JP6651115B1 - Method for recovering lithium from lithium ion battery - Google Patents
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- JP6651115B1 JP6651115B1 JP2019087800A JP2019087800A JP6651115B1 JP 6651115 B1 JP6651115 B1 JP 6651115B1 JP 2019087800 A JP2019087800 A JP 2019087800A JP 2019087800 A JP2019087800 A JP 2019087800A JP 6651115 B1 JP6651115 B1 JP 6651115B1
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 117
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 116
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 51
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 76
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 74
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 67
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 239000011149 active material Substances 0.000 claims abstract description 22
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 19
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 18
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 18
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 44
- 239000000706 filtrate Substances 0.000 claims description 39
- 239000012298 atmosphere Substances 0.000 claims description 22
- 239000001569 carbon dioxide Substances 0.000 claims description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 20
- 239000007773 negative electrode material Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000013058 crude material Substances 0.000 abstract 1
- 238000010586 diagram Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 239000007774 positive electrode material Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 239000002699 waste material Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 7
- 239000008151 electrolyte solution Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010828 elution Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 3
- 229910001947 lithium oxide Inorganic materials 0.000 description 3
- -1 lithium-ion compound Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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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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- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
【課題】リチウムを低コストかつ高収率で回収することができるリチウムイオン電池からのリチウムの回収方法を提供する。【解決手段】本発明は、リチウムイオン電池から有機溶媒を除去する工程と、有機溶媒が除去されたリチウムイオン電池から活物質を分離する工程と、活物質に含まれるリチウム化合物を還元して粗炭酸リチウムを得る工程と、粗炭酸リチウムに、難溶性炭酸塩を生成し得る金属水酸化物溶液を添加し、水酸化リチウム溶液を得る工程と、水酸化リチウム溶液に炭酸ガスを供給し、析出した炭酸リチウムを回収する工程とを備える。【選択図】 なしProvided is a method for recovering lithium from a lithium ion battery, which can recover lithium at a low cost and in a high yield. The present invention includes a step of removing an organic solvent from a lithium ion battery, a step of separating an active material from the lithium ion battery from which the organic solvent has been removed, and a step of reducing a lithium compound contained in the active material to obtain a crude material. A step of obtaining lithium carbonate, a step of adding a metal hydroxide solution capable of forming a hardly soluble carbonate to the crude lithium carbonate, and a step of obtaining a lithium hydroxide solution; Recovering the removed lithium carbonate. [Selection diagram] None
Description
本発明は、リチウムイオン電池からのリチウムの回収方法に関する。 The present invention relates to a method for recovering lithium from a lithium ion battery.
近年、リチウムイオン電池の普及に伴い、主として廃リチウムイオン電池からリチウム等の有価金属を回収する方法が種々提案されている。 In recent years, with the spread of lithium ion batteries, various methods have been proposed for recovering valuable metals such as lithium mainly from waste lithium ion batteries.
例えば、従来、リチウムイオン電池からリチウムを回収する方法として、廃リチウムイオン電池を５５０〜６５０℃の温度で焙焼して、該廃リチウムイオン電池に含まれるリチウムを酸化リチウム、炭酸リチウム、水酸化リチウム等の形態とした後、該廃リチウムイオン電池を粉砕し、得られた粉末を水又は酸性溶液に溶解し、得られた溶液に炭酸イオンを供給してリチウムを炭酸水素リチウムとして溶解させた後、加熱して脱炭酸することにより析出する炭酸リチウムを回収する方法が知られている（例えば、特許文献１参照）。 For example, conventionally, as a method of recovering lithium from a lithium ion battery, a waste lithium ion battery is roasted at a temperature of 550 to 650 ° C., and lithium contained in the waste lithium ion battery is converted to lithium oxide, lithium carbonate, and hydroxide. After being in the form of lithium or the like, the waste lithium ion battery was pulverized, the obtained powder was dissolved in water or an acidic solution, and carbonate ions were supplied to the obtained solution to dissolve lithium as lithium hydrogen carbonate. Then, a method of recovering lithium carbonate precipitated by heating and decarbonating is known (for example, see Patent Document 1).
尚、前記廃リチウムイオン電池としては、電池製品としての寿命の消尽した使用済みのリチウムイオン電池、製造不良等の原因により廃棄されたリチウムイオン電池等が用いられる。 As the waste lithium ion battery, a used lithium ion battery whose life as a battery product has been exhausted, a lithium ion battery discarded due to a manufacturing defect, or the like is used.
しかしながら、特許文献１記載の方法では、廃リチウムイオン電池を５５０〜６５０℃の温度で焙焼した後、粉砕しているので、該廃リチウムイオン電池に含まれるリチウムの酸化リチウム、炭酸リチウム、水酸化リチウム等への変換率が低下し、リチウムを十分に回収できないという不都合がある。 However, in the method described in Patent Document 1, the waste lithium ion battery is roasted at a temperature of 550 to 650 ° C. and then pulverized, so that lithium oxide, lithium carbonate, and water contained in the waste lithium ion battery are contained. There is a disadvantage that the conversion rate to lithium oxide or the like decreases, and lithium cannot be sufficiently recovered.
また、リチウムは過去に一時的に価格が高騰したことはあるものの、基本的には安価であり、リチウムを含む廃水をそのまま河川等に放流することもできるので、低コストかつ高収率で回収することが望まれる。 In addition, although lithium prices have temporarily risen in the past, they are basically inexpensive, and wastewater containing lithium can be discharged directly to rivers, etc., so it can be recovered at low cost and high yield. It is desired to do.
本発明は、かかる不都合を解消して、リチウムイオン電池からリチウムを低コストかつ高収率で回収することができるリチウムイオン電池からのリチウムの回収方法を提供することを目的とする。 An object of the present invention is to provide a method for recovering lithium from a lithium ion battery, which can solve such a disadvantage and can recover lithium from a lithium ion battery at low cost and with high yield.
かかる目的を達成するために、本発明のリチウムイオン電池からのリチウムの回収方法は、リチウムイオン電池を不活性雰囲気下で焙焼して、該リチウムイオン電池から有機溶媒を除去する工程と、有機溶媒が除去されたリチウムイオン電池から活物質を分離する工程と、前記リチウムイオン電池から分離された活物質を、不活性雰囲気下、リチウムイオン電池の負極活物質に含まれる還元性物質としての炭素と共に６００℃以上の温度で焙焼して、前記活物質に含まれるリチウム化合物を還元して粗炭酸リチウムを得る工程と、前記粗炭酸リチウムに、難溶性炭酸塩を生成し得る金属水酸化物溶液を添加し、水酸化リチウム溶液を得る工程と、前記水酸化リチウム溶液に炭酸ガスを供給し、析出した炭酸リチウムを回収する工程とを備えることを特徴とする。 In order to achieve the object, a method for recovering lithium from a lithium ion battery of the present invention comprises the steps of: roasting a lithium ion battery under an inert atmosphere to remove an organic solvent from the lithium ion battery; A step of separating the active material from the lithium ion battery from which the solvent has been removed, and removing the active material separated from the lithium ion battery under an inert atmosphere by using carbon as a reducing material contained in the negative electrode active material of the lithium ion battery. And roasting at a temperature of 600 ° C. or more to reduce a lithium compound contained in the active material to obtain crude lithium carbonate, and a metal hydroxide capable of forming a hardly soluble carbonate in the crude lithium carbonate. A step of adding a solution to obtain a lithium hydroxide solution, and a step of supplying carbon dioxide to the lithium hydroxide solution and collecting the precipitated lithium carbonate. And wherein the door.
本発明のリチウムイオン電池からのリチウムの回収方法において、前記リチウムイオン電池は、電池製品としての寿命の消尽した使用済みのリチウムイオン電池、製造不良等の原因により廃棄されたリチウムイオン電池等であってもよく、未使用のリチウムイオン電池であってもよい。 In the method for recovering lithium from a lithium-ion battery according to the present invention, the lithium-ion battery may be a used lithium-ion battery having a depleted life as a battery product, a lithium-ion battery discarded due to a manufacturing defect, or the like. Or an unused lithium ion battery.
本発明のリチウムイオン電池からのリチウムの回収方法では、まず、リチウムイオン電池を不活性雰囲気下で焙焼して、リチウムイオン電池から有機溶媒を除去し、有機溶媒が除去されたリチウムイオン電池から活物質を分離し、分離された活物質に含まれるリチウム化合物を還元して粗炭酸リチウムを得る。リチウムイオン電池は、一般に有機溶媒を含む電解液、有機高分子膜及びアルミニウム箔等を含んでおり、焙焼した際に該有機溶媒が自発的に燃焼することで、該有機溶媒や有機高分子膜が炭化したりアルミニウム箔が溶融すると、リチウムを含む活物質粉の分離性が低下するとともに、該リチウムイオン電池に含まれるリチウムが還元されにくくなり、リチウムの回収率が低下する。本発明のリチウムイオン電池からのリチウムの回収方法では、予め、リチウムイオン電池を不活性雰囲気下で焙焼して、リチウムイオン電池から前記溶媒を除去しておくことにより、リチウムイオン化合物を還元して粗炭酸リチウムを得る工程において、該リチウムイオン電池に含まれるリチウムを十分に還元することができる。
また、本発明のリチウムイオン電池からのリチウムの回収方法において、前記活物質に含まれるリチウム化合物を還元して粗炭酸リチウムを得る工程は、前記リチウムイオン電池から分離された活物質を、不活性雰囲気下、リチウムイオン電池の負極活物質に含まれる還元性物質としての炭素と共に６００℃以上の温度で焙焼する。前記活物質の焙焼を６００℃未満の温度で行うと、前記活物質に含まれるリチウム化合物の還元を十分に行うことができないことがある。
In the method for recovering lithium from a lithium-ion battery of the present invention, first, the lithium-ion battery is roasted in an inert atmosphere to remove the organic solvent from the lithium-ion battery, and from the lithium-ion battery from which the organic solvent has been removed. The active material is separated, and a lithium compound contained in the separated active material is reduced to obtain crude lithium carbonate. Lithium-ion batteries generally include an electrolytic solution containing an organic solvent, an organic polymer film, an aluminum foil, and the like. When the organic solvent burns spontaneously during roasting, the organic solvent or organic polymer When the film is carbonized or the aluminum foil is melted, the separability of the active material powder containing lithium is reduced, and the lithium contained in the lithium ion battery is not easily reduced, and the lithium recovery rate is reduced. In the method for recovering lithium from a lithium-ion battery of the present invention, the lithium-ion compound is reduced by previously roasting the lithium-ion battery in an inert atmosphere and removing the solvent from the lithium-ion battery. In the step of obtaining crude lithium carbonate, lithium contained in the lithium ion battery can be sufficiently reduced.
Further, in the method for recovering lithium from a lithium ion battery of the present invention, the step of reducing the lithium compound contained in the active material to obtain crude lithium carbonate includes the step of inactivating the active material separated from the lithium ion battery. Under an atmosphere, it is roasted at a temperature of 600 ° C. or more together with carbon as a reducing substance contained in a negative electrode active material of a lithium ion battery. If the roasting of the active material is performed at a temperature lower than 600 ° C., the lithium compound contained in the active material may not be sufficiently reduced.
本発明のリチウムイオン電池からのリチウムの回収方法では、次に、前記粗炭酸リチウムに、難溶性炭酸塩を生成し得る金属水酸化物溶液を添加する。このようにすると、前記金属水酸化物を構成する金属が炭酸と反応して難溶性炭酸塩を生成する一方、前記粗炭酸リチウムに含まれるリチウムが水酸化リチウムに転換されて溶解し、水酸化リチウム溶液を得ることができる。このとき、前記粗炭酸リチウムは、リチウムの他に、前記電解液由来のフッ素やリン酸を含むことがあるが、前記電解液由来のフッ素やリン酸の化合物は前記金属水酸化物を構成する金属と反応してそれ自体難溶性塩を形成し、あるいは前記難溶性炭酸塩に捕捉されるので、純度の高い水酸化リチウム溶液を得ることができる。 In the method for recovering lithium from a lithium ion battery according to the present invention, a metal hydroxide solution capable of forming a hardly soluble carbonate is added to the crude lithium carbonate. In this case, the metal constituting the metal hydroxide reacts with carbonic acid to form a hardly soluble carbonate, while lithium contained in the crude lithium carbonate is converted into lithium hydroxide and dissolved, and A lithium solution can be obtained. At this time, the crude lithium carbonate may contain, in addition to lithium, fluorine or phosphoric acid derived from the electrolytic solution, but the compound of fluorine or phosphoric acid derived from the electrolytic solution constitutes the metal hydroxide. Since it reacts with the metal to form a sparingly soluble salt or is captured by the sparingly soluble carbonate, a highly pure lithium hydroxide solution can be obtained.
本発明のリチウムイオン電池からのリチウムの回収方法では、次に、前記水酸化リチウム溶液に炭酸ガスを供給する。このようにすると、前記水酸化リチウムが炭酸と反応して生成した炭酸リチウムが前記水酸化リチウム溶液中に析出する。そこで、析出した炭酸リチウムを回収することにより、リチウムイオン電池からリチウムを低コストかつ高収率で回収することができる。 Next, in the method for recovering lithium from a lithium ion battery of the present invention, carbon dioxide is supplied to the lithium hydroxide solution. In this case, lithium carbonate produced by the reaction of the lithium hydroxide with the carbonic acid is deposited in the lithium hydroxide solution. Therefore, by recovering the precipitated lithium carbonate, lithium can be recovered from the lithium ion battery at low cost and high yield.
本発明のリチウムイオン電池からのリチウムの回収方法において、前記リチウムイオン電池から有機溶媒を除去する工程は、２００〜３００℃の範囲の温度で焙焼することが好ましい。このようにすることにより、前記リチウムイオン電池の正負極間に配設されているセパレータが分解することなく、前記有機溶媒を蒸発させて除去することができる。 In the method for recovering lithium from a lithium ion battery of the present invention, the step of removing the organic solvent from the lithium ion battery is preferably performed by roasting at a temperature in the range of 200 to 300 ° C. By doing so, the organic solvent can be evaporated and removed without decomposing the separator provided between the positive and negative electrodes of the lithium ion battery.
前記焙焼を２００℃未満の温度で行うと、前記有機溶媒を蒸発させることができないことがある。また、前記焙焼を、大気雰囲気等の酸化雰囲気下、３００℃超の温度で行うと前記セパレータが分解又は炭化し、リチウムの回収率が低下することがある。 If the roasting is performed at a temperature lower than 200 ° C., the organic solvent may not be able to be evaporated. Further, when the roasting is performed in an oxidizing atmosphere such as an air atmosphere at a temperature higher than 300 ° C., the separator may be decomposed or carbonized, and the lithium recovery may decrease.
本発明のリチウムイオン電池からのリチウムの回収方法では、前記のように焙焼を行うときには、該焙焼に先立って、前記リチウムイオン電池の放電を行うことが好ましい。放電を行うことなく、前記リチウムイオン電池を前記焙焼に供すると、該リチウムイオン電池が爆発することがある。 In the method for recovering lithium from a lithium ion battery according to the present invention, when performing the roasting as described above, it is preferable to discharge the lithium ion battery prior to the roasting. If the lithium ion battery is subjected to the roasting without discharging, the lithium ion battery may explode.
また、本発明のリチウムイオン電池からのリチウムの回収方法において、有機溶媒が除去されたリチウムイオン電池から活物質を分離する工程は、例えば該リチウムイオン電池を破砕することにより行うことができる。リチウムイオン電池は、一般に、アルミニウム泊等からなる正極電極板に塗布された正極活物質と、銅箔等の負極電極板に塗布された負極活物質とが、セパレータを介して重ね合わされた状態でアルミニウム等からなる筐体に収容されている。 In the method for recovering lithium from a lithium ion battery of the present invention, the step of separating the active material from the lithium ion battery from which the organic solvent has been removed can be performed, for example, by crushing the lithium ion battery. Lithium-ion batteries generally have a state in which a positive electrode active material applied to a positive electrode plate made of aluminum or the like and a negative electrode active material applied to a negative electrode plate such as a copper foil are laminated via a separator. It is housed in a housing made of aluminum or the like.
そこで、前記リチウムイオン電池を破砕することにより、前記正極活物質及び前記負極活物質が、前記筐体、正極電極板、負極電極板、セパレータ等から分離され、次いで、篩い分けを行うことにより、篩上に前記筐体、正極電極板、負極電極板、セパレータ等を得ることができ、篩下に前記正極活物質及び前記負極活物質を得ることができる。前記正極活物質は、例えば、前記リチウム化合物として、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム、アルミン酸リチウム等のリチウムと他の金属との複合酸化物を含んでおり、前記負極活物質は、例えば、炭素を含んでいる。 Therefore, by crushing the lithium ion battery, the positive electrode active material and the negative electrode active material are separated from the housing, the positive electrode plate, the negative electrode plate, the separator, and the like, and then sieved. The housing, the positive electrode plate, the negative electrode plate, the separator, and the like can be obtained on the sieve, and the positive electrode active material and the negative electrode active material can be obtained below the sieve. The positive electrode active material includes, for example, as the lithium compound, a composite oxide of lithium and another metal such as lithium cobaltate, lithium nickelate, lithium manganate, and lithium aluminate. , For example, contains carbon.
また、本発明のリチウムイオン電池からのリチウムの回収方法において、前記活物質に含まれるリチウム化合物を還元して粗炭酸リチウムを得る工程は、前記リチウムイオン電池から分離された活物質を、６５０〜７２０℃の範囲の温度で焙焼することが好ましい。 Further, in the method for recovering lithium from a lithium-ion battery of the present invention, to obtain a reduced crude lithium carbonate lithium compound contained in the active material, the active material separated from the lithium-ion battery, 6 50 it is good preferable roasting at a temperature in the range of to 720 ° C..
前記活物質の焙焼は６５０℃以上の温度で行うことにより、前記活物質に含まれるリチウム化合物の還元を十分に行うことができるが、大気雰囲気等の酸化雰囲気下、さらに高温の７２０℃超の温度で行うと還元物質が燃焼により失われたり、生成した粗炭酸リチウムが溶融することにより、リチウムの回収率が低下したりする。 By performing temperature roasting over 6 50 ° C. before Kikatsu material, wherein at the reduction of lithium compound contained in the active material can be sufficiently, under an oxidizing atmosphere such as air atmosphere, further hot 720 When the temperature is higher than 0 ° C., the reducing substance is lost by burning, or the produced crude lithium carbonate is melted, so that the recovery rate of lithium is reduced.
また、本発明のリチウムイオン電池からのリチウムの回収方法において、難溶性炭酸塩を生成し得る金属水酸化物としては、例えば、水酸化カルシウム、水酸化マグネシウム又は水酸化バリウムからなる群から選択される１種の金属水酸化物を用いることができるが、分子量が小さく、安価であることから水酸化カルシウムであることが好ましい。 Further, in the method for recovering lithium from a lithium ion battery of the present invention, the metal hydroxide capable of forming a hardly soluble carbonate is, for example, selected from the group consisting of calcium hydroxide, magnesium hydroxide and barium hydroxide. Although one kind of metal hydroxide can be used, calcium hydroxide is preferable because of its low molecular weight and low cost.
また、本発明のリチウムイオン電池からのリチウムの回収方法においては、前記水酸化リチウム溶液に炭酸ガスを供給する前に、該水酸化リチウム溶液を濾過し、得られた第１の濾液に炭酸ガスを供給し、析出した炭酸リチウムを回収することが好ましい。 Further, in the method for recovering lithium from a lithium ion battery of the present invention, before supplying carbon dioxide to the lithium hydroxide solution, the lithium hydroxide solution is filtered, and carbon dioxide gas is added to the obtained first filtrate. And recovering the precipitated lithium carbonate.
前記水酸化リチウム溶液は、前工程で生成した難溶性炭酸塩を含むので、炭酸ガスを供給する前に濾過して該難溶性炭酸塩を除去しておくことにより、高純度の炭酸リチウムを得ることができる。 Since the lithium hydroxide solution contains the hardly soluble carbonate generated in the previous step, high-purity lithium carbonate is obtained by filtering and removing the hardly soluble carbonate before supplying carbon dioxide gas. be able to.
また、本発明のリチウムイオン電池からのリチウムの回収方法においては、前記第１の濾液に炭酸ガスを供給した後、析出した炭酸リチウムを回収する前に、該第１の濾液を加熱することが好ましい。炭酸リチウムは、溶液の温度が高いほど溶解度が小さくなるので、析出した炭酸リチウムを回収する前に、前記第１の濾液を加熱することにより、炭酸リチウムの収率を高くすることができる。 Further, in the method for recovering lithium from a lithium ion battery according to the present invention, after supplying carbon dioxide to the first filtrate, the first filtrate may be heated before recovering the precipitated lithium carbonate. preferable. Since the solubility of lithium carbonate decreases as the temperature of the solution increases, the yield of lithium carbonate can be increased by heating the first filtrate before collecting the precipitated lithium carbonate.
また、本発明のリチウムイオン電池からのリチウムの回収方法において、前記水酸化リチウム溶液に炭酸ガスを供給し、析出した炭酸リチウムを回収する工程は、析出した炭酸リチウムを濾別することにより行うことができる。 In the method for recovering lithium from a lithium ion battery according to the present invention, the step of supplying carbon dioxide to the lithium hydroxide solution and recovering the precipitated lithium carbonate is performed by filtering the precipitated lithium carbonate. Can be.
また、前記析出した炭酸リチウムを濾別した後の第２の濾液は、微量ながら炭酸リチウムを含んでいるので、該第２の濾液を、前記難溶性炭酸塩を生成し得る金属水酸化物の溶媒に用いることにより、さらにリチウムの回収率を高くすることができる。 Further, since the second filtrate after filtering out the precipitated lithium carbonate by filtration contains a small amount of lithium carbonate, the second filtrate is converted to a metal hydroxide capable of producing the hardly soluble carbonate. By using the solvent, the recovery rate of lithium can be further increased.
また、本発明のリチウムイオン電池からのリチウムの回収方法において、前記不活性雰囲気は、窒素ガス、アルゴンガス又は炭酸ガスからなる群から選択される１種のガスからなるものを用いることができる。 Further, in the method for recovering lithium from a lithium ion battery of the present invention, the inert atmosphere may be one composed of one kind of gas selected from the group consisting of nitrogen gas, argon gas and carbon dioxide gas.
次に、本発明の実施の形態についてさらに詳しく説明する。 Next, embodiments of the present invention will be described in more detail.
本実施形態において、リチウムを回収する対象となるリチウムイオン電池は、電池製品としての寿命の消尽した使用済みのリチウムイオン電池、製造不良等の原因により廃棄されたリチウムイオン電池等であってもよく、未使用のリチウムイオン電池であってもよい。 In the present embodiment, the lithium-ion battery from which lithium is to be collected may be a used lithium-ion battery whose life as a battery product has been exhausted, a lithium-ion battery discarded due to a manufacturing defect, or the like. Or an unused lithium ion battery.
前記リチウムイオン電池は、一般に、アルミニウム箔等からなる正極電極板に塗布された正極活物質と、銅箔等の負極電極板に塗布された負極活物質とが、セパレータを介して重ね合わされた状態で、電解液と共にアルミニウム等からなる筐体に収容されている。 In general, the lithium ion battery has a state in which a positive electrode active material applied to a positive electrode plate made of aluminum foil or the like and a negative electrode active material applied to a negative electrode plate made of copper foil or the like are stacked via a separator. Thus, it is housed in a housing made of aluminum or the like together with the electrolytic solution.
前記正極活物質は、例えば、前記リチウム化合物として、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム、アルミン酸リチウム等のリチウムと他の金属との複合酸化物を含んでおり、前記負極活物質は、例えば、炭素を含んでいる。また、前記電解液は、例えば、六フッ化リン酸リチウム等の電解質が有機溶媒に溶解されている。 The positive electrode active material includes, for example, as the lithium compound, a composite oxide of lithium and another metal such as lithium cobaltate, lithium nickelate, lithium manganate, and lithium aluminate. , For example, contains carbon. Further, in the electrolytic solution, for example, an electrolyte such as lithium hexafluorophosphate is dissolved in an organic solvent.
本実施形態のリチウムイオン電池からのリチウムの回収方法では、まず、該リチウムイオン電池の放電を行う。前記放電は、例えば、水中でギアクラッシャー等の放電装置を用いて行うことができる。 In the method for recovering lithium from a lithium ion battery according to the present embodiment, first, the lithium ion battery is discharged. The discharge can be performed, for example, in water using a discharge device such as a gear crusher.
本実施形態のリチウムイオン電池からのリチウムの回収方法では、次に、放電されたリチウムイオン電池から、前記有機溶媒を除去する。前記有機溶媒の除去は、例えば、リチウムイオン電池を、窒素ガス、アルゴンガス又は炭酸ガス等からなる不活性雰囲気下、２００〜３００℃の範囲の温度で焙焼することにより行うことができる。 In the method for recovering lithium from a lithium-ion battery according to the present embodiment, the organic solvent is removed from the discharged lithium-ion battery. The removal of the organic solvent can be performed, for example, by roasting the lithium ion battery at a temperature in the range of 200 to 300 ° C. in an inert atmosphere composed of nitrogen gas, argon gas, carbon dioxide gas, or the like.
本実施形態のリチウムイオン電池からのリチウムの回収方法では、次に、前記有機溶媒が除去されたリチウムイオン電池から正極活物質及び負極活物質を分離する。前記リチウムイオン電池から正極活物質及び負極活物質を分離する操作は、例えば該リチウムイオン電池を二軸式破砕機等を用いて破砕することにより行うことができる。前記破砕により、前記正極活物質及び前記負極活物質が、前記筐体、正極電極板、負極電極板、セパレータ等から分離され、次いで、篩い分けを行うことにより、篩上に前記筐体、正極電極板、負極電極板、セパレータ等を得ることができ、篩下に前記正極活物質及び前記負極活物質を得ることができる。 In the method for recovering lithium from a lithium ion battery according to the present embodiment, next, the positive electrode active material and the negative electrode active material are separated from the lithium ion battery from which the organic solvent has been removed. The operation of separating the positive electrode active material and the negative electrode active material from the lithium ion battery can be performed, for example, by crushing the lithium ion battery using a biaxial crusher or the like. By the crushing, the positive electrode active material and the negative electrode active material are separated from the housing, the positive electrode plate, the negative electrode plate, the separator, and the like, and then, by performing sieving, the housing, the positive electrode An electrode plate, a negative electrode plate, a separator and the like can be obtained, and the positive electrode active material and the negative electrode active material can be obtained under a sieve.
前記篩い分けは、例えば目開き０．５〜２ｍｍの範囲の振動篩機により行うことができ、篩下に、前記正極活物質及び前記負極活物質の粉末を得ることができる。 The sieving can be performed by, for example, a vibration sieve having a mesh size of 0.5 to 2 mm, and the powder of the positive electrode active material and the powder of the negative electrode active material can be obtained under the sieve.
本実施形態のリチウムイオン電池からのリチウムの回収方法では、次に、前記正極活物質に含まれるリチウム化合物を還元して粗炭酸リチウムを得る。前記正極活物質に含まれるリチウム化合物を還元して粗炭酸リチウムを得る工程は、前記正極活物質及び前記負極活物質を、窒素ガス、アルゴンガス又は炭酸ガス等からなる不活性雰囲気下、還元性物質と共に６００℃以上の温度、好ましくは６５０〜７２０℃の範囲の温度で焙焼することにより行うことができる。このとき、前記負極活物質は前記還元性物質としての炭素を含むので好都合である。 In the method of recovering lithium from a lithium ion battery according to the present embodiment, next, the lithium compound contained in the positive electrode active material is reduced to obtain crude lithium carbonate. The step of obtaining a crude lithium carbonate by reducing a lithium compound contained in the positive electrode active material includes reducing the positive electrode active material and the negative electrode active material under an inert atmosphere comprising nitrogen gas, argon gas, carbon dioxide gas, or the like. It can be carried out by roasting at a temperature of 600 ° C. or higher, preferably 650 to 720 ° C., together with the substance. At this time, the negative electrode active material is convenient because it contains carbon as the reducing material.
この結果、前記正極活物質に含まれるコバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウム、アンミン酸リチウム等に含まれるリチウムが還元されて、粗炭酸リチウムを得ることができる。尚、前記粗炭酸リチウムは、前記電解液由来のフッ素やリン酸の化合物の他、前記複合酸化物に由来するニッケル、コバルト等の金属を含んでいる。 As a result, lithium contained in the lithium cobaltate, lithium nickelate, lithium manganate, lithium aminate and the like contained in the positive electrode active material is reduced, and crude lithium carbonate can be obtained. The crude lithium carbonate contains metals such as nickel and cobalt derived from the composite oxide, in addition to compounds of fluorine and phosphoric acid derived from the electrolytic solution.
本実施形態のリチウムイオン電池からのリチウムの回収方法では、次に、前記粗炭酸リチウムに、難溶性炭酸塩を生成し得る金属水酸化物溶液を添加する。このようにすると、前記金属水酸化物を構成する金属が炭酸と反応して難溶性炭酸塩が生成する一方、前記粗炭酸リチウムが水酸化リチウムに転換されて溶解し、水酸化リチウム溶液を得ることができる。このとき、前記電解液由来のフッ素やリン酸の化合物は前記金属水酸化物を構成する金属と反応してそれ自体難溶性塩を形成し、あるいは前記難溶性炭酸塩に捕捉されるので、純度の高い水酸化リチウム溶液を得ることができる。 In the method for recovering lithium from a lithium ion battery according to the present embodiment, next, a metal hydroxide solution capable of forming a hardly soluble carbonate is added to the crude lithium carbonate. In this case, the metal constituting the metal hydroxide reacts with carbonic acid to generate a sparingly soluble carbonate, while the crude lithium carbonate is converted and dissolved in lithium hydroxide to obtain a lithium hydroxide solution. be able to. At this time, the fluorine or phosphoric acid compound derived from the electrolytic solution reacts with the metal constituting the metal hydroxide to form a sparingly soluble salt itself, or is trapped by the sparingly soluble carbonate, so that the purity is low. And a lithium hydroxide solution having a high pH can be obtained.
本実施形態のリチウムイオン電池からのリチウムの回収方法では、次に、前記水酸化リチウム溶液を濾過して、前記難溶性炭酸塩や前記粗炭酸リチウムに含まれるニッケル、コバルト等の金属を濾過残渣として除去し、得られた第１の濾液に炭酸ガスを供給する。前記第１の濾液に対する前記炭酸ガスの供給は、前記第１の濾液中に炭酸ガスをバブリングする等の公知の方法により行うことができる。 In the method for recovering lithium from a lithium ion battery according to the present embodiment, the lithium hydroxide solution is then filtered to remove metals such as nickel and cobalt contained in the hardly soluble carbonate and the crude lithium carbonate as a filtration residue. And carbon dioxide gas is supplied to the obtained first filtrate. The supply of the carbon dioxide gas to the first filtrate can be performed by a known method such as bubbling the carbon dioxide gas into the first filtrate.
このようにすると、水酸化リチウムと炭酸ガスとが反応して炭酸リチウムが生成し、該炭酸リチウムが析出する。そこで、前記炭酸リチウムを含む第１の濾液を加熱した後、該第１の濾液から前記炭酸リチウムを濾別して回収する。前記炭酸リチウムを含む溶液は高温になるほど炭酸リチウムの溶解度が小さくなるので、前記第１の溶液の温度は装置の耐熱性の範囲で高いほど好ましく、例えば、６０℃とすることができる。 In this case, lithium hydroxide reacts with carbon dioxide gas to generate lithium carbonate, and the lithium carbonate is precipitated. Therefore, after heating the first filtrate containing the lithium carbonate, the lithium carbonate is filtered and recovered from the first filtrate. Since the solubility of lithium carbonate decreases as the temperature of the solution containing lithium carbonate increases, the temperature of the first solution is preferably as high as possible within the range of the heat resistance of the apparatus, and may be, for example, 60 ° C.
また、前記のように炭酸リチウムの溶解度を小さくしたとしても、前記炭酸リチウムを濾別した後の第２の濾液は微量の炭酸リチウムを含んでいる。そこで、前記炭酸リチウムを濾別した後の第２の濾液を前記難溶性炭酸塩を生成し得る金属水酸化物の溶媒に用いることにより、さらにリチウムの回収率を高くすることができる。 Further, even if the solubility of lithium carbonate is reduced as described above, the second filtrate after filtering the lithium carbonate contains a trace amount of lithium carbonate. Therefore, the recovery rate of lithium can be further increased by using the second filtrate obtained by filtering the lithium carbonate as a solvent of a metal hydroxide capable of producing the hardly soluble carbonate.
また、本実施形態では、前記水酸化リチウム溶液を濾過することにより得られる濾過残渣を洗浄することにより、ニッケル、コバルト等の金属を回収することができる。また、前記濾過残渣を洗浄することにより得られた洗浄濾液を前記難溶性炭酸塩を生成し得る金属水酸化物の溶媒に用いることによっても、リチウムの回収率を高くすることができる。 Further, in the present embodiment, metals such as nickel and cobalt can be recovered by washing the filtration residue obtained by filtering the lithium hydroxide solution. Further, the recovery rate of lithium can also be increased by using a washing filtrate obtained by washing the filtration residue as a solvent of a metal hydroxide capable of producing the hardly soluble carbonate.
次に、本発明の実施例及び比較例を示す。 Next, Examples and Comparative Examples of the present invention will be described.
〔実施例１〕
本実施例では、円筒型の廃リチウムイオン電池を用い、まず、放電装置を用いて該廃リチウムイオン電池の放電を行った。
[Example 1]
In this example, a cylindrical waste lithium ion battery was used, and first, the waste lithium ion battery was discharged using a discharge device.
次に、放電後の前記廃リチウムイオン電池を窒素雰囲気下、２５０℃の温度で５時間焙焼して有機溶媒を除去した後、常温（２５℃）まで冷却し、二軸式破砕機で破砕し、目開き１ｍｍの振動篩機にかけて、該廃リチウムイオン電池に含まれる正極活物質及び負極活物質を篩下に得た。次に、篩下に得られた粉体（前記正極活物質及び負極活物質）を窒素雰囲気下、７００℃の温度で２時間焙焼した後、窒素雰囲気下で常温（２５℃）まで冷却し、粗炭酸リチウムの粉体を得た。前記粗炭酸リチウムの粉体は、全量の５．５質量％のリチウムを含有していた。 Next, the waste lithium ion battery after discharging is roasted in a nitrogen atmosphere at a temperature of 250 ° C. for 5 hours to remove the organic solvent, cooled to room temperature (25 ° C.), and crushed by a biaxial crusher. Then, the resultant was passed through a vibrating sieve having an opening of 1 mm to obtain a positive electrode active material and a negative electrode active material contained in the waste lithium ion battery below the sieve. Next, the powder obtained under the sieve (the positive electrode active material and the negative electrode active material) was roasted at a temperature of 700 ° C. for 2 hours in a nitrogen atmosphere, and then cooled to a normal temperature (25 ° C.) in a nitrogen atmosphere. Thus, a powder of crude lithium carbonate was obtained. The powder of the crude lithium carbonate contained 5.5% by mass of the total amount of lithium.
次に、前記粗炭酸リチウムの粉体を２ｋｇ分取し、水酸化カルシウム４００ｇと１０リットルの水とを加えて十分撹拌した後、濾過し、水酸化リチウムを含む第１の濾液８．４リットルを得た。前記第１の濾液のリチウム濃度は９．８ｇ／リットルであった。 Next, 2 kg of the powder of the crude lithium carbonate was taken, 400 g of calcium hydroxide and 10 liters of water were added, and the mixture was sufficiently stirred, filtered, and 8.4 liters of the first filtrate containing lithium hydroxide. I got The lithium concentration of the first filtrate was 9.8 g / liter.
前記濾過残渣を１０リットルの水で洗浄し、リチウム濃度１．６ｇ／リットルの洗浄濾液９．８リットルを得た。 The filtration residue was washed with 10 liters of water to obtain 9.8 liters of a washing filtrate having a lithium concentration of 1.6 g / liter.
次に、前記第１の濾液に炭酸ガスを吹き込み、炭酸リチウムを沈殿させ、該第１の濾液を６０℃に加熱した後、濾過して炭酸リチウム３５５ｇ（乾燥重量）と、リチウム濃度１．９ｇ／リットルの第２の濾液８．１リットルを得た。本実施例における炭酸リチウムの回収率は６０．７％であった。 Next, carbon dioxide gas was blown into the first filtrate to precipitate lithium carbonate. The first filtrate was heated to 60 ° C., and then filtered to obtain 355 g (dry weight) of lithium carbonate and a lithium concentration of 1.9 g. A second filtrate of 8.1 l / l was obtained. The recovery of lithium carbonate in this example was 60.7%.
〔実施例２〕
本実施例では、実施例１で得られた前記粗炭酸リチウムの粉体を２ｋｇ分取し、水酸化カルシウム４００ｇと、実施例１で得られた洗浄濾液３．９リットルと、実施例１で得られた第２の濾液８．１リットルとを加えて十分撹拌した後、濾過し、水酸化リチウムを含む第１の濾液１０．４リットルを得た。前記第１の濾液のリチウム濃度は１０．０ｇ／リットルであった。
[Example 2]
In this example, 2 kg of the powder of the crude lithium carbonate obtained in Example 1 was dispensed, 400 g of calcium hydroxide, 3.9 liters of the washing filtrate obtained in Example 1, and The obtained second filtrate (8.1 liter) was added thereto, and the mixture was sufficiently stirred and filtered. Thus, a first filtrate containing lithium hydroxide (10.4 liter) was obtained. The lithium concentration of the first filtrate was 10.0 g / liter.
次に、前記第１の濾液に炭酸ガスを吹き込み、炭酸リチウムを沈殿させ、該第１の濾液を６０℃に加熱した後、濾過して炭酸リチウム４５０ｇ（乾燥重量）を得た。本実施例における炭酸リチウムの回収率は７６．９％であった。 Next, carbon dioxide gas was blown into the first filtrate to precipitate lithium carbonate. The first filtrate was heated to 60 ° C. and filtered to obtain 450 g (dry weight) of lithium carbonate. The recovery of lithium carbonate in this example was 76.9%.
〔参考例１〕
本参考例では、実施例１で得られた前記粗炭酸リチウムの粉体を１００ｇ分取し、１０リットルの水を加えて十分撹拌した後、濾過し、得られた濾液中のリチウム濃度をＩＣＰにて測定したところ、４９０ｐｐｍであり、前記粗炭酸リチウムから前記濾液中に溶出したリチウムの溶出率は８９％であった。結果を表１に示す。
[Reference Example 1]
In this reference example, 100 g of the above-mentioned crude lithium carbonate powder obtained in Example 1 was taken, 10 liters of water was added thereto, and the mixture was sufficiently stirred, followed by filtration. Was 490 ppm, and the elution rate of lithium eluted from the crude lithium carbonate into the filtrate was 89%. Table 1 shows the results.
〔参考例２〕
本参考例では、実施例１と全く同一にして放電した廃リチウムイオン電池を、有機溶媒を除去することなく、大気雰囲気下７００℃の温度で５時間焙焼した後、自然冷却し、二軸式破砕機で破砕し、目開き１ｍｍの振動篩機にかけて、篩下に粉体を得た。前記粉体は、全量の６．２質量％のリチウムを含有していた。
[Reference Example 2]
In this reference example, a waste lithium ion battery discharged in exactly the same manner as in Example 1 was roasted at a temperature of 700 ° C. for 5 hours in an air atmosphere without removing an organic solvent, and then naturally cooled, The powder was crushed by a crusher and passed through a vibrating sieve having an opening of 1 mm to obtain a powder under the sieve. The powder contained 6.2% by mass of lithium based on the total amount.
次に、本参考例で得られた前記粉体を１００ｇ分取し、１０リットルの水を加えて十分撹拌した後、濾過し、得られた濾液中のリチウム濃度をＩＣＰにて測定したところ、２６７ｍｇ／リットルであり、前記粉体から前記濾液中に溶出したリチウムの溶出率は４３％であった。結果を表１に示す。 Next, 100 g of the powder obtained in the present reference example was collected, 10 liters of water was added thereto, and the mixture was sufficiently stirred, filtered, and the lithium concentration in the obtained filtrate was measured by ICP. 267 mg / liter, and the elution rate of lithium eluted from the powder into the filtrate was 43%. Table 1 shows the results.
〔参考例３〕
本参考例では、篩下に得られた粉体（前記正極活物質及び負極活物質）を大気雰囲気下、７００℃の温度で２時間焙焼した以外は、実施例１と全く同一にして、粗炭酸リチウムの粉体を得た。本参考例で得られた前記粗炭酸リチウムの粉体は、全量の６．６質量％のリチウムを含有していた。
[Reference Example 3]
In this reference example, except that the powder obtained under the sieve (the positive electrode active material and the negative electrode active material) was roasted at a temperature of 700 ° C. for 2 hours in an air atmosphere, A powder of crude lithium carbonate was obtained. The powder of the crude lithium carbonate obtained in the present reference example contained 6.6% by mass of the total amount of lithium.
次に、本参考例で得られた前記粗炭酸リチウムの粉体を１００ｇ分取し、１０リットルの水を加えて十分撹拌した後、濾過し、得られた濾液中のリチウム濃度をＩＣＰにて測定したところ、２３１ｍｇ／リットルであり、前記粗炭酸リチウムの粉体から前記濾液中に溶出したリチウムの溶出率は３５％であった。結果を表１に示す。 Next, 100 g of the above-mentioned crude lithium carbonate powder obtained in the present reference example was taken, 10 liters of water was added thereto, and the mixture was sufficiently stirred and filtered. The lithium concentration in the obtained filtrate was measured by ICP. As a result of measurement, it was 231 mg / liter, and the elution rate of lithium eluted from the crude lithium carbonate powder into the filtrate was 35%. Table 1 shows the results.
〔参考例４〕
本参考例では、放電した廃リチウムイオン電池を、大気雰囲気下、２５０℃の温度で５時間焙焼した以外は、実施例１と全く同一にして、粗炭酸リチウムの粉体を得た。本参考例で得られた前記粗炭酸リチウムの粉体は、全量の５．８質量％のリチウムを含有していた。
[Reference Example 4]
In this reference example, crude lithium carbonate powder was obtained in exactly the same manner as in Example 1 except that the discharged waste lithium ion battery was roasted at a temperature of 250 ° C. for 5 hours in an air atmosphere. The powder of the crude lithium carbonate obtained in the present reference example contained 5.8% by mass of the total amount of lithium.
次に、本参考例で得られた前記粗炭酸リチウムの粉体を１００ｇ分取し、１０リットルの水を加えて十分撹拌した後、濾過し、得られた濾液中のリチウム濃度をＩＣＰにて測定したところ、３７７ｍｇ／リットルであり、前記粗炭酸リチウムの粉体から前記濾液中に溶出したリチウムの溶出率は６５％であった。結果を表１に示す。 Next, 100 g of the above-mentioned crude lithium carbonate powder obtained in the present reference example was taken, 10 liters of water was added thereto, and the mixture was sufficiently stirred, followed by filtration. The lithium concentration in the obtained filtrate was measured by ICP. As a result of measurement, it was 377 mg / liter, and the elution rate of lithium eluted from the crude lithium carbonate powder into the filtrate was 65%. Table 1 shows the results.
表１から、有機溶媒除去のための焙焼と、リチウム化合物の還元のための焙焼との両方を窒素雰囲気（不活性雰囲気）下で行う参考例１によれば、有機溶媒除去のための焙焼を行わず、リチウム化合物の還元のための焙焼を大気雰囲気下で行う参考例２、有機溶媒除去のための焙焼と、リチウム化合物の還元のための焙焼とのいずれか一方を大気雰囲気下で行う参考例３，４に比較して、濾液に対するリチウムの溶出率が大きく、リチウムをより高収率で回収することができることがあきらかである。 From Table 1, according to Reference Example 1 in which both the roasting for removing the organic solvent and the roasting for reducing the lithium compound are performed under a nitrogen atmosphere (inert atmosphere), the roasting for removing the organic solvent is performed. Reference Example 2 in which roasting for reduction of a lithium compound is performed in an air atmosphere without performing roasting. One of roasting for removing an organic solvent and roasting for reduction of a lithium compound. Compared to Reference Examples 3 and 4 performed in an air atmosphere, the elution rate of lithium in the filtrate is large, and it is clear that lithium can be recovered in a higher yield.
Claims (12)
有機溶媒が除去されたリチウムイオン電池から活物質を分離する工程と、
前記リチウムイオン電池から分離された活物質を、不活性雰囲気下、リチウムイオン電池の負極活物質に含まれる還元性物質としての炭素と共に６００℃以上の温度で焙焼して、前記活物質に含まれるリチウム化合物を還元して粗炭酸リチウムを得る工程と、
前記粗炭酸リチウムに、難溶性炭酸塩を生成し得る金属水酸化物溶液を添加し、水酸化リチウム溶液を得る工程と、
前記水酸化リチウム溶液に炭酸ガスを供給し、析出した炭酸リチウムを回収する工程とを備えることを特徴とするリチウムイオン電池からのリチウムの回収方法。 Roasting the lithium ion battery under an inert atmosphere to remove the organic solvent from the lithium ion battery;
Separating the active material from the lithium-ion battery from which the organic solvent has been removed,
The active material separated from the lithium ion battery is roasted at a temperature of 600 ° C. or more together with carbon as a reducing material contained in the negative electrode active material of the lithium ion battery under an inert atmosphere, and contained in the active material. Reducing the lithium compound to obtain crude lithium carbonate,
A step of adding a metal hydroxide solution capable of producing a hardly soluble carbonate to the crude lithium carbonate to obtain a lithium hydroxide solution;
Supplying a carbon dioxide gas to the lithium hydroxide solution and recovering the precipitated lithium carbonate.
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