JP5535717B2 - Lithium recovery method - Google Patents
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- JP5535717B2 JP5535717B2 JP2010068685A JP2010068685A JP5535717B2 JP 5535717 B2 JP5535717 B2 JP 5535717B2 JP 2010068685 A JP2010068685 A JP 2010068685A JP 2010068685 A JP2010068685 A JP 2010068685A JP 5535717 B2 JP5535717 B2 JP 5535717B2
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- 229910052744 lithium Inorganic materials 0.000 title claims description 124
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 122
- 238000000034 method Methods 0.000 title claims description 51
- 238000011084 recovery Methods 0.000 title claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 77
- 229910052799 carbon Inorganic materials 0.000 claims description 63
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 46
- 229910001416 lithium ion Inorganic materials 0.000 claims description 46
- 238000002386 leaching Methods 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 14
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 14
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 239000000571 coke Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229910017052 cobalt Inorganic materials 0.000 description 18
- 239000010941 cobalt Substances 0.000 description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 18
- 239000007774 positive electrode material Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052596 spinel Chemical group 0.000 description 2
- 239000011029 spinel Chemical group 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940063821 oxygen 21 % Drugs 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000013022 venting Methods 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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- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Description
本発明は、リチウムイオン二次電池の正極材料であるコバルト酸リチウムから、リチウムを効率よく回収することができ、リチウムイオン二次電池の再利用を行うことができるリチウムの回収方法に関する。 The present invention relates to a lithium recovery method capable of efficiently recovering lithium from lithium cobalt oxide, which is a positive electrode material of a lithium ion secondary battery, and enabling reuse of the lithium ion secondary battery.
リチウムイオン二次電池は、従来の鉛蓄電池、ニッカド二次電池等に比較して軽量、高容量、高起電力の優れた二次電池であり、携帯電話、ノートパソコン等のモバイル機器などに広く使用されている。
このようなリチウムイオン二次電池の正極材料には、コバルト酸リチウム（ＬｉＣｏＯ２）、マンガン酸リチウム（ＬｉＭｎ２Ｏ４）などが用いられており、これらには希少有価物質であるコバルトやリチウムが含まれている。そこで、使用済みのリチウムイオン二次電池からこれらの有価物質を回収し、再びリチウムイオン二次電池の正極材料としてリサイクル利用を図ることが望まれている。
Lithium-ion secondary batteries are secondary batteries that are lighter, have higher capacity, and have higher electromotive force than conventional lead-acid batteries and nickel-cadmium secondary batteries, and are widely used in mobile devices such as mobile phones and laptop computers. It is used.
As a positive electrode material of such a lithium ion secondary battery, lithium cobaltate (LiCoO 2 ), lithium manganate (LiMn 2 O 4 ), and the like are used, and these include rare metals such as cobalt and lithium. include. Therefore, it is desired to recover these valuable substances from the used lithium ion secondary battery and to recycle them as a positive electrode material for the lithium ion secondary battery.
前記コバルト酸リチウムは、層状岩塩型構造又はスピネル構造を有していると考えられており、例えば硝酸、硫酸、塩酸等の強酸を使用して溶解した後、中和反応を行って、リチウム及びコバルトを回収していた（特許文献１参照）。
しかし、前記回収方法では、硝酸、硫酸に対する溶解度が小さいという問題に加えて、多量の還元剤が必要となる。また、リチウム及びコバルトを溶解させた後、リチウムとコバルトの分離回収を行う必要があり、設備が増大する。更に、塩酸を使用した場合には、有害な塩素ガスが発生してしまうという、安全上の問題があった。
The lithium cobaltate is considered to have a layered rock salt structure or a spinel structure. For example, the lithium cobaltate is dissolved using a strong acid such as nitric acid, sulfuric acid, hydrochloric acid, etc. Cobalt was recovered (see Patent Document 1).
However, the recovery method requires a large amount of reducing agent in addition to the problem of low solubility in nitric acid and sulfuric acid. Further, after lithium and cobalt are dissolved, it is necessary to separate and recover lithium and cobalt, which increases equipment. Further, when hydrochloric acid is used, there is a safety problem that harmful chlorine gas is generated.
また、特許文献２には、コバルト酸リチウムに炭素を添加し、７００℃以上の温度で、不活性ガス雰囲気中にて、還元焙焼することにより、焙焼物を得て、該焙焼物を水で浸出することにより、焙焼物中のリチウム分を溶出させて、回収する方法が提案されている。
この提案の実施例２では、コバルト酸リチウム５０ｇに炭素６．９ｇを添加（炭素濃度１２．１質量％）し、不活性ガス雰囲気中、８００℃にて２時間、焙焼を行っており、リチウムが９９％以上の浸出率を示したと記載されている。しかし、前記特許文献２の実施例ではコバルト酸リチウムそのものを管状炉に装入して焙焼しており、コバルト酸リチウムの単品を焙焼することを想定しており、リチウムイオン二次電池の正極材料、リチウムイオン二次電池の粉砕物を回収原料として用いることを全く予定していないものである。
In Patent Document 2, carbon is added to lithium cobaltate, and reduced roasting is performed in an inert gas atmosphere at a temperature of 700 ° C. or higher to obtain a roasted product. A method has been proposed in which the lithium content in the baked product is eluted and leached and then recovered.
In Example 2 of this proposal, 6.9 g of carbon was added to 50 g of lithium cobaltate (carbon concentration 12.1% by mass), and roasting was performed at 800 ° C. for 2 hours in an inert gas atmosphere. It is described that lithium showed a leaching rate of 99% or more. However, in the embodiment of Patent Document 2, it is assumed that lithium cobaltate itself is charged into a tubular furnace and roasted, and it is assumed that a single lithium cobaltate is roasted. There is no plan to use the pulverized material of the positive electrode material or the lithium ion secondary battery as a recovered raw material.
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、リチウムイオン二次電池の正極材料であるコバルト酸リチウムから、リチウムを効率よく回収することができ、リチウムイオン二次電池の再利用を行うことができる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 solve the above-described problems and achieve the following objects. That is, the present invention provides a lithium recovery method capable of efficiently recovering lithium from lithium cobalt oxide, which is a positive electrode material of a lithium ion secondary battery, and reusing the lithium ion secondary battery. The purpose is to do.
前記課題を解決するため本発明者らが鋭意検討を重ねた結果、安定な層状岩塩型構造又はスピネル構造をとるコバルト酸リチウムと炭素を混合した混合物を、所定の焙焼条件で、焙焼するとリチウムが酸化リチウム（Ｌｉ２Ｏ）となり、この焙焼物を水で浸出すると、水酸化リチウム（ＬｉＯＨ）及び炭酸リチウム（Ｌｉ２ＣＯ３）となって溶出し、極めて効率よく、かつ簡便な操作でリチウムを回収できることを知見した。 As a result of repeated studies by the present inventors in order to solve the above problems, a mixture of lithium cobaltate and carbon having a stable layered rock salt structure or spinel structure is roasted under predetermined roasting conditions. When lithium becomes lithium oxide (Li 2 O) and this baked product is leached with water, it elutes as lithium hydroxide (LiOH) and lithium carbonate (Li 2 CO 3 ), which is extremely efficient and easy to operate. It was found that lithium can be recovered.
本発明は、本発明者らによる前記知見に基づくものであり、前記課題を解決するための手段としては、以下の通りである。即ち、
＜１＞ コバルト酸リチウム１００質量部に対し、１質量部以上の炭素を混合した混合物を、大気雰囲気下、酸化雰囲気下、及び還元性雰囲気下のいずれかで焙焼してなる酸化リチウムを含有する焙焼物を水で浸出することを特徴とするリチウムの回収方法である。
＜２＞ コバルト酸リチウム１００質量部に対し、１質量部以上の炭素を混合した混合物を、大気雰囲気下、５００℃以上の温度で焙焼してなる酸化リチウムを含有する焙焼物を水で浸出する前記＜１＞に記載のリチウムの回収方法である。
＜３＞ コバルト酸リチウム１００質量部に対し、１質量部以上の炭素を混合した混合物を、酸化雰囲気下、５００℃以上の温度で焙焼してなる酸化リチウムを含有する焙焼物を水で浸出する前記＜１＞に記載のリチウムの回収方法である。
＜４＞ コバルト酸リチウム１００質量部に対し、１質量部〜５０質量部の炭素を混合する前記＜１＞から＜３＞のいずれかに記載のリチウムの回収方法である。
＜５＞ コバルト酸リチウム１００質量部に対し、１０質量部以上の炭素を混合した混合物を、大気雰囲気下、７００℃以上の温度で焙焼してなる酸化リチウムを含有する焙焼物を水で浸出する前記＜１＞から＜２＞のいずれかに記載のリチウムの回収方法である。
＜６＞ コバルト酸リチウム１００質量部に対し、１質量部以上の炭素を混合した混合物を、不活性雰囲気下、５００℃以上７００℃未満の温度で焙焼してなる酸化リチウムを含有する焙焼物を水で浸出することを特徴とするリチウムの回収方法である。
＜７＞ コバルト酸リチウム１００質量部に対し、１５質量部〜５０質量部の炭素を混合する前記＜６＞に記載のリチウムの回収方法である。
＜８＞ コバルト酸リチウムと炭素を混合した混合物が、使用済リチウムイオン二次電池より得られたものである前記＜１＞から＜７＞のいずれかに記載のリチウムの回収方法である。
＜９＞ 炭素が、カーボンブラック、黒鉛、活性炭、石炭、コークス、木炭、及び使用済リチウムイオン二次電池の負極、及び還元性を有する有機物のいずれかより得られたものである前記＜１＞から＜８＞のいずれかに記載のリチウムの回収方法である。
The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> Contains lithium oxide formed by roasting a mixture in which 1 part by mass or more of carbon is mixed with 100 parts by mass of lithium cobaltate in an air atmosphere, an oxidizing atmosphere, or a reducing atmosphere. The method for recovering lithium is characterized by leaching the roasted product to be washed with water.
<2> For 100 parts by mass of lithium cobaltate, a mixture obtained by mixing 1 part by mass or more of carbon is calcined at a temperature of 500 ° C. or higher in an air atmosphere, and a roasted product containing lithium oxide is leached with water. The method for recovering lithium according to <1>.
<3> For 100 parts by mass of lithium cobaltate, a mixture obtained by mixing 1 part by mass or more of carbon is baked at a temperature of 500 ° C. or higher in an oxidizing atmosphere, and a roasted product containing lithium oxide is leached with water. The method for recovering lithium according to <1>.
<4> The lithium recovery method according to any one of <1> to <3>, wherein 1 to 50 parts by mass of carbon is mixed with 100 parts by mass of lithium cobalt oxide.
<5> A baked product containing lithium oxide obtained by roasting a mixture obtained by mixing 10 parts by mass or more of carbon with respect to 100 parts by mass of lithium cobaltate at a temperature of 700 ° C. or higher in an air atmosphere with water. The method for recovering lithium according to any one of <1> to <2>.
<6> A roasted product containing lithium oxide obtained by roasting a mixture in which 1 part by mass or more of carbon is mixed with 100 parts by mass of lithium cobaltate in an inert atmosphere at a temperature of 500 ° C. or higher and lower than 700 ° C. This is a lithium recovery method characterized by leaching with water.
<7> The lithium recovery method according to <6>, wherein 15 parts by mass to 50 parts by mass of carbon are mixed with 100 parts by mass of lithium cobalt oxide.
<8> The lithium recovery method according to any one of <1> to <7>, wherein the mixture obtained by mixing lithium cobaltate and carbon is obtained from a used lithium ion secondary battery.
<9> The above <1>, wherein the carbon is obtained from any one of carbon black, graphite, activated carbon, coal, coke, charcoal, a negative electrode of a used lithium ion secondary battery, and a reducing organic substance. To <8>. The method for recovering lithium according to any one of <8>.
本発明によると、従来における問題を解決することができ、リチウムイオン二次電池の正極材料であるコバルト酸リチウムから、リチウムを効率よく回収することができ、リチウムイオン二次電池の再利用を行うことができるリチウムの回収方法を提供することができる。 According to the present invention, conventional problems can be solved, lithium can be efficiently recovered from lithium cobaltate, which is a positive electrode material of a lithium ion secondary battery, and the lithium ion secondary battery is reused. It is possible to provide a method for recovering lithium.
本発明のリチウムの回収方法は、第１の形態では、コバルト酸リチウム１００質量部に対し、１質量部以上の炭素を混合した混合物を、大気雰囲気下、酸化雰囲気下、及び還元性雰囲気下のいずれかで焙焼してなる酸化リチウムを含有する焙焼物を水で浸出する。
本発明のリチウムの回収方法は、第２の形態では、コバルト酸リチウム１００質量部に対し、１質量部以上の炭素を混合した混合物を、不活性雰囲気下、５００℃以上７００℃未満の温度で焙焼してなる酸化リチウムを含有する焙焼物を水で浸出する。この場合、コバルト酸リチウム１００質量部に対し、１５質量部〜５０質量部の炭素を混合することが好ましい。
ここで、前記第１の及び第２の形態において、前記コバルト酸リチウムと炭素を混合した混合物には、コバルト酸リチウムと炭素を個別に混合した混合物以外にも、リチウムイオン二次電池の粉砕物等のコバルト酸リチウム及び炭素を一緒に含むものも含まれる。
In the first aspect of the lithium recovery method of the present invention, in a first embodiment, a mixture in which 1 part by mass or more of carbon is mixed with 100 parts by mass of lithium cobaltate is mixed in an air atmosphere, an oxidizing atmosphere, and a reducing atmosphere. A roasted product containing lithium oxide, which is roasted with either one, is leached with water.
In the second aspect of the lithium recovery method of the present invention, a mixture obtained by mixing 1 part by mass or more of carbon with respect to 100 parts by mass of lithium cobaltate is heated at a temperature of 500 ° C. or higher and lower than 700 ° C. in an inert atmosphere. A roasted product containing lithium oxide obtained by roasting is leached with water. In this case, it is preferable to mix 15 parts by mass to 50 parts by mass of carbon with respect to 100 parts by mass of lithium cobalt oxide.
Here, in the first and second embodiments, the mixture obtained by mixing lithium cobaltate and carbon is not limited to a mixture obtained by individually mixing lithium cobaltate and carbon, but is also a pulverized product of a lithium ion secondary battery. And those containing lithium cobaltate and carbon together.
−コバルト酸リチウム−
前記コバルト酸リチウムとしては、コバルト酸リチウム（ＬｉＣｏＯ２）を一定量以上含有しているものであれば特に制限はなく、目的に応じて適宜選択することができ、例えばコバルト酸リチウムの純品、使用済リチウムイオン二次電池の正極廃材、使用済リチウムイオン二次電池の正極廃材から分離したコバルト酸リチウム、マンガン・ニッケル・コバルト・リチウムにより形成される正極廃材、などが挙げられる。
これらの中でも、リチウムイオン二次電池のリサイクルを図れる点から、使用済リチウムイオン二次電池の正極廃材が特に好ましい。
-Lithium cobaltate-
The lithium cobaltate is not particularly limited as long as it contains a certain amount or more of lithium cobaltate (LiCoO 2 ), and can be appropriately selected according to the purpose. For example, a pure product of lithium cobaltate, Examples include a positive electrode waste material of a used lithium ion secondary battery, a lithium cobaltate separated from a positive electrode waste material of a used lithium ion secondary battery, and a positive electrode waste material formed of manganese, nickel, cobalt, and lithium.
Among these, a positive electrode waste material of a used lithium ion secondary battery is particularly preferable from the viewpoint that the lithium ion secondary battery can be recycled.
−炭素−
前記炭素としては、特に制限はなく、目的に応じて適宜選択することができ、例えばカーボンブラック、黒鉛、活性炭、石炭、コークス、木炭、使用済リチウムイオン二次電池の負極、還元性を有する有機物などが挙げられる。これらの中でも、リチウムイオン二次電池のリサイクルを図れる点から、使用済リチウムイオン二次電池の負極が特に好ましい。
前記還元性を有する有機物としては、例えば電解質の材料であるプロピレンカーボネート、エチレンカーボネート等、セパレーターの材料であるポリオレフィンフィルム等が挙げられる。
-Carbon-
The carbon is not particularly limited and may be appropriately selected depending on the intended purpose. For example, carbon black, graphite, activated carbon, coal, coke, charcoal, a negative electrode of a used lithium ion secondary battery, an organic substance having reducibility Etc. Among these, the negative electrode of the used lithium ion secondary battery is particularly preferable because the lithium ion secondary battery can be recycled.
Examples of the organic substance having reducibility include propylene carbonate and ethylene carbonate, which are electrolyte materials, and polyolefin films, which are separator materials.
前記炭素と前記コバルト酸リチウムを混合する方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えばリチウムイオン二次電池の正極材料のみを取り出した場合、正極材料と炭素をミキサーで混合する方法がある。
前記ミキサーとしては、特に制限はなく、目的に応じて適宜選択することができ、例えばＶ型ブレンダー、回転型ミキサー、ラインミキサーなどを使用でき、ロータリーキルンのような混合性能を含む炉を用いて、混合と焙焼を同時に行ってもよい。
なお、リチウムイオン二次電池の負極には、炭素（黒鉛）が含まれているので、リチウムイオン二次電池より得られたものを焙焼する場合には炭素の添加は不要である。
The method of mixing the carbon and the lithium cobalt oxide is not particularly limited and may be appropriately selected depending on the purpose. For example, when only the positive electrode material of a lithium ion secondary battery is taken out, the positive electrode material and the carbon are mixed. There is a method of mixing with a mixer.
The mixer is not particularly limited and can be appropriately selected according to the purpose. For example, a V-type blender, a rotary mixer, a line mixer, etc. can be used, and using a furnace having mixing performance such as a rotary kiln, Mixing and roasting may be performed simultaneously.
In addition, since carbon (graphite) is contained in the negative electrode of the lithium ion secondary battery, the addition of carbon is not necessary when the product obtained from the lithium ion secondary battery is roasted.
前記炭素の混合量は、第１の形態では、コバルト酸リチウム１００質量部に対し１質量部以上であり、１質量部〜５０質量部であることが好ましい。
また、前記炭素の混合量は、第２の形態では、コバルト酸リチウム１００質量部に対し１質量部以上であり、１５質量部〜５０質量部であることが好ましい。
前記炭素の混合量が、１質量部未満であると、リチウムイオン二次電池の正極の結晶構造を破壊できないために、リチウムを溶出できないことがあり、５０質量部を超えると、コバルト酸リチウムと炭素を混合した混合物を焙焼後に炭素成分が残留するため、炭素除去工程が必要となることがある。
In the first embodiment, the mixing amount of the carbon is 1 part by mass or more and 100 parts by mass to 50 parts by mass with respect to 100 parts by mass of lithium cobalt oxide.
Moreover, in the 2nd form, the mixing amount of the carbon is 1 part by mass or more and preferably 15 parts by mass to 50 parts by mass with respect to 100 parts by mass of lithium cobalt oxide.
If the amount of carbon is less than 1 part by mass, the crystal structure of the positive electrode of the lithium ion secondary battery cannot be destroyed, so lithium may not be eluted. If the amount exceeds 50 parts by mass, Since a carbon component remains after baking the mixture which mixed carbon, a carbon removal process may be needed.
前記コバルト酸リチウムと炭素を混合した混合物としては、代表的には、使用済リチウムイオン二次電池より得られたものを用いることが好ましい。
これは、前記前記コバルト酸リチウムと炭素を混合した混合物として、使用済リチウムイオン二次電池より得られたものを用いる場合には、特別な前処理（コバルト酸リチウムの分離処理）を施すことなく、リチウムを回収できる点から好ましい。
また、前記コバルト酸リチウムと炭素を混合した混合物として、使用済リチウムイオン二次電池より得られたものを用いる場合には、使用済リチウムイオン二次電池の負極には黒鉛（炭素）がコバルト酸リチウムに対し最大４０質量％の量で含まれているので、炭素を添加する必要が無く、そのまま焙焼することができる点で特に好ましい。
更に、通常の正極分離の際には放電工程を必要とするが、リチウムイオン二次電池を焙焼することで放電を行うことができ、放電設備を設けなくてもよい点で優れている。
使用済リチウムイオン二次電池は、焙焼前に粉砕してもよく、粉砕を行う順序に特に制限はない。
使用済リチウムイオン二次電池を粉砕する方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えばハンマークラッシャー、ロッドミル、ボールミル、ジョークラッシャー、ロールクラッシャー、カッターミル、ロータリークラッシャー等の粉砕機により、篩をかけた粉砕物を用いることができる。
As the mixture of lithium cobaltate and carbon, it is typically preferable to use a mixture obtained from a used lithium ion secondary battery.
This is because when the mixture obtained from the used lithium ion secondary battery is used as a mixture of the lithium cobaltate and carbon, a special pretreatment (separation treatment of lithium cobaltate) is not performed. From the viewpoint of recovering lithium.
Moreover, when using what was obtained from the used lithium ion secondary battery as a mixture which mixed the said lithium cobaltate and carbon, graphite (carbon) is cobalt acid in the negative electrode of a used lithium ion secondary battery. Since it is contained in a maximum amount of 40% by mass with respect to lithium, it is particularly preferable in that it is not necessary to add carbon and can be roasted as it is.
Further, although a discharge process is required for normal cathode separation, the discharge can be performed by roasting the lithium ion secondary battery, which is excellent in that it is not necessary to provide a discharge facility.
The used lithium ion secondary battery may be pulverized before roasting, and the order of pulverization is not particularly limited.
There is no restriction | limiting in particular as a method of grind | pulverizing a used lithium ion secondary battery, According to the objective, it can select suitably, For example, a hammer crusher, a rod mill, a ball mill, a jaw crusher, a roll crusher, a cutter mill, a rotary crusher etc. A pulverized product obtained by sieving with a pulverizer can be used.
−焙焼に用いる雰囲気−
前記焙焼に用いる雰囲気としては、特に制限はなく、焙焼条件などに応じて適宜選択することができ、例えば大気雰囲気、酸化雰囲気、不活性雰囲気、還元性雰囲気、などが挙げられる。なお、前記雰囲気は、焙焼中は、通気させておくことが好ましい。
ここで、前記大気雰囲気とは、酸素が２１％、窒素７８％の大気（空気）を用いた雰囲気を意味する。
前記酸化雰囲気とは、窒素又はアルゴン等の不活性雰囲気中に酸素を１質量％〜２１質量％含む雰囲気を意味し、酸素を１質量％〜５質量％含む雰囲気が好ましい。
前記不活性雰囲気とは、窒素又はアルゴンからなる雰囲気を意味する。
前記還元性雰囲気とは、例えば、窒素又はアルゴン等の不活性雰囲気中にＣＯ、Ｈ２、Ｈ２Ｓ、ＳＯ２などを含む雰囲気を意味する。
-Atmosphere used for roasting-
There is no restriction | limiting in particular as atmosphere used for the said baking, According to baking conditions etc., it can select suitably, For example, an air atmosphere, an oxidizing atmosphere, an inert atmosphere, a reducing atmosphere etc. are mentioned. The atmosphere is preferably aerated during roasting.
Here, the air atmosphere means an atmosphere using air (air) of 21% oxygen and 78% nitrogen.
The oxidizing atmosphere means an atmosphere containing 1% by mass to 21% by mass of oxygen in an inert atmosphere such as nitrogen or argon, and an atmosphere containing 1% by mass to 5% by mass of oxygen is preferable.
The inert atmosphere means an atmosphere made of nitrogen or argon.
The reducing atmosphere means an atmosphere containing CO, H 2 , H 2 S, SO 2 and the like in an inert atmosphere such as nitrogen or argon.
−焙焼−
前記焙焼は、焙焼炉を用いて行うことが好ましい。前記焙焼炉としては、特に制限はなく、目的に応じて適宜選択することができ、例えばロータリーキルン、流動床炉、トンネル炉、マッフル等のバッチ式炉、キュウポラ、ストーカー炉、などが挙げられる。本発明においては、大気雰囲気下でも焙焼することができるので、例えばロータリーキルン炉等の普通に用いられている焙焼炉を使用することができ、焙焼炉の選択幅が広くなる。
前記焙焼温度は、特に制限はなく、目的に応じて適宜選択することができ、不活性雰囲気下では５００℃以上７００℃未満である。大気雰囲気下では５００℃以上、酸化雰囲気下では５００℃以上であることが好ましく、上限温度は、１，２００℃以下であることが好ましい。
前記焙焼温度が、５００℃未満であると、例えばリチウムイオン二次電池の正極の結晶構造を破壊できないために、リチウムを溶出させることができないことがあり、１，２００℃を超えると、多大なエネルギーを必要とすると共に、焙焼物が焼結するため、粉砕工程が必要となることがある。
-Roasting-
The roasting is preferably performed using a roasting furnace. There is no restriction | limiting in particular as said roasting furnace, According to the objective, it can select suitably, For example, batch type furnaces, such as a rotary kiln, a fluidized bed furnace, a tunnel furnace, a muffle, a cupola, a stalker furnace, etc. are mentioned. In the present invention, since roasting can be performed even in an air atmosphere, a commonly used roasting furnace such as a rotary kiln furnace can be used, and the selection range of the roasting furnace is widened.
The roasting temperature is not particularly limited and may be appropriately selected depending on the purpose. The roasting temperature is 500 ° C. or higher and lower than 700 ° C. under an inert atmosphere. It is preferably 500 ° C. or higher in an air atmosphere and 500 ° C. or higher in an oxidizing atmosphere, and the upper limit temperature is preferably 1,200 ° C. or lower.
When the roasting temperature is less than 500 ° C., for example, the crystal structure of the positive electrode of the lithium ion secondary battery cannot be destroyed, so that lithium may not be eluted. A large amount of energy is required, and the baked product is sintered, which may require a pulverization step.
−リチウムの浸出−
得られた焙焼物を水で浸出することにより、焙焼物中からリチウムを溶出させて、リチウムを回収することができる。
前記焙焼物の水での浸出方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば水中に浸漬させた焙焼物に、必要に応じて超音波を当てながら緩やかに攪拌することにより行うことができる。
浸出によりリチウムが溶出した液をろ過し、残渣とろ液に分け、ろ液からリチウムを回収できる。回収方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えばろ液を自然乾燥する方法、加熱により乾燥固化する方法、炭酸を吹き込みながら晶析させる方法、などが挙げられる。
-Lithium leaching-
By leaching the obtained roasted product with water, lithium can be eluted from the roasted product and lithium can be recovered.
The method for leaching the roasted product with water is not particularly limited and can be appropriately selected according to the purpose. For example, the roasted product immersed in water is gently stirred while applying ultrasonic waves as necessary. This can be done.
The liquid from which lithium is eluted by leaching is filtered and separated into a residue and a filtrate, and lithium can be recovered from the filtrate. The recovery method is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method of naturally drying the filtrate, a method of drying and solidifying by heating, and a method of crystallizing while blowing carbonic acid. .
本発明のリチウムの回収方法は、焙焼条件に応じて以下の第１の実施形態から第３の実施形態のいずれかであることが好ましい。 The lithium recovery method of the present invention is preferably one of the following first to third embodiments depending on roasting conditions.
＜第１の実施形態＞
前記第１の実施形態に係るリチウムの回収方法は、コバルト酸リチウム１００質量部に対し、１質量部以上の炭素を混合した混合物を、大気雰囲気下、５００℃以上の温度で焙焼してなる焙焼物を水で浸出するものである。
ここで、前記大気雰囲気とは、酸素が２１％、窒素７８％の大気（空気）を用いた雰囲気を意味する。この第１の実施形態では、大気雰囲気下において焙焼できるので、ロータリーキルン炉等の普通に用いられている焙焼炉を使用することができる。
前記炭素の混合量は、コバルト酸リチウム１００質量部に対し、１０質量部以上であることが好ましく、１０質量部〜５０質量部であることがより好ましく、１０質量部〜４０質量部であることが特に好ましい。
前記焙焼温度は、５００℃以上であることが好ましく、７００℃以上であることがより好ましく、７００℃〜１，０００℃であることが特に好ましい。前記焙焼温度が、５００℃未満であると、例えばリチウムイオン二次電池の正極の結晶構造を破壊できないために、リチウムを溶出できないことがある。
焙焼時間は、昇温時間を含め１時間以上であることが好ましく、時間が長くなっても溶出効果は大きく変化しないため、省エネルギーの観点から１時間〜２時間がより好ましい。
<First Embodiment>
The lithium recovery method according to the first embodiment is obtained by roasting a mixture obtained by mixing 1 part by mass or more of carbon with respect to 100 parts by mass of lithium cobaltate at a temperature of 500 ° C. or more in an air atmosphere. The roasted product is leached with water.
Here, the air atmosphere means an atmosphere using air (air) of 21% oxygen and 78% nitrogen. In the first embodiment, since roasting can be performed in an air atmosphere, a commonly used roasting furnace such as a rotary kiln furnace can be used.
The amount of carbon mixed is preferably 10 parts by mass or more, more preferably 10 parts by mass to 50 parts by mass, and more preferably 10 parts by mass to 40 parts by mass with respect to 100 parts by mass of lithium cobalt oxide. Is particularly preferred.
The roasting temperature is preferably 500 ° C. or higher, more preferably 700 ° C. or higher, and particularly preferably 700 ° C. to 1,000 ° C. If the roasting temperature is lower than 500 ° C., for example, the crystal structure of the positive electrode of the lithium ion secondary battery cannot be destroyed, so that lithium may not be eluted.
The roasting time is preferably 1 hour or more including the temperature rising time, and the elution effect does not change greatly even if the time is long. Therefore, 1 hour to 2 hours is more preferable from the viewpoint of energy saving.
＜第２の実施形態＞
前記第２の実施形態に係るリチウムの回収方法は、コバルト酸リチウム１００質量部に対し、１質量部以上の炭素を混合した混合物を、酸化雰囲気下、５００℃以上の温度で焙焼してなる焙焼物を水で浸出するものである。
前記炭素の混合量は、コバルト酸リチウム１００質量部に対し、１質量部〜５０質量部であることが好ましく、５質量部〜４０質量部であることがより好ましい。
前記焙焼温度は、５００℃以上であることが好ましく、５００℃〜１，０００℃であることがより好ましい。前記焙焼温度が、５００℃未満であると、例えばリチウムイオン二次電池の正極の結晶構造を破壊できないために、リチウムを溶出できないことがある。
焙焼時間は、昇温時間を含め１時間以上であることが好ましく、時間が長くなっても溶出効果は大きく変化しないため、省エネルギーの観点から１時間〜２時間がより好ましい。
<Second Embodiment>
The lithium recovery method according to the second embodiment is obtained by roasting a mixture obtained by mixing 1 part by mass or more of carbon with respect to 100 parts by mass of lithium cobaltate in an oxidizing atmosphere at a temperature of 500 ° C. or more. The roasted product is leached with water.
The mixing amount of carbon is preferably 1 part by mass to 50 parts by mass, and more preferably 5 parts by mass to 40 parts by mass with respect to 100 parts by mass of lithium cobalt oxide.
The roasting temperature is preferably 500 ° C. or higher, and more preferably 500 ° C. to 1,000 ° C. If the roasting temperature is lower than 500 ° C., for example, the crystal structure of the positive electrode of the lithium ion secondary battery cannot be destroyed, so that lithium may not be eluted.
The roasting time is preferably 1 hour or more including the temperature rising time, and the elution effect does not change greatly even if the time is long. Therefore, 1 hour to 2 hours is more preferable from the viewpoint of energy saving.
＜第３の実施形態＞
前記第３の実施形態に係るリチウムの回収方法は、コバルト酸リチウム１００質量部に対し、１質量部以上の炭素を混合した混合物を、不活性雰囲気下、５００℃以上７００℃未満の温度で焙焼してなる焙焼物を水で浸出するものである。
前記炭素の混合量は、コバルト酸リチウム１００質量部に対し、１５質量部〜５０質量部であることがより好ましく、１５質量部〜４０質量部であることが更に好ましい。
ここで、前記不活性雰囲気とは、窒素又はアルゴンからなる雰囲気を意味する。
前記焙焼温度は、５００℃以上７００℃未満である。前記焙焼温度が、５００℃未満であると、例えばリチウムイオン二次電池の正極の結晶構造を破壊できないために、リチウムを溶出できないことがある。
焙焼時間は、昇温時間を含め１時間以上であることが好ましく、時間が長くなっても溶出効果は大きく変化しないため、省エネルギーの観点から１時間〜２時間がより好ましい。
<Third Embodiment>
In the lithium recovery method according to the third embodiment, a mixture obtained by mixing 1 part by mass or more of carbon with respect to 100 parts by mass of lithium cobaltate is roasted at a temperature of 500 ° C. or higher and lower than 700 ° C. in an inert atmosphere. The baked product is leached with water.
The mixing amount of the carbon is more preferably 15 parts by mass to 50 parts by mass, and still more preferably 15 parts by mass to 40 parts by mass with respect to 100 parts by mass of lithium cobalt oxide.
Here, the inert atmosphere means an atmosphere made of nitrogen or argon.
The roasting temperature is 500 ° C. or higher and lower than 700 ° C. If the roasting temperature is lower than 500 ° C., for example, the crystal structure of the positive electrode of the lithium ion secondary battery cannot be destroyed, so that lithium may not be eluted.
The roasting time is preferably 1 hour or more including the temperature rising time, and the elution effect does not change greatly even if the time is long. Therefore, 1 hour to 2 hours is more preferable from the viewpoint of energy saving.
本発明のリチウムの回収方法は、リチウムイオン二次電池の正極材料であるコバルト酸リチウムから効率よくリチウムを回収することができ、リチウムイオン二次電池のリサイクルを図ることができる。
本発明のリチウムの回収方法においては、特別な前処理（コバルト酸リチウムの分離処理）を施すことなく、リチウムイオン二次電池より得られるものをそのまま粉砕して、焙焼できるので、極めて効率よくリチウムを回収することができる。
本発明のリチウムの回収方法においては、特に酸化雰囲気下で焙焼した場合には、カーボン残渣の発生が少なく、エネルギーの使用量が少なくて済むという利点がある。
本発明のリチウムの回収方法においては、特に大気雰囲気下で焙焼する場合には、一般的な焙焼炉で焙焼を行うことができ、気密性の高い焙焼炉を用いる必要がなく、焙焼炉の選択幅が広くなる利点がある。
本発明のリチウムの回収方法においては、簡単な操作により、リチウムの回収物の中にコバルトが検出されないほどに、リチウムとコバルトを高度に分離できる。そのため、回収したリチウムは、コバルト酸リチウムのみならず、マンガン酸リチウムなどの他のリチウム含有化合物への再利用が可能である。また、従来のリチウムの回収方法に必要であったリチウムとコバルトを分離回収する工程が不要となり、従来のリチウムの回収方法に比べ、回収工程の短縮及び回収コストの低減が可能である。
The lithium recovery method of the present invention can efficiently recover lithium from lithium cobaltate, which is a positive electrode material of a lithium ion secondary battery, and can recycle the lithium ion secondary battery.
In the method for recovering lithium according to the present invention, the product obtained from the lithium ion secondary battery can be pulverized and roasted as it is without performing any special pretreatment (separation treatment of lithium cobaltate). Lithium can be recovered.
The lithium recovery method of the present invention has the advantage that the generation of carbon residue is small and the amount of energy used is small, especially when roasting in an oxidizing atmosphere.
In the lithium recovery method of the present invention, in particular, when roasting in an air atmosphere, it can be roasted in a general roasting furnace, there is no need to use a highly airtight roasting furnace, There is an advantage that the selection range of the roasting furnace is widened.
In the lithium recovery method of the present invention, lithium and cobalt can be separated to a high degree by simple operations such that cobalt is not detected in the lithium recovery. Therefore, the recovered lithium can be reused not only for lithium cobaltate but also for other lithium-containing compounds such as lithium manganate. In addition, the process of separating and recovering lithium and cobalt, which is necessary for the conventional lithium recovery method, is not required, and the recovery process can be shortened and the recovery cost can be reduced as compared with the conventional lithium recovery method.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
（実施例１）
＜リチウム電池正極材料の分離＞
市販のリチウムイオン二次電池（ａｕ社製、正極にコバルト酸リチウム、負極に黒鉛を使用、炭素含有量はコバルト酸リチウムに対して４０質量％）を、電解液（５％ＮａＣｌ）中に浸漬し、０．１ｍＶになるまで放電させた。その後、手分解により正極材料を取り出し、カッターミルを用いて粉砕し正極材料粉体を得た。その組成を表１に示す。分析の結果、分離された粉体はコバルト酸リチウムであることが確認された。
Example 1
<Separation of lithium battery positive electrode material>
A commercially available lithium ion secondary battery (manufactured by AU, using lithium cobaltate as the positive electrode and graphite as the negative electrode, carbon content of 40% by mass with respect to lithium cobaltate) is immersed in an electrolytic solution (5% NaCl). Then, it was discharged until it became 0.1 mV. Thereafter, the positive electrode material was taken out by manual decomposition and pulverized using a cutter mill to obtain a positive electrode material powder. The composition is shown in Table 1. As a result of analysis, it was confirmed that the separated powder was lithium cobaltate.
＜コバルト酸リチウムの焙焼＞
得られたコバルト酸リチウム１０ｇに、コバルト酸リチウムの質量に対する炭素の質量の割合が表２に示す、炭素濃度（質量％）になるようにカーボンブラック（和光純薬工業株式会社製）を添加し、管状炉（ＫＯＹＯ ＬＩＮＤＢＥＲＧ社製）に挿入した。雰囲気として、表２に示す、５Ｌ／分の不活性雰囲気（窒素）を通気しながら焙焼を行った。焙焼時間は、表２に示す各温度に到達してから１時間とした。
得られた各焙焼物について、以下のようにして、組成を分析した。
<Roasting of lithium cobaltate>
Carbon black (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 10 g of the obtained lithium cobaltate so that the mass ratio of carbon to the mass of lithium cobaltate was the carbon concentration (mass%) shown in Table 2. And inserted into a tubular furnace (manufactured by KOYO LINDBERG). As the atmosphere, roasting was performed while passing an inert atmosphere (nitrogen) of 5 L / min shown in Table 2. The roasting time was 1 hour after reaching the temperatures shown in Table 2.
About each obtained roasted material, the composition was analyzed as follows.
＜焙焼物（固形物）中のリチウム及びコバルトの分析＞
０．１ｇの各焙焼物を王水中で乾固直前まで加温溶解し、ろ過後、イオン交換水で１００ｍＬまでメスアップし、分析用溶液を得た。その溶液を高周波プラズマ発光分光分析装置（日本ジャーレル・アッシュ株式会社製、ＩＣＡＰ−５７５ＩＩ）により分析し、焙焼物（固形物）中のリチウム濃度及びコバルト濃度を計算した。
<Analysis of Lithium and Cobalt in Roasted Product (Solid)>
0.1 g of each baked product was dissolved by heating in aqua regia until immediately before drying, and after filtration, it was made up to 100 mL with ion-exchanged water to obtain a solution for analysis. The solution was analyzed with a high frequency plasma emission spectroscopic analyzer (manufactured by Nippon Jarrell-Ash Co., Ltd., ICAP-575II), and the lithium concentration and cobalt concentration in the roasted product (solid material) were calculated.
＜リチウムの浸出操作＞
得られた各焙焼物０．５ｇを１００ｍＬのメスフラスコ内に入れ、水を１００ｍＬまでメスアップし、ビーカーに移した後、超音波を当てながら緩やかに攪拌しながら、３０分間リチウムを溶出させた。その液をろ過し、残渣とろ液に分け、それぞれを分析した。残渣は上述の方法により分析し、ろ液を直接、高周波プラズマ発光分光分析装置（日本ジャーレル・アッシュ株式会社製、ＩＣＡＰ−５７５ＩＩ）により分析した。
<Lithium leaching operation>
0.5 g of each of the obtained roasted products was placed in a 100 mL volumetric flask, water was made up to 100 mL, transferred to a beaker, and then lithium was eluted for 30 minutes while gently stirring while applying ultrasonic waves. . The liquid was filtered and divided into a residue and a filtrate, and each was analyzed. The residue was analyzed by the above-described method, and the filtrate was directly analyzed by a high-frequency plasma emission spectroscopic analyzer (manufactured by Nippon Jarrell-Ash, ICAP-575II).
リチウムの浸出率及びコバルトの浸出率は、焙焼物（固形物）中のリチウム含有量及びコバルト含有量と、ろ液中に溶けたリチウム量及びコバルト量とから算出した。結果を表２に示す。また、図１に、炭素濃度とＬｉ浸出率との関係を示し、図２に、焙焼温度とＬｉ浸出率との関係を示す。 The leaching rate of lithium and the leaching rate of cobalt were calculated from the lithium content and cobalt content in the roasted product (solid matter), and the lithium amount and cobalt amount dissolved in the filtrate. The results are shown in Table 2. FIG. 1 shows the relationship between the carbon concentration and the Li leaching rate, and FIG. 2 shows the relationship between the roasting temperature and the Li leaching rate.
（実施例２）
実施例１において、酸化雰囲気（酸素：５質量％、窒素：９５質量％）を５Ｌ／分で通気しながら、表３に示す焙焼温度で焙焼を行った以外は、実施例１と同様にして、各焙焼物を得た。
得られた各焙焼物について、実施例１と同様にして、組成を分析した。結果を表３に示す。また、図３に、炭素濃度とＬｉ浸出率との関係を示し、図４に、焙焼温度とＬｉ浸出率との関係を示す。
(Example 2)
In Example 1, it was the same as Example 1 except that the baking was performed at the baking temperature shown in Table 3 while ventilating the oxidizing atmosphere (oxygen: 5 mass%, nitrogen: 95 mass%) at 5 L / min. Thus, each roasted product was obtained.
About each obtained roasted material, it carried out similarly to Example 1, and analyzed the composition. The results are shown in Table 3. FIG. 3 shows the relationship between the carbon concentration and the Li leaching rate, and FIG. 4 shows the relationship between the roasting temperature and the Li leaching rate.
（実施例３）
実施例１において、酸化雰囲気（酸素：１０質量％、窒素：９０質量％）を５Ｌ／分で通気しながら、表４に示す焙焼温度で焙焼を行った以外は、実施例１と同様にして、各焙焼物を得た。
得られた各焙焼物について、実施例１と同様にして、組成を分析した。結果を表４に示す。また、図５に、炭素濃度とＬｉ浸出率との関係を示し、図６、焙焼温度とＬｉ浸出率との関係を示す。
(Example 3)
In Example 1, it was the same as Example 1 except that the baking was performed at the baking temperature shown in Table 4 while ventilating the oxidizing atmosphere (oxygen: 10% by mass, nitrogen: 90% by mass) at 5 L / min. Thus, each roasted product was obtained.
About each obtained roasted material, it carried out similarly to Example 1, and analyzed the composition. The results are shown in Table 4. FIG. 5 shows the relationship between carbon concentration and Li leaching rate, and FIG. 6 shows the relationship between roasting temperature and Li leaching rate.
（実施例４）
実施例１において、大気雰囲気（酸素２１％、窒素７８％）５Ｌ／分で通気しながら、表５に示す焙焼温度で焙焼を行った以外は、実施例１と同様にして、各焙焼物を得た。
得られた各焙焼物について、実施例１と同様にして、組成を分析した。結果を表５に示す。また、図７に、炭素濃度とＬｉ浸出率との関係を示し、図８に、焙焼温度とＬｉ浸出率との関係を示す。
Example 4
In Example 1, each roasting was performed in the same manner as in Example 1 except that the baking was performed at the roasting temperature shown in Table 5 while aeration was performed at 5 L / min in the air atmosphere (21% oxygen, 78% nitrogen). A pottery was obtained.
About each obtained roasted material, it carried out similarly to Example 1, and analyzed the composition. The results are shown in Table 5. FIG. 7 shows the relationship between the carbon concentration and the Li leaching rate, and FIG. 8 shows the relationship between the roasting temperature and the Li leaching rate.
（実施例５）
市販の使用済リチウムイオン二次電池（正極にコバルト酸リチウム、負極に黒鉛を使用、コバルト酸リチウムに対する炭素含有量は４０質量％）を、そのまま大気雰囲気（酸素２１％、窒素７８％）下、８５０℃で管状炉（ＫＯＹＯ ＬＩＮＤＢＥＲＧ社製）に挿入し、１．５時間焙焼を行った。加熱前の電池重量は１７ｇ、加熱後の焙焼物重量が１１．６ｇであった。
得られた焙焼物について、カッターミルで粉砕し、目に見える大きな金属部分は除去した。粉砕により得られた粉末の合計量は８．３ｇ、除去した金属部分は３．３ｇであった。得られた粉末の組成を実施例１と同様の方法で分析したところ、Ｌｉは２．９質量％、Ｃｏは３３．６質量％であった。
次に、得られた粉末について、実施例１と同様の方法でＬｉを浸出し、分析したところ、Ｌｉ浸出率は３０．７％、Ｃｏ浸出率は０．０１％以下（詳細には検出下限値（３．４６×１０−４％）以下）であった。
(Example 5)
A commercially available used lithium ion secondary battery (lithium cobaltate for the positive electrode, graphite for the negative electrode, carbon content with respect to lithium cobaltate is 40% by mass) as it is in an atmospheric atmosphere (oxygen 21%, nitrogen 78%), It inserted in the tubular furnace (made by KOYO LINDBERG) at 850 degreeC, and baked for 1.5 hours. The weight of the battery before heating was 17 g, and the weight of the roasted product after heating was 11.6 g.
The obtained baked product was pulverized by a cutter mill to remove a large metal portion that was visible. The total amount of powder obtained by grinding was 8.3 g, and the removed metal portion was 3.3 g. The composition of the obtained powder was analyzed in the same manner as in Example 1. As a result, Li was 2.9% by mass and Co was 33.6% by mass.
Next, the obtained powder was leached and analyzed in the same manner as in Example 1. As a result, the Li leaching rate was 30.7% and the Co leaching rate was 0.01% or less (in detail, the detection lower limit). Value (3.46 × 10 −4 %) or less).
（実施例６）
実施例５と同じ使用済リチウムイオン二次電池を用い、実施例５と同様の方法で、大気雰囲気（酸素２１％、窒素７８％）５Ｌ／分で通気しながら、焙焼温度を７００℃、炭素含有量を３０％とし、７００℃での保持時間を設けずに焙焼を行った。得られた焙焼物を実施例１と同様の方法により、粉砕し、金属部分を除去した粉末について、実施例１と同様の方法でＬｉを浸出し、分析したところ、Ｌｉ浸出率は６６％であった。
(Example 6)
Using the same used lithium-ion secondary battery as in Example 5, the roasting temperature was set to 700 ° C. while venting in the air atmosphere (21% oxygen, 78% nitrogen) at 5 L / min in the same manner as in Example 5. Roasting was carried out with a carbon content of 30% and no holding time at 700 ° C. The obtained roasted product was pulverized by the same method as in Example 1 and the powder from which the metal portion was removed was leached and analyzed in the same manner as in Example 1. As a result, the Li leaching rate was 66%. there were.
本発明のリチウムの回収方法は、リチウムイオン二次電池の正極材料であるコバルト酸リチウムから、リチウムを効率よく回収することができ、リチウムイオン二次電池の再利用を図ることができる。 The lithium recovery method of the present invention can efficiently recover lithium from lithium cobaltate, which is a positive electrode material of a lithium ion secondary battery, and can reuse the lithium ion secondary battery.
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