, Li, Mn, Co, and Ni begin to leach, and the pH also begins to rise. It is believed that Co and Ni precipitate with increasing pH, and this precipitation reduces the apparent recovery (leaching) of Co and Ni. Since this reaction proceeds faster at higher temperatures, the higher the temperature, the shorter the time required to separate Li, Mn from Co and Ni. Mn exhibits the same leaching rate as Li when the leaching time is within 2 hours. As the reaction time becomes longer, the recovery (leaching) rate of Mn tends to decrease.
工程Ｓ４では、工程Ｓ２で浸出したＬｉを回収する。回収は、中和や炭酸化等の公知の方法によって炭酸リチウムや水酸化リチウムの形態で行うことができる。工程Ｓ５では、工程Ｓ３で浸出したＬｉとＭｎを分離・回収する。ＬｉとＭｎは、浸出液のｐＨと酸化還元電位（ＯＲＰ）を適宣調整する事で分離できる。例えば、ｐＨを３．０～１０．０、より好ましくは３．５～７．０の範囲に調整し、ＯＲＰを４００～６００ｍＶ（Ｖｖｓ．Ａｇ／ＡｇＣｌ）とする事で、ＭｎをＭｎ酸化物として沈殿させ、液中のＬｉイオンと分離する事が出来る。なお、ＬｉとＭｎと同時に浸出されたＣｏおよびＮｉは、Ｍｎの分離後にさらにｐＨを調整する事で、ＣｏおよびＮｉの水酸化物として沈殿回収する事ができる。 In step S4, Li leached out in step S2 is recovered. Recovery can be performed in the form of lithium carbonate or lithium hydroxide by a known method such as neutralization or carbonation. In step S5, Li and Mn leached out in step S3 are separated and recovered. Li and Mn can be separated by appropriately adjusting the pH and oxidation-reduction potential (ORP) of the leachate. For example, by adjusting the pH in the range of 3.0 to 10.0, more preferably in the range of 3.5 to 7.0, and setting the ORP to 400 to 600 mV (V vs. Ag/AgCl), Mn is replaced with Mn oxide. can be separated from the Li ions in the liquid. Co and Ni leached simultaneously with Li and Mn can be precipitated and recovered as hydroxides of Co and Ni by further adjusting the pH after separating Mn.
図２は、図１の工程Ｓ１で準備する本発明の一実施形態のリチウムイオン電池滓の製造方法の工程を示す図である。以下、図２を参照しながらリチウムイオン電池滓の製法とその特徴について説明する。 FIG. 2 is a diagram showing steps of a method for manufacturing a lithium ion battery slag according to one embodiment of the present invention prepared in step S1 of FIG. Hereinafter, the method for producing the lithium ion battery residue and its characteristics will be described with reference to FIG.
工程Ｓ１１では、原料となるリチウムイオン電池を準備する。対象となるリチウムイオン電池は、携帯電話、スマートフォン、ノートブックＰＣ、その他の種々の電子機器、自動車等の様々な機械や装置で使用され得るリチウムイオン電池を含むことができる。その形態としては、寿命を終えて市場から回収されたリチウムイオン電池、製造不良のリチウムイオン電池、正極電極および負極電極、正極活物質を含む工程不良材、正極活物質、正極活物質前駆体などを単独もしくは混合して用いても良い。ただし、下記の要件（１）～（３）を満たすことが求められる。 In step S11, a lithium ion battery as a raw material is prepared. Lithium-ion batteries of interest can include lithium-ion batteries that can be used in various machines and devices such as mobile phones, smart phones, notebook PCs, various other electronic devices, and automobiles. The forms include lithium-ion batteries collected from the market at the end of their life, defective lithium-ion batteries, positive electrodes and negative electrodes, process-defective materials containing positive electrode active materials, positive electrode active materials, positive electrode active material precursors, etc. may be used singly or in combination. However, it is required to satisfy the following requirements (1) to (3).
（１）正極活物質としては、リチウム（Ｌｉ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、またはマンガン（Ｍｎ）を含み得る、コバルト酸リチウム（ＬＣＯ）、または三元系正極活物質であるニッケル・コバルト・マンガン（ＮＣＭ）、ニッケル・コバルト・アルミニウム（ＮＣＡ）、あるいはニッケル・コバルト・マンガン・アルミニウム（ＮＣＭＡ）が対象となる。リン酸鉄(オリビン鉄)は対象外である。 (1) As the positive electrode active material, lithium cobalt oxide (LCO), which may contain lithium (Li), cobalt (Co), nickel (Ni), or manganese (Mn), or nickel, which is a ternary positive electrode active material • Cobalt-manganese (NCM), nickel-cobalt-aluminum (NCA), or nickel-cobalt-manganese-aluminum (NCMA). Iron phosphate (olivine iron) is excluded.
（２）負極活物質としては、黒鉛（Ｃ）が対象となる。以下、本明細書中で「黒鉛」または「Ｃ」とも表記する。黒鉛は還元剤として機能している可能性が最も高いので、十分な量の黒鉛を加熱前に含んでいる必要がある。したがって、黒鉛は、リチウムイオン電池滓に１０～３５質量％、より好ましくは、２０～３２質量％含まれる必要がある。１０質量％未満では、ＣｏやＮｉの還元効果が不十分であり、３５質量％を超えると回収目的の金属の含有量が低くなってしまうからである。負極活物質が黒鉛のみで構成されるリチウムイオン電池を選択してもよい。黒鉛が必要量残る事を前提に、チタン酸リチウム、ニオブ酸リチウム、酸化ケイ素系などの黒鉛以外の負極活物質が混ざっていてもよい。また、鉄（Ｆｅ）や銅（Ｃｕ）が含まれていても良い。 (2) Graphite (C) is targeted as the negative electrode active material. Hereinafter, it is also referred to as “graphite” or “C” in this specification. Since graphite is most likely acting as a reducing agent, a sufficient amount of graphite should be present prior to heating. Therefore, graphite should be included in the lithium ion battery slag in an amount of 10-35% by weight, more preferably 20-32% by weight. This is because if it is less than 10% by mass, the effect of reducing Co or Ni is insufficient, and if it exceeds 35% by mass, the content of the metal to be recovered becomes low. A lithium ion battery in which the negative electrode active material is composed only of graphite may be selected. A negative electrode active material other than graphite, such as lithium titanate, lithium niobate, and silicon oxide, may be mixed on the premise that a necessary amount of graphite remains. Also, iron (Fe) and copper (Cu) may be contained.
（３）その他のリチウムイオン電池構成要素としては、通常の物が使用出来る。例えば、正極活物質が、ポリフッ化ビニリデン（ＰＶＤＦ）、その他の有機や水系バインダー等によって塗布され固着されたアルミニウム箔（正極基材）や、リチウムイオン電池の周囲を包む外装としてアルミニウムを含む筐体が含まれていても良い。 (3) As other lithium-ion battery components, ordinary ones can be used. For example, the positive electrode active material is polyvinylidene fluoride (PVDF), an aluminum foil (positive electrode base material) coated and fixed with other organic or water-based binders, etc., and a housing containing aluminum as an exterior wrapping around the lithium ion battery. may be included.
リチウムイオン電池の状態としては、例えば３Ｖ以下に放電されている事が好ましい。その放電方法は、塩水（５～２０質量％のＮａＣｌ水溶液）に浸して放電、放電機能を有する放電機での放電、抵抗を繋いでの放電等、放電可能であればいかなる方法でも良い。車載用や定置用途等のバッテリー・マネジメント・システム（ＢＭＳ）での電圧調整機能を用いても良い。塩水放電の場合、電解液を塩水中に拡散させて脱電解液を行っても良い。放電後に予備加熱もしくは直接次工程の本加熱（熱処理）を行う。予備加熱では、リチウムイオン電池を例えば２５０～３５０℃程度で加熱して、電解液を本加熱前に先に蒸発させることができる。 As for the state of the lithium ion battery, it is preferable that it is discharged to, for example, 3 V or less. The discharge method may be immersed in salt water (5 to 20% by mass NaCl aqueous solution), discharge with a discharge machine having a discharge function, discharge by connecting a resistor, or any other method as long as discharge is possible. A voltage adjustment function in a battery management system (BMS) for in-vehicle or stationary use may also be used. In the case of salt water discharge, electrolyte removal may be performed by diffusing the electrolyte in salt water. After discharging, preheating or main heating (heat treatment) in the next step is performed directly. In the preheating, the lithium-ion battery can be heated, for example, at about 250 to 350° C. to evaporate the electrolytic solution before the main heating.
工程Ｓ１２では、工程Ｓ１１で準備したリチウムイオン電池の熱処理を行う。ここで言う熱処理は、焙焼や焼成等と同様な意味で用いられ、リチウムイオン電池を、加熱炉内で大気（酸素濃度：約２１体積％）中または酸素濃度が制御された雰囲気中で所定の温度で加熱することを意味する。酸素濃度が制御された雰囲気は、例えば酸素を１～２１体積％含む不活性ガス（例えば窒素または過熱水蒸気）雰囲気が該当し、好ましくは１～３体積％の酸素を含む過熱水蒸気雰囲気が良い。電解液が残存しているリチウムイオン電池を原料として用いる場合は、酸素濃度を１～３体積％に制御することが好ましい。 In step S12, the lithium ion battery prepared in step S11 is heat-treated. The heat treatment referred to here is used in the same sense as roasting, baking, etc., and the lithium ion battery is heated in a heating furnace in the atmosphere (oxygen concentration: about 21% by volume) or in an atmosphere with a controlled oxygen concentration. means heating at a temperature of The atmosphere in which the oxygen concentration is controlled corresponds to, for example, an inert gas (eg, nitrogen or superheated steam) atmosphere containing 1 to 21% by volume of oxygen, preferably a superheated steam atmosphere containing 1 to 3% by volume of oxygen. When a lithium-ion battery in which electrolyte solution remains is used as a raw material, it is preferable to control the oxygen concentration to 1 to 3% by volume.
所定の温度は、例えば４５０～６５０℃が該当し、好ましくは５００～６００℃が良い。黒鉛は６００℃を超える温度で酸化されるため、この点からも加熱温度は５００～６００℃とする事が好ましい。温度が高いと、（１）Ｌｉとアルミ箔との反応が生じＬｉＡｌＯ２が多量に生成する、（２）アルミニウムの融点の６６０℃以上であればアルミ箔が融解して有価金属が溶融物に取り込まれて回収できなくなる、あるいは（３）加熱炉内でプラスチックが燃焼する等の不都合が生じてしまう。加熱時間は、例えば０．３～１０時間が該当し、好ましくは１０分～６時間が良い。 The predetermined temperature is, for example, 450 to 650.degree. C., preferably 500 to 600.degree. Since graphite is oxidized at temperatures exceeding 600° C., it is preferable to set the heating temperature to 500 to 600° C. in this respect as well. If the temperature is high, (1) Li and the aluminum foil react with each other to form a large amount of LiAlO2 , and (2) if the melting point of aluminum is 660°C or higher, the aluminum foil melts and the valuable metal becomes a melt. (3) Inconveniences such as the plastic burning in the heating furnace may occur. The heating time is, for example, 0.3 to 10 hours, preferably 10 minutes to 6 hours.
加熱条件は、使用する加熱炉の加熱方式、廃リチウムイオン電池の種類によって適宜使い分ける。上述した条件下で加熱すると、加熱時に円筒型や角型のリチウムイオン電池では、筐体の内部までは酸素が行き渡らず、セパレーター等のプラスチックが燃える事はない。ラミネート型リチウムイオン電池の場合は、電解液の蒸発時に開口部が大きく開く可能性があるため、１～３体積％の酸素を含む過熱水蒸気雰囲気下で加熱する事が好ましい。正極や負極に含まれるＰＶＤＦ等のバインダー成分の分解が生じ、正極活物質の正極集電体からの剥離および負極活物質の負極集電体からの剥離が容易に生じるようになるが、温度や時間が不十分であればこれらの作用が大量に生じることは無い。 The heating conditions are appropriately selected depending on the heating method of the heating furnace to be used and the type of the waste lithium ion battery. When heated under the above-mentioned conditions, oxygen does not reach the inside of the case of cylindrical or prismatic lithium-ion batteries during heating, and plastics such as separators do not burn. In the case of a laminated lithium-ion battery, since the opening may be greatly opened when the electrolyte evaporates, it is preferable to heat the battery in a superheated steam atmosphere containing 1 to 3% by volume of oxygen. Binder components such as PVDF contained in the positive electrode and the negative electrode are decomposed, and peeling of the positive electrode active material from the positive electrode current collector and peeling of the negative electrode active material from the negative electrode current collector easily occur. If the time is insufficient, these effects will not occur to a great extent.
使用する加熱炉は、基本的にどのような形式でもよい。例えば、連続式炉であるロータリーキルン、トンネル炉、ローラーハースキルン、台車炉、流動床炉等、あるいはバッチ式炉であるマッフル炉等を用いることができる。加熱後には冷却を行う。冷却を行わずに次工程の粉砕を行うと、残留しているプラスチックが燃える等の危険があるからである。冷却は１００℃以下、より好ましくは４０℃以下まで冷却する。冷却は、チラーを用いて冷却速度を速めても良いが、大気雰囲気で行うことが設備や雰囲気調整のコストを軽減する上で好ましい。 The heating furnace used can basically be of any type. For example, a continuous furnace such as a rotary kiln, a tunnel furnace, a roller hearth kiln, a bogie furnace, a fluidized bed furnace, or a batch type furnace such as a muffle furnace can be used. Cooling is performed after heating. This is because if the next step of pulverization is carried out without cooling, there is a danger that the remaining plastic will burn. Cooling is performed to 100° C. or lower, more preferably to 40° C. or lower. Cooling may be carried out using a chiller to increase the cooling rate, but it is preferable to carry out in an air atmosphere in order to reduce the cost of equipment and atmosphere adjustment.
工程Ｓ１３では、熱処理後のリチウムイオン電池を粉砕して粉砕物を得る。粉砕は、常用の粉砕機を使用出来、目的に応じて適宜選択することができる。衝撃により破砕して破砕物を得ても良い。切断機により熱処理物を切断する予備破砕を行っても良い。粉砕機としては、例えば、ハンマークラッシャーを用いることができる。セラミック等のボールにより被破砕物を叩く方法でも良く、ボールミル等により行うことができる。二軸破砕機あるいは必要に応じてジェットミルなどの気流粉砕機を用いても良い。 In step S13, the heat-treated lithium ion battery is pulverized to obtain a pulverized material. For pulverization, a commonly used pulverizer can be used and can be appropriately selected according to the purpose. A crushed material may be obtained by crushing by impact. Preliminary crushing may be performed by cutting the heat-treated material with a cutting machine. As the crusher, for example, a hammer crusher can be used. A method of hitting the object to be crushed with a ceramic ball or the like may also be used, and a ball mill or the like can be used. A twin-screw crusher or, if necessary, a pneumatic crusher such as a jet mill may be used.
工程Ｓ１４では、粉砕物を篩分けして所定サイズの粉状（粒状）のリチウムイオン電池滓を得る。この篩分けでは適度な粉径（粒径）に揃えることが望ましい。粉砕物を篩分けして篩上と篩下に選別して、それぞれにおいて回収物を得る。篩分けられた分離物に対して、磁力選別をする工程を含めてもよい。ここで、篩上物に磁選を実施する場合は、磁選後の非磁着物を粗粒産物、篩下に分離されるものを微粒産物という。 In step S14, the pulverized material is sieved to obtain powdery (granular) lithium-ion battery residue of a predetermined size. In this sieving, it is desirable to arrange the particles to have an appropriate powder size (particle size). The pulverized material is sieved and sorted into an upper sieve and an under sieve to obtain recovered materials in each case. A step of subjecting the sieved segregation to magnetic separation may be included. Here, when the sieved material is magnetically separated, the non-magnetic material after the magnetic separation is called the coarse-grained product, and the material separated under the sieve is called the fine-grained product.
篩上には、銅、アルミ箔、プラスチック、鉄が主として残る。篩下に有価金属を含む正極活物質等の処理物、粉砕工程で粉砕されて篩を通過した銅、アルミ箔、鉄や負極活物質の黒鉛などが含まれる。磁力選別を施せば、鉄は磁力によって除かれる。篩分け方法としては、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。例えば、振動篩、多段式振動篩、サイクロン、ＪＩＳ Ｚ８８０１の標準篩などを用いることができる。篩の篩目開きとしては、目的に応じて適宜選択することができるが、その範囲は０．０１～１０ｍｍ程度が好ましい。以下、得られる黒色のリチウムイオン電池滓を本出願ではブラックマス（ＢＭ）とも呼ぶ。 Copper, aluminum foil, plastic and iron are mainly left on the sieve. This includes processed materials such as positive electrode active materials containing valuable metals under the sieve, copper that has been pulverized in the pulverization process and passed through the sieve, aluminum foil, iron, graphite of the negative electrode active material, and the like. If magnetic separation is applied, the iron will be removed by magnetic force. The sieving method is not particularly limited and can be appropriately selected depending on the purpose. For example, a vibrating sieve, a multistage vibrating sieve, a cyclone, a JIS Z8801 standard sieve, or the like can be used. The mesh opening of the sieve can be appropriately selected according to the purpose, but the range is preferably about 0.01 to 10 mm. The resulting black lithium ion battery residue is hereinafter also referred to as black mass (BM) in this application.
工程Ｓ１５では、工程Ｓ１４で得られたリチウムイオン電池滓（ＢＭ）をＸ線回折（ＸＲＤ）測定する。Ｘ線回折（ＸＲＤ）測定は、リチウムイオン電池滓（ＢＭ）中の含有元素がどのような状態（化合物等）で存在するかを分析し、Ｌｉ／Ｍｎの浸出／回収との関係を解析するために行う。 In step S15, the lithium ion battery residue (BM) obtained in step S14 is subjected to X-ray diffraction (XRD) measurement. X-ray diffraction (XRD) measurement analyzes the state (compounds, etc.) of the elements contained in the lithium ion battery slag (BM), and analyzes the relationship with Li/Mn leaching/recovery. do for
本発明のリチウムイオン電池滓（ＢＭ）のＸＲＤ測定では、正極活物質に用いた材料や工程Ｓ２の熱処理条件により内容は変わるが、例えば、黒鉛（Ｃ）、ＣｏＮｉ、Ｌｉ２ＣＯ３、Ｃｏ３Ｏ４、ＬｉＡｌＯ２、Ｃｕ、ＣｏＯ、ＭｎＯ等の存在を示すピークが検出される。さらに、本発明では、検出された特定のピークを比較し、それらの強度比（ピーク強度比）Ａ／Ｂに着目する。その理由は以下の通りである。 In the XRD measurement of the lithium ion battery residue (BM) of the present invention, graphite (C), CoNi, Li 2 CO 3 , Co 3 , for example, varies depending on the material used for the positive electrode active material and the heat treatment conditions in step S2. Peaks indicating the presence of O 4 , LiAlO 2 , Cu, CoO, MnO, etc. are detected. Furthermore, in the present invention, the detected specific peaks are compared and their intensity ratio (peak intensity ratio) A/B is focused. The reason is as follows.
正極活物質がＬＣＯ、ＮＣＭ、ＮＣＭＡまたはＮＣＡでは、空間群Ｒ－３ｍに属する結晶構造を持ち、組成の違いに関わらずＸＲＤ測定によれば、回折角度：ｄｉｆｆｒａｃｔｉｏｎ ａｎｇｌｅ ２θ＝１８．７°、３６．８°、４４．５°などに結晶構造由来のピークを示す。ここで、１８．７°のピークが最も大きく、このピークの高さで試料中の正極活物質の結晶構造がどの程度維持されているかをおおよそ把握する事が出来る。その１８．７°のピーク高さが高いほど、結晶構造は維持されていると考えられる。 When the positive electrode active material is LCO, NCM, NCMA, or NCA, it has a crystal structure belonging to the space group R-3m, and according to XRD measurement, diffraction angle: diffraction angle 2θ = 18.7 °, 36 regardless of the difference in composition. Peaks derived from the crystal structure are shown at .8°, 44.5°, and so on. Here, the peak at 18.7° is the largest, and the height of this peak makes it possible to roughly grasp how much the crystal structure of the positive electrode active material in the sample is maintained. It is considered that the higher the peak height at 18.7° is, the more the crystal structure is maintained.
リチウムイオン電池中のＬｉは、放電状態では正極活物質の結晶内に取り込まれている。充電深度が高まるにつれて、正極活物質から負極活物質の黒鉛へ移動して、炭素（Ｃ）－Ｌｉの化合物の状態となる。今回対象としているリチウムイオン電池では、充電電圧が４．２Ｖ程度に制御されることから、正極活物質に元々存在するＬｉ量の約５０％が充電時に正極活物質から抜け出し、残りの約５０％は、正極活物質に残存したままであると考えられる。 Li in a lithium-ion battery is incorporated into crystals of the positive electrode active material in a discharged state. As the charge depth increases, it moves from the positive electrode active material to the negative electrode active material, graphite, and becomes a carbon (C)—Li compound. In the lithium-ion battery that is the subject of this study, since the charging voltage is controlled to about 4.2 V, about 50% of the amount of Li originally present in the positive electrode active material escapes from the positive electrode active material during charging, and the remaining about 50%. is thought to remain in the positive electrode active material.
そこで、本発明者らは正極活物質の結晶構造を加熱によって崩壊させる事で、正極活物質に残存するＬｉが取出しやすくなると考え、この崩壊の程度の指標として、ＸＲＤ測定における１８．７°のピーク（正極活物質の最強ピーク）の強度Ａと２６．５°のピーク（負極活物質での黒鉛の最強ピーク）の強度Ｂとの比（Ａ／Ｂ）に着目することにした。 Therefore, the present inventors considered that the Li remaining in the positive electrode active material can be easily extracted by heating to collapse the crystal structure of the positive electrode active material. Attention was paid to the ratio (A/B) between the intensity A of the peak (strongest peak of the positive electrode active material) and the intensity B of the peak at 26.5° (strongest peak of graphite in the negative electrode active material).
＜リチウムイオン電池滓（ＢＭ）の製造＞
ＮＣＭ５２３（Ｎ：Ｃ：Ｍ＝５：２：３）を正極活物質とする民生用円筒型リチウムイオン電池を、酸素が２体積％含まれる過熱水蒸気雰囲気のバッチ炉で、２００℃／時間の昇温速度で５００℃まで昇温し５．５時間維持した。この間、酸素濃度は維持し、加熱水蒸気の供給は継続した。その後、過熱水蒸気の供給は止め、室温まで１２時間かけて冷却した。その後、クロスフローシュレッダーで、リチウムイオ電池の熱処理物を粉砕、篩分けして０．０１～１０ｍｍの範囲内のサイズの篩下分を分取して、実施例１のＢＭ１を得た。
<Production of lithium-ion battery residue (BM)>
A consumer cylindrical lithium ion battery using NCM523 (N: C: M = 5: 2: 3) as a positive electrode active material was heated at a rate of 200 ° C. / hour in a batch furnace in a superheated steam atmosphere containing 2% by volume of oxygen. The temperature was raised to 500°C at a temperature rate and maintained for 5.5 hours. During this time, the oxygen concentration was maintained and the supply of heated steam was continued. After that, the supply of superheated steam was stopped, and the mixture was cooled to room temperature over 12 hours. After that, the heat-treated lithium ion battery was pulverized and sieved by a cross-flow shredder to obtain an under-sieved fraction having a size in the range of 0.01 to 10 mm, thereby obtaining BM1 of Example 1.
得られたＢＭ１について、ＩＣＰ－ＯＥＳ分析装置（島津製作所社製ＩＣＰＥ－９０００）にて定量分析を行い、さらにＣ量の測定はＴＧ－ＤＴＡを用いて行って、その含有成分を調べた上で、ＸＲＤ測定による結晶構造解析を行った。ＸＲＤ測定は、リガク社製Ｓｍａｒｔ ｌａｂを用いて行った。図３にＸＲＤ測定結果（チャート）ＢＭ１を示す。図３より、以下の（１）～（４）の内容が明らかになった。 The resulting BM1 was subjected to quantitative analysis using an ICP-OES analyzer (ICPE-9000 manufactured by Shimadzu Corporation), and the amount of C was measured using TG-DTA to examine the components contained therein. , crystal structure analysis was performed by XRD measurement. The XRD measurement was performed using Smart lab manufactured by Rigaku. FIG. 3 shows XRD measurement results (chart) BM1. From FIG. 3, the contents of the following (1) to (4) are clarified.
（１）１８．７°のピーク（正極活物質の最強ピーク）と２６．５°（負極活物質：黒鉛の最強ピーク）のピークの高さ（強度）比（１８．７／２６．５）は、０．１０２であった。
（２）ＣｏＮｉの生成を確認した。５１．７°と７６．２°のピークより判定した。なお、４４．４°のピークは、正極活物質と黒鉛に重なるため切り分け不可である。
（３）Ｌｉ２ＣＯ３の生成を確認した。２１．４°、２９．５°、３０．６°及び３１．８°のピークより判定した。
（４）Ｃｏ３Ｏ４の生成を確認した。３７．０°と３８．６°のピークより判定した。
(1) Peak height (intensity) ratio (18.7/26.5) of peaks at 18.7° (strongest peak of positive electrode active material) and 26.5° (strongest peak of negative electrode active material: graphite) was 0.102.
(2) The formation of CoNi was confirmed. Judgment was made from peaks at 51.7° and 76.2°. Note that the peak at 44.4° overlaps the positive electrode active material and graphite and cannot be separated.
(3) The formation of Li 2 CO 3 was confirmed. Judgment was made from the peaks at 21.4°, 29.5°, 30.6° and 31.8°.
(4) Production of Co 3 O 4 was confirmed. Judgment was made from peaks at 37.0° and 38.6°.
＜Ｌｉの水浸出＞
ＢＭ１ １０ｇを１００ｍＬの水道水に分散させ、ホットスターラーを用いて、１２０℃／時間の昇温速度で、３０℃、６０℃、８０℃の３つの温度まで加熱した。各温度に到達してから各々２時間、５時間、２４時間の間温度を保持しながら攪拌を続け（計９条件）、室温まで冷却した後に濾過した。得られた９条件での濾液（濾液Ａ）と濾過残渣中のＬｉ、Ｃｏ、ＮｉおよびＭｎの量を測定した。なお、濾過残渣中のＬｉ、Ｃｏ、ＮｉおよびＭｎ量は、濾過残渣を熱王水で溶解後、濾過によって回収された濾液（濾液Ｂ）中のＬｉ、Ｃｏ、ＮｉおよびＭｎの量とした。Ｌｉ、Ｃｏ、ＮｉおよびＭｎの分析は、濾液Ａおよび濾液Ｂを３％硝酸によって適宣希釈してからＩＣＰ（島津製作所社製ＩＣＰＥ－９０００）を用いて行った。Ｌｉ、Ｃｏ、ＮｉおよびＭｎの回収率は、濾液Ａ中の各金属質量／（濾液Ａ中の各金属質量＋濾液Ｂ中の各金属質量）＊１００で算出した。
<Water leaching of Li>
10 g of BM1 was dispersed in 100 mL of tap water, and heated to three temperatures of 30° C., 60° C., and 80° C. at a rate of 120° C./hour using a hot stirrer. After reaching each temperature, stirring was continued while maintaining the temperature for 2 hours, 5 hours, and 24 hours (9 conditions in total), and the mixture was cooled to room temperature and then filtered. The amounts of Li, Co, Ni and Mn in the filtrate (filtrate A) and the filtration residue under the nine conditions were measured. The amounts of Li, Co, Ni and Mn in the filtration residue were the amounts of Li, Co, Ni and Mn in the filtrate (filtrate B) collected by filtration after dissolving the filtration residue in hot aqua regia. Li, Co, Ni and Mn were analyzed by appropriately diluting filtrate A and filtrate B with 3% nitric acid and then using ICP (ICPE-9000 manufactured by Shimadzu Corporation). The recovery rates of Li, Co, Ni and Mn were calculated by mass of each metal in filtrate A/(mass of each metal in filtrate A+mass of each metal in filtrate B)*100.
Ｌｉの回収率（％）は、以下のようになった。Ｃｏ、Ｍｎ、及びＮｉの回収率はどの条件でもほぼ０％であった。
３０℃ ６０℃ ８０℃
２Ｈ： ４６．４ ４９．９ ４９．８
５Ｈ： ５２．３ ５０．２ ４７．８
２４Ｈ： ４７．３ ４９．９ ４０．９
この結果から、Ｌｉのみが高い割合で水に浸出し、ＣｏとＮｉは水に浸出させずに、Ｌｉと（Ｃｏ＋Ｎｉ）の固液分離が可能であることが分かった。
The recovery rate (%) of Li was as follows. The recoveries of Co, Mn and Ni were almost 0% under any conditions.
30°
2H: 46.4 49.9 49.8
5H: 52.3 50.2 47.8
24H: 47.3 49.9 40.9
From this result, it was found that solid-liquid separation of Li and (Co+Ni) is possible with only Li leaching into water at a high rate and Co and Ni not leaching into water.
＜ＬｉとＭｎの硫酸水溶液浸出＞
（ａ）ＢＭ１ １０ｇを１００ｍＬの１、２、３ｗｔ％の８０℃のＨ２ＳＯ４水溶液中で２時間浸出反応させたところ、Ｌｉ、Ｍｎ、Ｃｏ、及びＮｉの回収率（％）は、以下のようになった。
１ｗｔ％ ２ｗｔ％ ３ｗｔ％
Ｌｉ： ５２．０ ５８．２ ７４．３
Ｍｎ： ０．０２ ３９．３ ７７．２
Ｃｏ： ０．００ ０．４２ ２．４４
Ｎｉ： ０. ００ ０．３１ ０．１７
<Leaching of Li and Mn into a sulfuric acid aqueous solution>
(a) 10 g of BM1 was subjected to a leaching reaction in 100 mL of 1, 2, 3 wt% H 2 SO 4 aqueous solution at 80 ° C. for 2 hours. became like
1 wt% 2 wt% 3 wt%
Li: 52.0 58.2 74.3
Mn: 0.02 39.3 77.2
Co: 0.00 0.42 2.44
Ni: 0.00 0.31 0.17
（ｂ）ＢＭ１ １０ｇを１００ｍＬの３０℃、６０℃、８０℃の３ｗｔ％のＨ２ＳＯ４水溶液中で２時間浸出反応させたところ、Ｌｉ、Ｍｎ、Ｃｏ、及びＮｉの回収率（％）は、以下のようになった。
３０℃ ６０℃ ８０℃
Ｌｉ： ６６．１ ７１．２ ７４．３
Ｍｎ： ７２．０ ７２．０ ７７．２
Ｃｏ： １４．２ １０．３ ２．４４
Ｎｉ： ９．０５ ４．０７ ０．１７
(b) 10 g of BM1 was subjected to a leaching reaction in 100 mL of 3 wt% H2SO4 aqueous solution at 30°C, 60°C and 80°C for 2 hours. , became:
30°
Li: 66.1 71.2 74.3
Mn: 72.0 72.0 77.2
Co: 14.2 10.3 2.44
Ni: 9.05 4.07 0.17
（ｃ）ＢＭ１ １０ｇを０．５、２、５、２４時間の浸出時間（Ｈ）で、１００ｍＬの８０℃の３ｗｔ％のＨ２ＳＯ４水溶液中で浸出反応させたところ、Ｌｉ、Ｍｎ、Ｃｏ、及びＮｉの回収率（％）は、以下のようになった。
０．５Ｈ ２Ｈ ５Ｈ ２４Ｈ
Ｌｉ： ７９．４ ７２．６ ７０．７ ７９．８
Ｍｎ： ６９．４ ６４．９ ５２．３ ２３．７
Ｃｏ： ７．１４ ０．９１ ０．０９ ０．２１
Ｎｉ： １．８９ ０．１０ ０．９１ ０．２１
(c) 10 g of BM1 was leached in 100 mL of 3 wt% H 2 SO 4 aqueous solution at 80° C. with leaching times (H) of 0.5, 2, 5 and 24 hours, yielding Li, Mn, Co , and the recovery rate (%) of Ni were as follows.
0.5H 2H 5H 24H
Li: 79.4 72.6 70.7 79.8
Mn: 69.4 64.9 52.3 23.7
Co: 7.14 0.91 0.09 0.21
Ni: 1.89 0.10 0.91 0.21
上記（ａ）～（ｃ）のＢＭ１の浸出結果（回収率）から、温度３０℃～８０℃で濃度１～３ｗｔ％の硫酸水溶液中に浸出時間０．５～２４時間で、ＬｉとＭｎを高い割合で浸出させることができる一方で、ＣｏとＮｉはほとんど浸出させることなく、（Ｌｉ＋Ｍｎ）と（Ｃｏ＋Ｎｉ）の固液分離が可能であることが明らかになった。 From the leaching results (recovery rate) of BM1 in (a) to (c) above, Li and Mn were dissolved in an aqueous sulfuric acid solution with a concentration of 1 to 3 wt% at a temperature of 30 ° C to 80 ° C for a leaching time of 0.5 to 24 hours. It was clarified that solid-liquid separation of (Li+Mn) and (Co+Ni) is possible without leaching out Co and Ni at a high rate.
ＮＣＭ５２３を正極活物質とする民生用円筒型リチウムイオン電池を大気雰囲気下３００℃に設定したコンベアー式乾燥炉に１５分間搬送して、リチウムイオン電池内の電解液を蒸発させた。次に、大気雰囲気が流通可能なローターキルンに５６０℃で２０分間加熱した。得られた加熱済みリチウムイオン電池を室温まで冷却後、二軸破砕機で粉砕した。その後、振動篩で篩分けし、０．０１～１０ｍｍの範囲内のサイズの篩下分を分取して、実施例２のＢＭ２を得た。 A cylindrical lithium ion battery for consumer use using NCM523 as a positive electrode active material was transported to a conveyor-type drying furnace set at 300° C. in an air atmosphere for 15 minutes to evaporate the electrolyte in the lithium ion battery. Next, it was heated at 560° C. for 20 minutes in a rotor kiln through which an air atmosphere could flow. The resulting heated lithium-ion battery was cooled to room temperature and crushed with a twin-screw crusher. After that, BM2 of Example 2 was obtained by sieving with a vibrating sieve to fractionate the under-sieved portion having a size within the range of 0.01 to 10 mm.
実施例１のＢＭ１の場合と同様に、含有成分を調べた上で、ＸＲＤ測定による結晶構造解析を行った。図３にＸＲＤ測定結果（チャート）ＢＭ２を示す。図３より、以下の内容が明らかになった。
（１）１８．７°と２６．５°のピーク強度比（１８．７／２６．５）は、０．０９８４であった。
（２）ＣｏＮｉ、Ｌｉ２ＣＯ３、Ｃｏ３Ｏ４の生成を確認した。
As in the case of BM1 of Example 1, after examining the components, the crystal structure was analyzed by XRD measurement. FIG. 3 shows XRD measurement results (chart) BM2. From FIG. 3, the following contents became clear.
(1) The peak intensity ratio between 18.7° and 26.5° (18.7/26.5) was 0.0984.
(2) Production of CoNi, Li2CO3 , and Co3O4 was confirmed.
ＮＣＭ５２３を正極活物質とする民生用円筒型リチウムイオン電池を２００℃／時間の昇温速度で６００℃まで昇温し、５．５時間維持した以外は、実施例１と同様の方法で、実施例３のＢＭ３を得た。 In the same manner as in Example 1, except that a consumer cylindrical lithium ion battery using NCM523 as a positive electrode active material was heated to 600 ° C. at a temperature rising rate of 200 ° C./hour and maintained for 5.5 hours. BM3 of Example 3 was obtained.
実施例１のＢＭ１の場合と同様に、含有成分を調べた上で、ＸＲＤ測定による結晶構造解析を行った。図３にＸＲＤ測定結果（チャート）ＢＭ３を示す。図３より、以下の内容が明らかになった。
（１）１８．７°と２６．５°のピーク強度比（１８．７／２６．５）は、０．０３２８であった。
（２）ＣｏＮｉ、Ｌｉ２ＣＯ３、Ｃｏ３Ｏ４の生成を確認した。
As in the case of BM1 of Example 1, after examining the components, the crystal structure was analyzed by XRD measurement. FIG. 3 shows XRD measurement results (chart) BM3. From FIG. 3, the following contents became clear.
(1) The peak intensity ratio between 18.7° and 26.5° (18.7/26.5) was 0.0328.
(2) Production of CoNi, Li2CO3 , and Co3O4 was confirmed.
＜リチウムイオン電池滓（ＢＭ）の製造＞
実施例４として比較例１の実験を行った。ＮＣＭ５２３を正極活物質とする民生用円筒型リチウムイオン電池を大気雰囲気下２００℃に設定したコンベアー式乾燥炉に１５分間搬送した。次に、大気を流通可能なローターキルンに４００℃で２０分間加熱した。得られた熱処理済みリチウムイオン電池を室温まで冷却後、二軸破砕機で粉砕した。その後、振動篩で篩分けし、０．０１～１０ｍｍの範囲内のサイズの篩下分を分取して、比較例１のＢＭであるＢＭＲを得た。
<Production of lithium-ion battery residue (BM)>
As Example 4, an experiment of Comparative Example 1 was conducted. A consumer cylindrical lithium ion battery using NCM523 as a positive electrode active material was transported for 15 minutes to a conveyor-type drying furnace set at 200° C. in an air atmosphere. Next, it was heated at 400° C. for 20 minutes in a rotor kiln capable of circulating air. The obtained heat-treated lithium-ion battery was cooled to room temperature and then pulverized with a twin-screw crusher. After that, it was sieved with a vibrating sieve, and the under-sieved fraction having a size within the range of 0.01 to 10 mm was fractionated to obtain BMR, which is the BM of Comparative Example 1.
実施例１のＢＭ１の場合と同様に、含有成分を調べた上で、ＸＲＤ測定による結晶構造解析を行った。図３にＸＲＤ測定結果（チャート）ＢＭＲを示す。図３より、以下の（５）～（８）の内容が明らかになった。
（１）１８．７°と２６．５°のピーク強度比（１８．７／２６．５）は、０．１８であった。
（２）ＣｏＮｉの生成は確認できなかった。
（３）Ｌｉ２ＣＯ３の生成は、トレース量（微量で一定基準以下または測定限界値以下の量）しか確認できなかった。
（４）Ｃｏ３Ｏ４の生成を確認した。
As in the case of BM1 of Example 1, after examining the components, the crystal structure was analyzed by XRD measurement. FIG. 3 shows the XRD measurement results (chart) BMR. From FIG. 3, the contents of the following (5) to (8) are clarified.
(1) The peak intensity ratio between 18.7° and 26.5° (18.7/26.5) was 0.18.
(2) Formation of CoNi could not be confirmed.
(3) Only a trace amount of Li 2 CO 3 could be confirmed (a trace amount of less than a certain standard or less than the limit of measurement).
(4) Production of Co 3 O 4 was confirmed.
＜Ｌｉの水浸出＞
実施例１のＢＭ１の場合と同様な方法により、実施例４（比較例１）のＢＭＲ １０ｇを１００ｍＬの水道水に分散させ、浸出温度８０℃、浸出時間２時間でＬｉの浸出試験を行った。その結果、Ｌｉの浸出率は１５．３％となり、Ｃｏ、Ｍｎ、及びＮｉの回収率はいずれも０％であった。
<Water leaching of Li>
10 g of BMR of Example 4 (Comparative Example 1) was dispersed in 100 mL of tap water in the same manner as BM1 of Example 1, and a Li leaching test was performed at a leaching temperature of 80° C. and a leaching time of 2 hours. . As a result, the Li leaching rate was 15.3%, and the recovery rates of Co, Mn and Ni were all 0%.
＜ＬｉとＭｎの硫酸水溶液浸出＞
実施例４（比較例１）のＢＭＲに対して、５ｗｔ％の３０℃のＨ２ＳＯ４水溶液中で２時間浸出反応させたところ、Ｌｉ、Ｍｎ、Ｃｏ、及びＮｉの浸出率（％）は、以下のようになった。
Ｌｉ Ｍｎ Ｃｏ Ｎｉ
ＢＭＲ： ３６．９ ２６．３ ２５．２ ２２．８
ＬｉとＭｎの浸出率が低く、かつＣｏとＮｉも同様な割合（％）で浸出してしまうことから、（Ｌｉ＋Ｍｎ）と（Ｃｏ＋Ｎｉ）の固液分離が困難であることが確認できた。
<Leaching of Li and Mn into a sulfuric acid aqueous solution>
When the BMR of Example 4 (Comparative Example 1) was subjected to a leaching reaction in a 5 wt% H2SO4 aqueous solution at 30°C for 2 hours, the leaching rate (%) of Li, Mn, Co, and Ni was , became:
LiMnCoNi
BMR: 36.9 26.3 25.2 22.8
It was confirmed that solid-liquid separation of (Li + Mn) and (Co + Ni) is difficult because the leaching rate of Li and Mn is low, and Co and Ni are leached at the same ratio (%).
実施例１～３と実施例４（比較例１）の製造条件とＸＲＤ測定結果を比較する事により、
（ｉ）加熱温度が５００℃～６００℃であること、
（ｉｉ）加熱時の雰囲気中の酸素濃度が２～２１体積％（大気）以下であること、及び
（ｉｉｉ）加熱温度を０．３３～５．５時間維持することで、
（ａ）ＢＭのＸＲＤ測定チャートにおける、２θが１８．７°のピークと２６．５°のピークの高さ（強度）比が０．１０２以下となること
（ｂ）ＣｏＮｉ化合物が生成すること
（ｃ）Ｌｉ２ＣＯ３が生成すること
の３つが同時に生じ得る事が明らかとなった。また、その際のＢＭ中の黒鉛（Ｃ）の含有量は、約２０～３１質量％である事が分かった。
By comparing the production conditions and XRD measurement results of Examples 1 to 3 and Example 4 (Comparative Example 1),
(i) the heating temperature is 500° C. to 600° C.;
(ii) the oxygen concentration in the atmosphere during heating is 2 to 21% by volume (atmosphere) or less, and (iii) the heating temperature is maintained for 0.33 to 5.5 hours,
(a) In the BM XRD measurement chart, the height (intensity) ratio of the peak at 2θ of 18.7° and the peak at 26.5° should be 0.102 or less. c) the formation of Li 2 CO 3 can occur simultaneously. Also, it was found that the content of graphite (C) in the BM at that time was about 20 to 31% by mass.
実施例１と実施例４（比較例１）のＬｉの水浸出結果（回収率）の比較から、実施例１のＢＭ１は、比較例１のＢＭＲの回収率（約１５％）の３倍以上の高い回収率（約５０％）でＬｉを回収することができることが分かった。 From the comparison of the Li water leaching results (recovery rate) of Example 1 and Example 4 (Comparative Example 1), BM1 of Example 1 is more than three times the recovery rate of BMR of Comparative Example 1 (about 15%). It was found that Li can be recovered with a high recovery rate (approximately 50%).
実施例１と実施例４（比較例１）の硫酸水溶液浸出結果（回収率）から、実施例１のＢＭ１では、（Ｌｉ＋Ｍｎ）と（Ｃｏ＋Ｎｉ）の固液分離が可能であるが、実施例４（比較例１）のＢＭＲでは、困難であることが明らかになった。 From the sulfuric acid aqueous solution leaching results (recovery rate) of Examples 1 and 4 (Comparative Example 1), solid-liquid separation of (Li + Mn) and (Co + Ni) is possible in BM1 of Example 1, but in Example 4 It became clear that the BMR of (Comparative Example 1) is difficult.
本発明の実施形態について、図を参照しながら説明をした。しかし、本発明はこれらの実施形態に限られるものではない。本発明はその趣旨を逸脱しない範囲で当業者の知識に基づき種々なる改良、修正、変形を加えた態様で実施できるものである。 Embodiments of the present invention have been described with reference to the drawings. However, the invention is not limited to these embodiments. The present invention can be implemented with various improvements, modifications, and variations based on the knowledge of those skilled in the art without departing from the spirit of the invention.
リチウムイオン電池滓とその製造方法は、廃リチウムイオン電池からの金属の回収において幅広く利用することができる。
Lithium ion battery slag and method of making same can be widely used in the recovery of metals from waste lithium ion batteries.
Claims (8)
（ａ）Ｘ線回折（ＸＲＤ）測定において、Ｌｉを含む正極活物質による回折角度１８．７°のピーク強度Ａと負極活物質の黒鉛による回折角度２６．５°のピーク強度Ｂとの比（Ａ／Ｂ）が０～０．１５の範囲にある、前記リチウムイオン電池の電池滓を準備する工程と、
（ｂ）前記電池滓を水中に分散させ、３０～８０℃の浸出液中に２～２４時間かけてリチウムを浸出させる工程と、
を含む方法。 A method for recovering metals from a lithium ion battery containing lithium (Li), cobalt (Co) and nickel (Ni) as positive electrode active materials and graphite (C) as a negative electrode active material, comprising:
(a) In X-ray diffraction (XRD) measurement, the ratio of the peak intensity A at a diffraction angle of 18.7 ° due to the positive electrode active material containing Li to the peak intensity B at a diffraction angle of 26.5 ° due to graphite of the negative electrode active material ( A/B) is in the range of 0 to 0.15, providing a battery slag of the lithium ion battery;
(b) dispersing the battery slag in water and leaching lithium in a leaching solution at 30 to 80° C. for 2 to 24 hours;
method including.
（ａ）Ｘ線回折（ＸＲＤ）測定において、Ｌｉを含む正極活物質による回折角度１８．７°のピーク強度Ａと負極活物質の黒鉛による回折角度２６．５°のピーク強度Ｂとの比（Ａ／Ｂ）が０～０．１５の範囲にある、前記リチウムイオン電池の電池滓を準備する工程と、
（ｂ）前記電池滓を１～３質量％の濃度の硫酸水溶液中に分散させ、３０～８０℃の浸出液中に０．５～２４時間かけてリチウムとマンガンを浸出させる工程と、
を含む方法。 A method for recovering metals from a lithium ion battery containing lithium (Li), cobalt (Co) and nickel (Ni) as positive electrode active materials and graphite (C) as a negative electrode active material, comprising:
(a) In X-ray diffraction (XRD) measurement, the ratio of the peak intensity A at a diffraction angle of 18.7 ° due to the positive electrode active material containing Li to the peak intensity B at a diffraction angle of 26.5 ° due to graphite of the negative electrode active material ( A/B) is in the range of 0 to 0.15, providing a battery slag of the lithium ion battery;
(b) a step of dispersing the battery slag in an aqueous sulfuric acid solution having a concentration of 1 to 3% by mass, and leaching lithium and manganese into the leaching solution at 30 to 80° C. for 0.5 to 24 hours;
method including.
（ａ１）前記リチウムイオン電池を加熱炉内の大気中で５００～６００℃の温度で０．３～１０時間保持する熱処理工程と、
（ａ２）熱処理後の前記リチウムイオン電池を粉砕して粉砕物を得る粉砕工程と、
（ａ３）前記粉砕物を篩分けして粉状のリチウムイオン電池滓を得る篩分け工程と、
を含む、請求項１または２に記載の方法。 The step (a) of preparing the battery slag of the lithium ion battery comprises:
(a1) a heat treatment step of holding the lithium ion battery in the atmosphere in a heating furnace at a temperature of 500 to 600° C. for 0.3 to 10 hours;
(a2) a pulverizing step of pulverizing the heat-treated lithium ion battery to obtain a pulverized material;
(a3) a sieving step of sieving the pulverized material to obtain powdery lithium ion battery slag;
3. The method of claim 1 or 2, comprising:
The heat treatment step (a1) includes replacing the air in the heating furnace with an atmosphere of an inert gas or superheated steam with an oxygen concentration of 1 to 21% by volume and an inert gas or atmosphere with an oxygen concentration of 1 to 3% by volume. 8. The method of claim 7, comprising heating in any of an atmosphere of superheated steam.
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