JP5719792B2 - Method for producing chemical manganese dioxide from ternary positive electrode active material, chemical manganese dioxide produced by the production method, and secondary battery containing chemical manganese dioxide - Google Patents
Method for producing chemical manganese dioxide from ternary positive electrode active material, chemical manganese dioxide produced by the production method, and secondary battery containing chemical manganese dioxide Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims description 84
- 239000007774 positive electrode material Substances 0.000 title claims description 42
- 239000000126 substance Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000011572 manganese Substances 0.000 claims description 63
- 238000002386 leaching Methods 0.000 claims description 62
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910004499 Li(Ni1/3Mn1/3Co1/3)O2 Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052683 pyrite Inorganic materials 0.000 claims description 3
- 239000011028 pyrite Substances 0.000 claims description 3
- 239000010926 waste battery Substances 0.000 claims description 3
- -1 In step (c) Chemical compound 0.000 claims 1
- 239000013543 active substance Substances 0.000 claims 1
- 235000013312 flour Nutrition 0.000 claims 1
- 238000001556 precipitation Methods 0.000 description 42
- 239000000243 solution Substances 0.000 description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 229910052759 nickel Inorganic materials 0.000 description 23
- 229910052744 lithium Inorganic materials 0.000 description 19
- 239000002244 precipitate Substances 0.000 description 19
- 239000011734 sodium Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000007800 oxidant agent Substances 0.000 description 15
- 150000002739 metals Chemical class 0.000 description 14
- 238000005406 washing Methods 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 238000000975 co-precipitation Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 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
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 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 2
- 238000003921 particle size analysis Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910020677 Co—Mn—Ni Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、三元系正極活物質からの化学二酸化マンガンの製造方法、その製造方法によって製造された化学二酸化マンガン、及び化学二酸化マンガンを含む二次電池に関し、より詳しくは、廃棄されたリチウムイオン電池の三元系正極活物質からＭｎを選択的に沈殿させることにより、化学二酸化マンガン（Chemical Manganese Dioxide、CMD）を製造する方法に関する。 The present invention relates to a method for producing chemical manganese dioxide from a ternary positive electrode active material, chemical manganese dioxide produced by the production method, and a secondary battery containing chemical manganese dioxide, and more specifically, discarded lithium ions. The present invention relates to a method for producing chemical manganese dioxide (CMD) by selectively precipitating Mn from a ternary positive electrode active material of a battery.
二酸化マンガンは、高容量と低毒性を有する特徴があり、特に良好な電気化学的能力を有している物質であり、一次電池と二次電池の正極活物質として注目されている物質である。合成二酸化マンガンは、多様な製造分野において応用されている。商業的な観点から、二酸化マンガンの最も重要なことは、電気化学的な活性を有するという特徴であり、このような特性により、乾電池の正極材として多く用いられている。また、他の商業的な形態は、電子産業における、フェライトとサーミスタ用の超高純度の二酸化マンガンである。二酸化マンガンは、また、特に揮発性有機物の除去やオゾンの分解のような空気汚染物質の分解に用いられる酸化触媒としての使用量が増加し続けている。 Manganese dioxide has a characteristic of having high capacity and low toxicity, has a particularly good electrochemical ability, and has attracted attention as a positive electrode active material for primary batteries and secondary batteries. Synthetic manganese dioxide is applied in various manufacturing fields. From a commercial point of view, the most important thing of manganese dioxide is that it has electrochemical activity, and due to such characteristics, it is often used as a positive electrode material for dry batteries. Another commercial form is ultra-high purity manganese dioxide for ferrites and thermistors in the electronics industry. Manganese dioxide also continues to increase in use as an oxidation catalyst, especially for the removal of volatile organics and the decomposition of air pollutants such as the decomposition of ozone.
合成二酸化マンガンは、マンガン塩やマンガンを含んでいる溶液または自然状態の原鉱石から化学的な工程（Chemical Manganese Dioxide、CMD）や電気化学的方法（electrolytic Manganese Dioxide、EMD）によって製造が可能である。化学的二酸化マンガンは、ＭｎＣＯ３を熱処理して製造が可能であり、また、硫酸溶液からＮａＣｌＯ３を用いた酸化沈殿法によって製造が可能である。 Synthetic manganese dioxide can be produced by chemical processes (Chemical Manganese Dioxide, CMD) or electrochemical methods (electrolytic Manganese Dioxide, EMD) from manganese salts, manganese-containing solutions or natural ores. . Chemical manganese dioxide can be produced by heat-treating MnCO 3 , and can be produced by an oxidation precipitation method using NaClO 3 from a sulfuric acid solution.
最近になって、リチウムイオン電池の需要がだんだん増えてきており、その応用範囲は、携帯用電子機器のエネルギー源として用いられた範囲から、ハイブリッド車（ＨＥＶ）または電気自動車（ＥＶ）の動力源としての需要が増加している。それだけでなく、今後、ロボット産業、エネルギー貯蔵産業、及び航空宇宙産業にまで応用範囲が拡大するものと期待される。したがって、リチウムイオン電池の主要構成成分であるコバルト、リチウム、ニッケル、マンガン等の使用量も、大きく増加するものと予想され、使用後廃棄されるリチウムイオン電池の量も幾何級数的に増えるものと予想される。このような廃リチウムイオン電池から、希少金属であるコバルト、ニッケル、マンガン、リチウム等を分離／回収し、金属及び金属化合物としてリサイクルすることは、大部分を輸入に依存している電池の核心素材を韓国内で安定的に供給することができるという点で、その重要性が極めて高い。 Recently, the demand for lithium-ion batteries has been increasing, and its application range is from the range used as an energy source for portable electronic devices, to the power source of hybrid vehicles (HEV) or electric vehicles (EV). As demand has increased. In addition, it is expected that the range of applications will be expanded to the robot industry, energy storage industry, and aerospace industry in the future. Therefore, the amount of cobalt, lithium, nickel, manganese, etc., which are the main components of lithium ion batteries, is expected to increase greatly, and the amount of lithium ion batteries discarded after use will increase geometrically. is expected. Separating / recovering rare metals such as cobalt, nickel, manganese, lithium, etc. from such waste lithium ion batteries and recycling them as metals and metal compounds is the core material of batteries that are largely dependent on imports. Is extremely important in that it can be supplied stably in Korea.
以前の研究において、リチウムイオン電池からのコバルトの回収のための溶媒抽出工程を提案しているが、最近、高価なＣｏを代替したＣｏ−Ｍｎ−Ｎｉ系の新たなリチウムイオン電池の正極活物質が開発及び商用化するにつれて、正極活物質内のＭｎの含量が増加する趨勢にある。したがって、有価金属の分離回収のためには、Ｍｎの分離が先行されなければならない。 Previous research has proposed a solvent extraction process for the recovery of cobalt from lithium-ion batteries. Recently, a new cathode-active material for Co-Mn-Ni-based lithium-ion batteries replacing expensive Co As it develops and commercializes, the content of Mn in the positive electrode active material tends to increase. Therefore, in order to separate and recover valuable metals, separation of Mn must be preceded.
本発明は、上記問題点に鑑みなされたものであり、その目的は、携帯電話や電気自動車に用いられているリチウムイオン電池の正極活物質である三元系正極活物質（Ｌｉ（Ｎｉ１/３Ｍｎ１/３Ｃｏ１/３）Ｏ２）からのＭｎの選択的な分離のために、硫酸還元浸出溶液から酸化剤を用いてＭｎのみを選択的に沈殿させることにより、化学二酸化マンガンを製造する方法を提供することにある。 The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a ternary positive electrode active material (Li (Ni 1/1 /) that is a positive electrode active material of a lithium ion battery used in a mobile phone or an electric vehicle. 3 Mn 1/3 Co 1/3 ) For selective separation of Mn from O 2 ), the chemical manganese dioxide is precipitated by selectively precipitating only Mn from the sulfate reduction leaching solution using an oxidizing agent. It is to provide a method of manufacturing.
また、本発明の他の目的は、前記製造方法によって製造された化学二酸化マンガンを提供することにある。 Another object of the present invention is to provide a chemical manganese dioxide produced by the production method.
また、本発明の他の目的は、前記製造方法によって製造された化学二酸化マンガンを含む二次電池を提供することにある。 Another object of the present invention is to provide a secondary battery including chemical manganese dioxide manufactured by the manufacturing method.
上記目的を達成するために、本発明は、（ａ）硫酸及び還元剤の混合液で三元系正極活物質粉末を浸出させる第１段浸出のステップと、（ｂ）前記第１段浸出溶液を連続浸出させる第２段浸出のステップと、（ｃ）前記第２段浸出溶液にＮａ２Ｓ２Ｏ８を添加し、Ｍｎを選択的に沈殿させて化学二酸化マンガンを製造するステップと、を含む三元系正極活物質からの化学二酸化マンガンの製造方法を提供する。 In order to achieve the above object, the present invention includes (a) a first stage leaching step of leaching a ternary positive electrode active material powder with a mixed solution of sulfuric acid and a reducing agent, and (b) the first stage leaching solution. A second-stage leaching step for continuously leaching, and (c) adding Na 2 S 2 O 8 to the second-stage leaching solution to selectively precipitate Mn to produce chemical manganese dioxide. A method for producing chemical manganese dioxide from a ternary positive electrode active material is provided.
また、前記ステップ（ｃ）後、（ｄ）前記ステップ（ｃ）において製造された化学二酸化マンガンを酸洗浄するステップをさらに含むことを特徴とする。 In addition, after the step (c), the method further includes (d) a step of acid cleaning the chemical manganese dioxide produced in the step (c).
また、前記ステップ（ｄ）において、硫酸を用いて酸洗浄することを特徴とする。 In the step (d), acid cleaning is performed using sulfuric acid.
また、前記ステップ（ｃ）において、１当量以上のＮａ２Ｓ２Ｏ８を添加することを特徴とする。 In the step (c), 1 equivalent or more of Na 2 S 2 O 8 is added.
また、前記ステップ（ｃ）の反応温度は、９０℃以上であることを特徴とする。 The reaction temperature in step (c) is 90 ° C. or higher.
また、前記ステップ（ｃ）の反応時間は、３００〜４００分であることを特徴とする。 The reaction time in the step (c) is 300 to 400 minutes.
また、前記還元剤は、過酸化水素、Ｈ２Ｓ、ＳＯ２、ＦｅＳＯ４、石炭、及び黄鉄鉱からなる群より選ばれることを特徴とする。 The reducing agent may be selected from the group consisting of hydrogen peroxide, H 2 S, SO 2 , FeSO 4 , coal, and pyrite.
また、前記ステップ（ａ）の三元系正極活物質粉末は、廃電池の三元系正極活物質（Ｌｉ（Ｎｉ１/３Ｍｎ１/３Ｃｏ１/３）Ｏ２）スクラップから物理的な分離工程によってＡｌを分離除去したものであることを特徴とする。 In addition, the ternary positive electrode active material powder of the step (a) is physically obtained from a scrap battery ternary positive electrode active material (Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2 ) scrap. It is characterized in that Al is separated and removed by the separation step.
また、前記物理的な分離工程は、（イ）廃電池の三元系正極活物質（Ｌｉ（Ｎｉ１/３Ｍｎ１/３Ｃｏ１/３）Ｏ２）スクラップを切断するステップと、（ロ）前記切断後、熱処理するステップと、（ハ）前記熱処理後、粉砕するステップと、（ニ）前記粉砕後、４０メッシュ以下のサイズの粒子を分離して収去するステップと、を含むことを特徴とする。 The physical separation step includes (a) cutting a ternary positive electrode active material (Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2 ) scrap of a waste battery; A step of heat-treating after the cutting; (c) a step of pulverizing after the heat-treatment; and (d) a step of separating and removing particles having a size of 40 mesh or less after the pulverization. Features.
また、本発明は、前記製造方法によって製造された化学二酸化マンガンを提供する。 Moreover, this invention provides the chemical manganese dioxide manufactured by the said manufacturing method.
また、本発明は、前記化学二酸化マンガンを含む三元系正極活物質から製造された二次電池を提供する。 In addition, the present invention provides a secondary battery manufactured from a ternary positive electrode active material containing the chemical manganese dioxide.
本発明によると、携帯電話や電気自動車に用いられているリチウムイオン電池の正極活物質である三元系正極活物質（Ｌｉ（Ｎｉ１/３Ｍｎ１/３Ｃｏ１/３）Ｏ２）からのＭｎの選択的な分離のために、硫酸還元浸出溶液から酸化剤であるＮａ２Ｓ２Ｏ８を用いてＭｎのみを選択的に沈殿させることにより、化学二酸化マンガンを製造する方法、その製造方法によって製造された化学二酸化マンガンを提供することができる。 According to the present invention, from a ternary positive electrode active material (Li (Ni 1/3 Mn 1/3 Co 1/3 ) O 2 ) which is a positive electrode active material of a lithium ion battery used in a mobile phone or an electric vehicle. A method for producing chemical manganese dioxide by selectively precipitating only Mn from a sulfuric acid reduction leaching solution using Na 2 S 2 O 8 as an oxidizing agent for selective separation of Mn Chemical manganese dioxide produced by the method can be provided.
本発明は、（ａ）硫酸及び還元剤の混合液で三元系正極活物質粉末を浸出させる第１段浸出のステップと、（ｂ）前記第１段浸出溶液を連続浸出させる第２段浸出のステップと、（ｃ）前記第２段浸出溶液にＮａ２Ｓ２Ｏ８を添加し、Ｍｎを選択的に沈殿させて化学二酸化マンガンを製造するステップと、を含む三元系正極活物質からの化学二酸化マンガンの製造方法を提供する。 The present invention includes (a) a first stage leaching step in which ternary positive electrode active material powder is leached with a mixture of sulfuric acid and a reducing agent, and (b) a second stage leaching in which the first stage leaching solution is continuously leached. And (c) adding Na 2 S 2 O 8 to the second-stage leaching solution and selectively precipitating Mn to produce chemical manganese dioxide. A method for producing chemical manganese dioxide is provided.
以下、添付した図面に基づき、本発明について詳述する。 Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
本発明において、前記還元剤は、過酸化水素、Ｈ２Ｓ、ＳＯ２、ＦｅＳＯ４、石炭、及び黄鉄鉱からなる群より選ばれることを特徴としてもよい。酸性雰囲気において化学的に安定したマンガン酸化物の酸浸出時、還元剤の添加が、マンガン酸化物の浸出率の向上に多くの影響を及ぼすので、本発明では、マンガン酸化物の浸出率を最適化することができる還元剤の濃度、使用量、反応温度及び反応時間を適用し、マンガンの回収率を向上させることができる。 In the present invention, the reducing agent may be selected from the group consisting of hydrogen peroxide, H 2 S, SO 2 , FeSO 4 , coal, and pyrite. During the acid leaching of manganese oxide, which is chemically stable in an acidic atmosphere, the addition of a reducing agent has many effects on the improvement of the leaching rate of manganese oxide. Therefore, in the present invention, the leaching rate of manganese oxide is optimized. The concentration of the reducing agent that can be converted, the amount used, the reaction temperature, and the reaction time can be applied to improve the manganese recovery rate.
前記（ｂ）の第２段浸出のステップでは、前記ステップ（ａ）で収得した１段浸出溶液に還元剤を添加して連続的に浸出する。ここで、使用される還元剤は、上記に挙げた還元剤が用いられてもよく、特に、過酸化水素を用いることが好ましい。 In the second-stage leaching step (b), a reducing agent is added to the first-stage leaching solution obtained in the step (a) to continuously leach. Here, as the reducing agent used, the reducing agents listed above may be used, and it is particularly preferable to use hydrogen peroxide.
本発明において、前記ステップ（ｃ）の酸化剤は、Ｎａ２Ｓ２Ｏ８であり、Ｎａ２Ｓ２Ｏ８によるＭｎ（II）の沈殿反応式は、以下の通りである。 In the present invention, the oxidizing agent in the step (c) is Na 2 S 2 O 8 , and the precipitation reaction formula of Mn (II) with Na 2 S 2 O 8 is as follows.
ＭｎＳＯ４＋Ｎａ２Ｓ２Ｏ８＋２Ｈ２Ｏ＝Ｎａ２ＳＯ４＋ＭｎＯ２＋２Ｈ２ＳＯ４
２ＣｏＳＯ４＋Ｎａ２Ｓ２Ｏ８＋６Ｈ２Ｏ＝Ｎａ２ＳＯ４＋２Ｃｏ(ＯＨ)３＋３Ｈ２ＳＯ４
２ＮｉＳＯ４＋Ｎａ２Ｓ２Ｏ８＋６Ｈ２Ｏ＝Ｎａ２ＳＯ４＋２Ｎｉ(ＯＨ)３＋３Ｈ２ＳＯ４
MnSO 4 + Na 2 S 2 O 8 + 2H 2 O = Na 2 SO 4 + MnO 2 + 2H 2 SO 4
2CoSO 4 + Na 2 S 2 O 8 + 6H 2 O = Na 2 SO 4 + 2Co (OH) 3 + 3H 2 SO 4
2NiSO 4 + Na 2 S 2 O 8 + 6H 2 O = Na 2 SO 4 + 2Ni (OH) 3 + 3H 2 SO 4
上記式からみられるように、Ｍｎの沈殿過程において、Ｃｏ、Ｎｉの一部が一緒に沈殿されるものと判断され、ＣｏとＮｉの共沈を最小化するために、Ｍｎの酸化沈殿ステップにおいて、反応温度、反応時間、及び酸化剤の当量等の条件を特定の範囲内に調整することが好ましい。 As can be seen from the above equation, in the Mn precipitation process, it is determined that a part of Co and Ni are precipitated together, and in order to minimize the coprecipitation of Co and Ni, in the Mn oxidation precipitation step, It is preferable to adjust conditions such as reaction temperature, reaction time, and oxidant equivalent within a specific range.
本発明において、前記ステップ（ｄ）において、酸洗浄の際に用いられる洗浄水は、硫酸であることを特徴としてもよく、前記洗浄水を用いて酸洗浄することにより、ＣＭＤに残余するＣｏ、Ｎｉ、Ｌｉを洗浄除去してＣＭＤを製造することができ、この際、酸洗浄後の洗浄水は、前記第１段浸出の浸出液としてリサイクルすることができる。 In the present invention, in the step (d), the washing water used in the acid washing may be sulfuric acid, and Co remaining in the CMD by acid washing using the washing water, Ni and Li can be removed by washing to produce CMD. At this time, the washing water after the acid washing can be recycled as the leachate of the first stage leaching.
図１は、三元系正極活物質スクラップの物理的分離工程及び廃水低減型連続浸出工程を示した概略図である。前記物理的な分離工程は、以下のような工程からなってもよい。
（イ）廃電池の三元系正極活物質（Ｌｉ（Ｎｉ１/３Ｍｎ１/３Ｃｏ１/３）Ｏ２）スクラップを切断するステップ、
（ロ）前記切断後、熱処理するステップ、
（ハ）前記熱処理後、粉砕するステップ、及び
（ニ）前記粉砕後、４０メッシュ以下のサイズの粒子を分離して収去するステップ
FIG. 1 is a schematic view showing a physical separation process of a ternary positive electrode active material scrap and a waste water reduction type continuous leaching process. The physical separation step may include the following steps.
(A) cutting a scrap battery ternary positive electrode active material (Li (Ni 1/3 Mn 1/3 Co 1 ) O 2 ) scrap;
(B) a heat treatment step after the cutting;
(C) a step of pulverizing after the heat treatment; and (d) a step of separating and collecting particles having a size of 40 mesh or less after the pulverization.
上記のような物理的分離を通じて濃縮された三元系正極活物質の場合、第１段浸出及び第２段浸出を経る間、不純物の濃度が自動に制御され、このように得られた溶液は、有価金属の回収のための分離精製工程に直ちに投入することができる。 In the case of the ternary positive electrode active material concentrated through physical separation as described above, the concentration of impurities is automatically controlled during the first stage leaching and the second stage leaching, and the solution thus obtained is And can be immediately put into a separation and purification process for recovering valuable metals.
三元系正極活物質スクラップからの物理的処理を通じたＡｌ除去工程及び廃水低減型２段連続浸出を通じて、残余Ａｌを除去した溶液内のＬｉ、Ｃｏ、Ｍｎ、Ｎｉ等を対象として、酸化剤であるＮａ２Ｓ２Ｏ８を用いてＭｎを選択的に沈殿除去した。図２は、三元系正極活物質浸出溶液からＭｎの選択的な酸化沈殿のための反応装置を示した図である。 Oxidizing agent for Li, Co, Mn, Ni, etc. in the solution from which residual Al is removed through Al removal process through physical treatment from ternary positive electrode active material scrap and two-stage continuous leaching with reduced wastewater A certain Na 2 S 2 O 8 was used to selectively precipitate Mn. FIG. 2 is a view showing a reactor for selective oxidation precipitation of Mn from a ternary positive electrode active material leaching solution.
以下、本発明を下記の実施例に基づきさらに詳述する。下記の実施例は、本発明を説明するための例示であり、本発明の範囲は、以下添付された特許請求の範囲によるものであり、例示する実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail based on the following examples. The following examples are illustrative for explaining the present invention, and the scope of the present invention is defined by the appended claims below, and is not limited by the illustrated examples.
［実施例］
［実施例１：２Ｍ硫酸溶液による連続浸出工程］
三元系正極活物質から物理的処理を通じて濃縮された正極活物質から、２Ｍ Ｈ２ＳＯ４、Ｈ２Ｏ２ ５ｖｏｌ％、６０℃、５０ｇ／５００ｍｌ、２００ｒｐｍ、２ｈｒの条件下で、浸出実験を進行した。
[Example]
[Example 1: Continuous leaching step with 2M sulfuric acid solution]
A leaching experiment was conducted from a ternary positive electrode active material concentrated through physical treatment under the conditions of 2M H 2 SO 4 , H 2 O 2 5 vol%, 60 ° C., 50 g / 500 ml, 200 rpm, 2 hr. Progressed.
図３は、三元系正極活物質スクラップ試料の２Ｍ硫酸溶液による第１段浸出挙動を示したグラフである。図３に示すように、２Ｍ硫酸浸出の場合、第１段浸出において６０分以内で、全ての元素の場合、浸出率は、それぞれ９５．７％ Ｃｏ、９５．７％ Ｎｉ、９１．４％ Ｍｎ、９８．２％ Ｌｉ、９７．１％ Ａｌであった。この際、不純物であるＡｌの場合、溶液内に約５９ｍｇ／Ｌが存在することが確認された。 FIG. 3 is a graph showing the first stage leaching behavior of a ternary positive electrode active material scrap sample with a 2M sulfuric acid solution. As shown in FIG. 3, in the case of 2M sulfuric acid leaching, within 60 minutes in the first stage leaching, in the case of all elements, the leaching rates were 95.7% Co, 95.7% Ni, 91.4%, respectively. Mn, 98.2% Li, 97.1% Al. At this time, in the case of Al as an impurity, it was confirmed that about 59 mg / L was present in the solution.
第１段浸出溶液を用いて第２段浸出実験を進行した。実験条件は、第１段浸出溶液、５ｖｏｌ％ Ｈ２Ｏ２、６０℃、５０ｇ/５００ｍｌ、２００ｒｐｍ、４ｈｒの条件で進行した。 A second stage leaching experiment was performed using the first stage leaching solution. The experimental conditions were the first stage leaching solution, 5 vol% H 2 O 2 , 60 ° C., 50 g / 500 ml, 200 rpm, 4 hr.
図４は、三元系正極活物質スクラップ試料の第２段浸出挙動（第１段浸出溶液、５ｖｏｌ％ Ｈ２Ｏ２、６０℃、５０ｇ/５００ｍｌ、２００ｒｐｍ、４ｈｒ）を示したグラフである。 FIG. 4 is a graph showing the second-stage leaching behavior (first-stage leaching solution, 5 vol% H 2 O 2 , 60 ° C., 50 g / 500 ml, 200 rpm, 4 hr) of the ternary positive electrode active material scrap sample.
図４に示すように、経時による有価金属の浸出率が、比較的一定に維持されることが確認され、特に、１０分以上の浸出時間で、全ての元素の場合、浸出挙動が平衡に到達することが確認された。第１段浸出において浸出された有価金属の量を除いた第２段浸出においてのみの有価金属の浸出率は、Ｃｏ、Ｎｉ、Ｍｎの場合、約２５〜３０％のみ浸出することが確認され、Ｌｉの場合も、３８％程度と低い浸出率を示すのを観察することができた。この際、浸出溶液のｐＨの場合、浸出時間１０分以降に５〜５．４程度を維持することが確認された。不純物であるＡｌの場合は、浸出時間６０分以降に濃度が８ｍｇ／Ｌにまで減少することが確認された。表１は、２Ｍ硫酸浸出において、第１段浸出ろ液及び第２段浸出ろ液の有価金属の濃度（ｍｇ／Ｌ）を示している。 As shown in FIG. 4, it was confirmed that the leaching rate of valuable metals over time was kept relatively constant. In particular, in the case of all elements, the leaching behavior reached equilibrium in the leaching time of 10 minutes or more. Confirmed to do. The leaching rate of valuable metals only in the second stage leaching excluding the amount of valuable metals leached in the first stage leaching was confirmed to leach only about 25-30% in the case of Co, Ni, Mn, In the case of Li, it was possible to observe a low leaching rate of about 38%. At this time, in the case of the pH of the leaching solution, it was confirmed that the leaching time was maintained at about 5 to 5.4 after 10 minutes. In the case of Al as an impurity, it was confirmed that the concentration decreased to 8 mg / L after 60 minutes of leaching time. Table 1 shows the concentration (mg / L) of valuable metals in the first stage leaching filtrate and the second stage leaching filtrate in 2M sulfuric acid leaching.
表１からみられるように、不純物であるＡｌの場合、８６％程度が除去されたことが確認された。第２段浸出後、浸出ろ液内の有価金属の濃度は、Ｃｏの場合、２２ｇ/Ｌ, Ｍｎ ２１．６ｇ／Ｌ, Ｎｉ ２４．２ｇ／Ｌ、及びＬｉ ９．５ｇ／Ｌであり、Ａｌは、８ｍｇ／Ｌであった。 As can be seen from Table 1, in the case of Al as an impurity, it was confirmed that about 86% was removed. After the second stage leaching, the concentrations of valuable metals in the leaching filtrate are 22 g / L, Mn 21.6 g / L, Ni 24.2 g / L, and Li 9.5 g / L in the case of Co. Was 8 mg / L.
図５は、Ｍｎ−Ｓ−Ｈ２ＯシステムのｐＨ−Ｅｈ ダイアグラムを示したグラフである。このグラフにおいて、ｐＨ５〜６の範囲で、Ｅｈを１Ｖ以上の範囲に維持させると、Ｍｎ（II）をＭｎ（IV）で酸化沈殿させることが可能である。図６乃至図８は、それぞれＣｏとＮｉ、ＬｉのＥｈ−ｐＨ ダイアグラムを示したグラフである。これらからｐＨ２以下、Ｅｈ１．５Ｖ以上の条件で、Ｍｎの選択的な沈殿が可能であるものと判断された。 FIG. 5 is a graph showing a pH-Eh diagram of the Mn—S—H 2 O system. In this graph, Mn (II) can be oxidized and precipitated with Mn (IV) when Eh is maintained in the range of 1 V or more in the range of pH 5-6. 6 to 8 are graphs showing Eh-pH diagrams of Co, Ni, and Li, respectively. From these, it was judged that selective precipitation of Mn was possible under conditions of pH 2 or lower and Eh 1.5 V or higher.
［実施例２：Ｎａ２Ｓ２Ｏ８を酸化剤として用いたＭｎの沈殿］
１．反応時間によるＭｎの沈殿挙動、及びＣｏ、Ｎｉ、Ｌｉの共沈挙動
攪拌速度５００ｒｐｍ、９０℃の温度条件において、浸出溶液内のＭｎ（II）の濃度に対する酸化剤１当量を用いてＭｎの沈殿挙動を確認した。
[Example 2: Precipitation of Mn using Na 2 S 2 O 8 as an oxidizing agent]
1. Precipitation behavior of Mn depending on reaction time and Co-precipitation behavior of Co, Ni and Li Precipitation of Mn using 1 equivalent of oxidizing agent with respect to the concentration of Mn (II) in the leaching solution at a stirring speed of 500 rpm and a temperature of 90 ° C. The behavior was confirmed.
図９は、反応時間によるＭｎの沈殿挙動と、Ｃｏ、Ｎｉ、Ｌｉの共沈挙動（５００ｒｐｍ、Ｎａ２Ｓ２Ｏ８１当量、９０℃、３００分）を示したグラフである。図９に示すように、反応時間が増加するにつれてＭｎの沈殿率が増加することが認められ、同時にＣｏ、Ｎｉ、Ｌｉの沈殿率も２０％まで増加したことが確認された。 FIG. 9 is a graph showing the precipitation behavior of Mn depending on the reaction time and the coprecipitation behavior of Co, Ni, and Li (500 rpm, 1 equivalent of Na 2 S 2 O 8 , 90 ° C., 300 minutes). As shown in FIG. 9, it was confirmed that the precipitation rate of Mn increased as the reaction time increased, and at the same time, the precipitation rates of Co, Ni, and Li were also increased to 20%.
２．反応温度及び酸化剤当量比の変化によるＭｎの沈殿挙動、及びＣｏ、Ｎｉ、Ｌｉの共沈挙動
反応温度を７０℃、８０℃、９０℃、９５℃に変化させ、Ｍｎの沈殿挙動及びＣｏ、Ｎｉ、Ｌｉの共沈挙動を観察した。
2. Precipitation behavior of Mn due to change in reaction temperature and oxidant equivalent ratio, and co-precipitation behavior of Co, Ni, Li The reaction temperature was changed to 70 ° C., 80 ° C., 90 ° C., and 95 ° C. The coprecipitation behavior of Ni and Li was observed.
図１０は、反応温度に対する時間別のＭｎの沈殿挙動（三元系正極活物質の第２段浸出液５００ｍｌ、５００ｒｐｍ、Ｎａ２Ｓ２Ｏ８当量数１，３００分）を示したグラフである。図１０に示すように、反応温度が増加するにつれてＭｎの沈殿率が急に増加することが観察され、反応温度９０℃と９５℃の場合、Ｍｎの沈殿反応速度が少し差はあるが、全てＭｎが９９．５％以上沈殿することが確認された。 FIG. 10 is a graph showing precipitation behavior of Mn according to time with respect to the reaction temperature (second-stage leaching solution of ternary positive electrode active material 500 ml, 500 rpm, Na 2 S 2 O 8 equivalent number 1,300 minutes). As shown in FIG. 10, it is observed that the precipitation rate of Mn rapidly increases as the reaction temperature increases. When the reaction temperature is 90 ° C. and 95 ° C., the Mn precipitation reaction rate is slightly different, It was confirmed that Mn was precipitated at 99.5% or more.
図１１は、時間別のｐＨ及びＥｈの変化挙動（三元系正極活物質の第２段浸出液５００ｍｌ、９０℃、５００ｒｐｍ、Ｎａ２Ｓ２Ｏ８当量数１，３００分）を示したグラフである。反応時間によるＥｈとｐＨの変化をみると、Ｅｈの場合、反応初期に急に上昇して１．４Ｖ以上を維持することが確認され、ｐＨの場合は、酸化剤が投入されることにより、上述した反応式からみられるように、沈殿反応が進行するにつれて硫酸が生成し、ｐＨが０．５まで減少することが確認された。 FIG. 11 is a graph showing the change behavior of pH and Eh according to time (second-stage leaching solution of ternary positive electrode active material 500 ml, 90 ° C., 500 rpm, Na 2 S 2 O 8 equivalent number 1,300 minutes). is there. Looking at the changes in Eh and pH depending on the reaction time, it was confirmed that Eh suddenly rose at the beginning of the reaction and maintained at 1.4 V or higher. In the case of pH, the oxidizing agent was added, As can be seen from the above reaction formula, it was confirmed that sulfuric acid was generated as the precipitation reaction progressed, and the pH decreased to 0.5.
各反応温度別の生成した沈殿物の有価金属の含量（％）を分析した結果を、表２に示している。 Table 2 shows the result of analyzing the valuable metal content (%) of the generated precipitate for each reaction temperature.
表２からみられるように、反応温度が増加するにつれてＭｎの沈殿率も急に増加することが確認され、９０℃以上の条件で９９．７％以上沈殿されることが確認された。また、分離対象であるＣｏ、Ｎｉ、Ｌｉの場合は、殆ど沈殿されなかったことが確認され、沈殿が選択的に行われることが認められた。但し、Ｃｏの場合、反応温度が増加するにつれて沈殿率が０．５％から２．４％まで増加することが認められ、沈殿反応後、共沈されるＣｏの場合、追加の処理が必要であることがわかった。 As can be seen from Table 2, it was confirmed that the precipitation rate of Mn suddenly increased as the reaction temperature increased, and it was confirmed that 99.7% or more was precipitated at 90 ° C. or higher. In addition, in the case of Co, Ni, and Li to be separated, it was confirmed that almost no precipitation occurred, and it was confirmed that precipitation was performed selectively. However, in the case of Co, it is recognized that the precipitation rate increases from 0.5% to 2.4% as the reaction temperature increases. In the case of Co that is co-precipitated after the precipitation reaction, additional treatment is required. I found out.
３．酸化剤当量によるＭｎの沈殿挙動、及びＣｏ、Ｎｉ、Ｌｉの共沈挙動
９０℃の温度条件下で、酸化剤の当量比を１、１．１、１．２と増加させ、Ｍｎの沈殿挙動及びＣｏ、Ｎｉ、Ｌｉの共沈挙動を観察した。
3. Precipitation behavior of Mn by oxidant equivalent and coprecipitation behavior of Co, Ni, Li Under the temperature condition of 90 ° C., the equivalent ratio of oxidant was increased to 1, 1.1, 1.2, and Mn precipitation behavior And the coprecipitation behavior of Co, Ni and Li was observed.
図１２は、酸化剤の当量比によるＭｎの沈殿挙動を示したグラフである。図１２に示すように、酸化剤の当量比が増加するにつれてＭｎの沈殿率も増加しており、１当量以上の条件では、反応時間３００分以上で大部分のＭｎが沈殿されることが確認された。表３に酸化剤当量比の変化による有価金属の沈殿率（％）を示している。 FIG. 12 is a graph showing the precipitation behavior of Mn depending on the equivalent ratio of the oxidizing agent. As shown in FIG. 12, the precipitation rate of Mn increases as the equivalent ratio of the oxidizing agent increases, and it is confirmed that most of Mn is precipitated in the reaction time of 300 minutes or more under the condition of 1 equivalent or more. It was done. Table 3 shows the precipitation rate (%) of valuable metals due to changes in the oxidant equivalent ratio.
表２と表３における沈殿物の分析結果に基づき、Ｍｎが沈殿される間、共沈されるＣｏ、Ｌｉ、Ｎｉの含量が微々たることが確認された。しかし、Ｍｎが酸化沈殿される間、溶液内のこれらの有価金属の濃度は、２０％程度低くなることが確認された。これは、生成した二酸化マンガンの表面電位が負の値を有し、溶液内のカチオンが二酸化マンガンの表面に吸着されるからである。したがって、製造された二酸化マンガンを回収するために、固液分離後、得られた二酸化マンガンを対象として水洗を通じて、吸着されたＮｉ、Ｃｏ、Ｌｉイオンを洗浄分離し、この過程によって回収可能なＮｉ、Ｃｏ、Ｌｉの含量を調査した。 Based on the analysis results of the precipitates in Tables 2 and 3, it was confirmed that the contents of Co, Li, and Ni that were coprecipitated while Mn was precipitated were insignificant. However, it was confirmed that the concentration of these valuable metals in the solution decreased by about 20% while Mn was oxidized and precipitated. This is because the surface potential of the produced manganese dioxide has a negative value, and the cations in the solution are adsorbed on the surface of the manganese dioxide. Therefore, in order to recover the produced manganese dioxide, after solid-liquid separation, the adsorbed Ni, Co, and Li ions are washed and separated through water washing on the obtained manganese dioxide, and Ni that can be recovered by this process The contents of Co, Co and Li were investigated.
表４は、５００ｍｌの初期溶液に対する最終溶液、沈殿物に対するマスバランスの計算値から得られた沈殿率（％）を示している。 Table 4 shows the precipitation rate (%) obtained from the calculated value of the mass balance for the final solution and the precipitate for 500 ml of the initial solution.
表４からみられるように、各沈殿率の基準による有価金属の沈殿率の計算値を検討すると、溶液基準沈殿率は、Ｍｎを除いて約２３〜２９％を示している。 As can be seen from Table 4, when the calculated value of the precipitation rate of the valuable metal based on each precipitation rate criterion is examined, the solution-based precipitation rate is about 23 to 29% excluding Mn.
また、沈殿物基準沈殿率の場合は、Ｍｎを除いてＮｉとＬｉの場合、殆ど沈殿が発生せず、Ｃｏの場合、約２．７％の沈殿率を示すことが確認された。 In addition, in the case of the precipitation standard precipitation rate, it was confirmed that almost no precipitation was generated in the case of Ni and Li except for Mn, and the precipitation rate was about 2.7% in the case of Co.
沈殿過程において、一部の有価金属が沈殿物の表面に吸着されるので、これらを回収する洗浄過程が必要であり、洗浄後、有価金属を含有している洗浄溶液は、必ず浸出溶液等としてリサイクルして有価金属を回収することが重要であるものと判断された。 In the precipitation process, some valuable metals are adsorbed on the surface of the precipitate, so a cleaning process is required to collect them. After washing, the cleaning solution containing valuable metals must be a leaching solution. It was judged that it was important to recover valuable metals by recycling.
［実施例３：生成した沈殿物内の不純物の除去］
生成した沈殿物内に含まれているＣｏ、Ｎｉ、Ｌｉを除去するために、４Ｍ Ｈ２ＳＯ４、１０ｇ／１００ｍｌ、８０℃、５００ｒｐｍ、２時間の洗浄実験を実施した。表５に酸洗浄による沈殿物内の不純物の除去率（％）を示している。
[Example 3: Removal of impurities in generated precipitate]
In order to remove Co, Ni, and Li contained in the generated precipitate, 4 MH 2 SO 4 , 10 g / 100 ml, 80 ° C., 500 rpm, 2 hours washing experiment was performed. Table 5 shows the removal rate (%) of impurities in the precipitate by acid washing.
表５からみられるように、Ｃｏの除去率は２４．８％であり、Ｎｉは４５．６％であった。Ｌｉの場合は、酸洗浄前後の含量変化が殆どないことから、製造された沈殿物の表面に吸着される量が殆どないものと判断された。以上の結果から酸洗浄を通じて、９８％以上の純度を有する沈殿物の回収が可能であることが確認された。 As can be seen from Table 5, the removal rate of Co was 24.8% and Ni was 45.6%. In the case of Li, since there was almost no change in the content before and after acid washing, it was judged that there was almost no amount adsorbed on the surface of the produced precipitate. From the above results, it was confirmed that a precipitate having a purity of 98% or more can be recovered through acid washing.
［実験結果］
不純物が洗浄された沈殿物を対象としてＸＲＤを用いて化学結晶型を分析してみた。図１３は、製造されたＭｎ沈殿物のＸＲＤ分析結果のグラフである。図１３に示すように、沈殿物の化学結晶型は、γ-ＭｎＯ２であることが確認された。
[Experimental result]
The chemical crystal form was analyzed using XRD for the precipitate from which impurities were washed. FIG. 13 is a graph of the XRD analysis result of the produced Mn precipitate. As shown in FIG. 13, the chemical crystal type of the precipitate was confirmed to be γ-MnO 2 .
この沈殿物を対象として熱重量分析を行い、熱処理による重量減少挙動を検討した。 A thermogravimetric analysis was performed on this precipitate, and the weight reduction behavior by heat treatment was examined.
図１４は、製造されたＭｎ沈殿物のＴＧ-ＤＴＡ分析結果のグラフである。図１４に示すように、５０２．０８℃、５９０．０２℃、７５６．８４℃において重量減少が生じることが確認された。したがって、重量減少による相変化を観察するために、２５０℃、５００℃、６２０℃、７８０℃の条件で沈殿物を熱処理し、それぞれＸＲＤ分析を行った。 FIG. 14 is a graph of a TG-DTA analysis result of the produced Mn precipitate. As shown in FIG. 14, it was confirmed that weight loss occurred at 502.08 ° C., 590.02 ° C., and 756.84 ° C. Therefore, in order to observe the phase change due to weight loss, the precipitates were heat-treated at 250 ° C., 500 ° C., 620 ° C., and 780 ° C., and XRD analysis was performed respectively.
図１５は、製造されたＭｎ沈殿物の熱処理条件によるＸＲＤ分析結果のグラフである。図１５に示すように、５００℃の熱処理試料までは、γ-ＭｎＯ２の結晶型を有することが確認されたが、それ以上の温度条件では、Ｍｎ２Ｏ３の結晶型を有することが確認された。表６に熱処理試料の化学成分分析結果（％）を示している。 FIG. 15 is a graph of the XRD analysis result according to the heat treatment conditions of the produced Mn precipitate. As shown in FIG. 15, it was confirmed that the heat-treated sample at 500 ° C. had a crystal form of γ-MnO 2 , but it was confirmed that it had a crystal form of Mn 2 O 3 at higher temperature conditions. It was done. Table 6 shows the chemical composition analysis result (%) of the heat-treated sample.
表６からみられるように、原試料のＭｎ含量は６５．１％として、ＭｎＯ２の組成を有することが確認され、熱処理温度が増加するにつれてＭｎの含量が７７．８％と増加することが確認された。この際、主な不純物はＣｏであり、不純物の含量を１〜１．１％程度含有していることが確認された。 As can be seen from Table 6, it was confirmed that the Mn content of the original sample was 65.1% and that it had a composition of MnO 2 , and that the Mn content increased to 77.8% as the heat treatment temperature increased. It was done. At this time, it was confirmed that the main impurity is Co and the content of the impurity is about 1 to 1.1%.
図１６は、製造された二酸化マンガンの平均粒度分析を示したグラフである。図１６に示すように、粒径分析器の分析を通じて、１０．７μｍの平均粒径を有する二酸化マンガンが製造されることが確認された。 FIG. 16 is a graph showing an average particle size analysis of the manufactured manganese dioxide. As shown in FIG. 16, it was confirmed that manganese dioxide having an average particle size of 10.7 μm was produced through analysis by a particle size analyzer.
以上の結果から、次のような三元系正極活物質のリサイクル工程を提案することができるものと判断される。リチウムイオン電池に用いられる正極活物質内のＭｎの含量が増加し続けている状況で、湿式製錬法を用いてこれらを分離回収するとき、先ず、Ｍｎを酸化沈殿法を用いてＣＭＤとして選択的に製造した後、回収されるろ液内のＣｏ、Ｎｉ、Ｌｉは、溶媒抽出を用いてＣｏを回収し、ラフィネートに残っているＮｉとＬｉは、もう一回の溶媒抽出を通じてＮｉを回収する工程、及び２回目の溶媒抽出後に発生するＬｉ溶液は、炭酸ナトリウムを用いた炭酸塩沈殿を通じて炭酸リチウムとして回収することができる。 From the above results, it is determined that the following ternary positive electrode active material recycling process can be proposed. In the situation where the content of Mn in the positive electrode active material used for the lithium ion battery continues to increase, when these are separated and recovered using the wet smelting method, first, Mn is selected as the CMD using the oxidation precipitation method. Co, Ni, and Li in the recovered filtrate are recovered using solvent extraction, and Ni and Li remaining in the raffinate are recovered through another solvent extraction. And the Li solution generated after the second solvent extraction can be recovered as lithium carbonate through carbonate precipitation using sodium carbonate.
Claims (6)
（ｂ）第１段浸出溶液を連続浸出させる第２段浸出のステップと、
（ｃ）第２段浸出溶液にＮａ２Ｓ２Ｏ８を添加し、Ｍｎを選択的に沈殿させて化学二酸化マンガンを製造するステップと、
を含み、
前記ステップ（ｃ）において、１当量以上のＮａ２Ｓ２Ｏ８を添加し、
前記ステップ（ｃ）の反応温度は、９０℃以上であり、
前記ステップ（ｃ）の反応時間は、３００〜４００分である、
ことを特徴とする三元系正極活物質からの化学二酸化マンガンの製造方法。 (A) a mixture of sulfuric acid and a reducing agent, ternary positive electrode active substance containing Al (Li (Ni 1/3 Mn 1/3 Co 1/3) O 2) first stage leach flour powder leaching And the steps
(B ) a second stage leaching step for continuously leaching the first stage leaching solution;
(C ) adding Na 2 S 2 O 8 to the second stage leaching solution and selectively precipitating Mn to produce chemical manganese dioxide;
Including
In step (c), 1 equivalent or more of Na 2 S 2 O 8 is added,
The reaction temperature of the step (c) is 90 ° C. or higher,
The reaction time in step (c) is 300 to 400 minutes.
A method for producing chemical manganese dioxide from a ternary positive electrode active material.
（イ）Ａｌを含む廃電池の三元系正極活物質スクラップを切断するステップと、
（ロ）前記切断後、熱処理するステップと、
（ハ）前記熱処理後、粉砕するステップと、
（ニ）前記粉砕後、４０メッシュ以下のサイズの粒子を分離して収去するステップと、 を含むことを特徴とする請求項５に記載の三元系正極活物質からの化学二酸化マンガンの製造方法。 The physical separation step includes
(B) a step of cutting the ternary positive electrode active material scrap waste batteries including Al,
(B) a heat treatment step after the cutting;
(C) crushing after the heat treatment;
(D) separating the particles having a size of 40 mesh or less after the crushing and removing the particles, and producing chemical manganese dioxide from the ternary positive electrode active material according to claim 5 Method.
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| JP6070898B2 (en) * | 2014-04-21 | 2017-02-01 | Ｊｆｅスチール株式会社 | Method and facility for recovering valuable components from waste dry batteries |
| CN107002171A (en) * | 2014-09-30 | 2017-08-01 | 捷客斯金属株式会社 | The leaching method of lithium ion battery waste material and come from lithium ion battery waste material metal recovery method |
| KR101528507B1 (en) * | 2015-01-13 | 2015-06-12 | 한국지질자원연구원 | Co-recovery method of cobalt and manganese from litium cells |
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| CN107986335A (en) * | 2017-12-14 | 2018-05-04 | 上海第二工业大学 | A kind of method that manganese dioxide particle is prepared using waste and old ternary dynamic lithium battery positive electrode |
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| KR102154600B1 (en) | 2018-10-24 | 2020-09-10 | 코스모에코켐(주) | Selective leaching method of cathode active material from lithium ion battery |
| KR102442036B1 (en) | 2020-03-27 | 2022-09-08 | 코스모화학 주식회사 | Method for recovery of manganese compounds from cathode active material of waste lithium ion battery |
| CN112271351B (en) * | 2020-10-26 | 2021-08-31 | 宁波互邦新材料有限公司 | Process for efficiently leaching and recovering ternary cathode material |
| KR20240065463A (en) | 2022-10-28 | 2024-05-14 | 고등기술연구원연구조합 | Method of selective recovery of Lithium by persulfate-based oxdizing agent from wate LFP cathode |
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