CN115786731A - Method for selectively recovering lithium from lithium manganese iron phosphate - Google Patents
Method for selectively recovering lithium from lithium manganese iron phosphate Download PDFInfo
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- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 52
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000000843 powder Substances 0.000 claims abstract description 74
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 33
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims description 15
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 54
- 238000002386 leaching Methods 0.000 description 21
- 239000012535 impurity Substances 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 239000003575 carbonaceous material Substances 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for selectively recovering lithium from lithium manganese iron phosphate using a sulfuric acid solution, whereinComprises the following steps: lithium manganese iron phosphate (LiMnFePO) 4 LMFP) powder is reacted with a sulfuric acid solution having a concentration of more than 1M and less than 3M for at least more than 30 minutes and less than 120 minutes, and the lithium manganese iron phosphate (LiMnFePO) 4 LMFP) the weight ratio of powder to sulfuric acid solution is greater than 1.
Description
Technical Field
The present invention relates to a method for selectively recovering lithium from lithium manganese iron phosphate using a sulfuric acid solution.
Background
With the development of battery performance, lithiumA cathode active material for a secondary battery has been developed in various ways. LiCoO used initially 2 The performance of the materials in the initial stage of the continuous development of doping or surface modification and the like can be applied even under the charging voltage of close to 4.3V recently.
On the other hand, as the application equipment becomes complicated, the characteristics required for the lithium secondary battery are further enhanced. New materials requiring high operating voltages and high capacities are being developed. In recent years, with the enhancement of carbon regulation at home and abroad, secondary batteries for electric vehicles have been actively developed to meet the carbon regulation, and new materials with high output and high safety have been required. In view of the above requirements, for example, liMn has been developed 2 O 4 、 LiFePO 4 ,LiMnFePO 4 The safety of (2) is very excellent.
Lithium manganese iron phosphate (LiMnFePO) 4 LMFP), because of its advantages of high output, low cost, low toxicity, excellent thermal stability, high reversibility, etc., is recognized as one of the most promising cathode materials for lithium ion batteries. Thus, lithium ion batteries using LMFP as a positive electrode material have recently been widely used in Electric Vehicles (EV) and Hybrid Electric Vehicles (HEV), particularly electric buses.
The amount of discarded secondary batteries for Electric Vehicles (EV), which have reached a service life (5 to 10 years), has entered a stage of a substantial increase, "fraught surliin consultant (Frost & Sullican)" predicts an average annual increase in the battery market after global use of 99.8%, and will reach 78 billion dollars in 2025. Due to the rapid increase in demand for LMFP batteries, disposal of the LMFP batteries after use is expected to be a problem.
In particular, the toxic LiPF of LMFP batteries 6 And organic electrolytes containing metal ions migrate into soil and groundwater to cause environmental pollution when discarded into landfill sites, and thus, post-treatment processes such as recovery and reuse are important. In addition, with the development of Electric Vehicles (EV) and Hybrid Electric Vehicles (HEV), demand for lithium, a main raw material of LMFP batteries, has also sharply increased, and lithium supply and demand in korea has completely relied on import, and thus, an increased risk is expected in terms of stability of lithium supply and demand in the future. Therefore, the used LMFP batteryThe recycling of (b) is not only environmentally friendly but also contributes to the stability of lithium supply and demand in korea.
As a conventional method for recycling the LMFP battery after use, a hydrometallurgical method and a direct regeneration method can be mentioned. The hydrometallurgical method is a method mainly used when recycling a used lithium ion battery, and is a method of leaching a positive electrode active material obtained in a pretreatment step, selectively separating a metal from a leaching solution, and then refining the metal. The hydrometallurgical method of the LMFP battery which is recycled and used at present is to use H in the leaching process 2 SO 4 HCl and H 3 PO 4 Etc., and then leaching all elements of the cathode active material using NaOH or NH 3 、H 2 O undergoes a complex chemical precipitation separation process. At this time, in order to leach all metals into the solution, an excess of acid is added and a high concentration is obtained, and thus, there is a problem that a large amount of alkali is required in the separation process.
The direct regeneration method is a method of recovering and reusing a used battery positive electrode material as a raw material of the battery positive electrode material by immersing the battery positive electrode material in an organic solvent. As a method for directly regenerating a used LMFP battery, there is a method in which LMFP powder is separated directly from a positive electrode and then heated at a high temperature or immersed in an organic solvent and then recovered. However, the recovered positive electrode material is likely to contain a large amount of impurities, and generally, after many charge-discharge cycles, the structure is destroyed, resulting in poor electrochemical performance during recycling. Therefore, in order to develop an industrially feasible recycling process for the LMFP battery after use, it is necessary to make the process simpler, more efficient, and more environmentally friendly.
Disclosure of Invention
The invention aims to provide a method for selectively recovering lithium from lithium manganese iron phosphate by controlling the reaction conditions of the lithium manganese iron phosphate and a sulfuric acid solution.
A method for selectively recovering lithium from lithium manganese iron phosphate according to an embodiment of the present invention includes; lithium manganese iron phosphate (LiMnFePO) 4 LMFP) powder with a sulfuric acid solution at a concentration of more than 30 minutes and less than 120 minutesMore than 1M and less than 3M, the lithium manganese iron phosphate (LiMnFePO) 4 LMFP) the weight ratio of powder to sulfuric acid solution is greater than 1.
In one embodiment, the reacting step may be performed at ambient temperature.
In one embodiment, the reacting step may include reacting the lithium manganese iron phosphate (LiMnFePO) 4 LMFP) a step of stirring a mixture of the powder and the sulfuric acid solution at a speed of 250 to 350 rpm.
In one embodiment, only lithium ions may be selectively leached from the lithium manganese iron phosphate powder in the reaction step.
In one embodiment, the present invention may further include a step of performing solid-liquid separation on the reaction solution after the reaction step.
In one embodiment, the solution filtered through the solid-liquid separation step includes lithium sulfate, and Mn, which does not contain impurities 2+ Fe 3+ 4 (PO 4 ) 3 (OH) 5 ,Mn(C 6 H 5 COO) 2 N 2 H 4 ,Li 6 P 6 O 18 H 2 O,MnSO 4 ,Fe 2 (SO 4 ) 3 , Fe 5 (PO 4 ) 3 (OH) 5 ,Fe 2 PO 5 ,Mn(SO 4 )(H 2 O) and Fe 2 (SO 4 ) 4 (H 2 O) 2 。
In one embodiment, the solid-liquid separation may be performed by a reduced pressure filtration method.
In one embodiment, the present invention may further include a step of drying the filtered solution after the solid-liquid separation.
In one embodiment, the drying step may be performed at a temperature of 350 to 500 ℃ for 22 hours or more and 26 hours or less.
In one embodiment, lithium sulfate powder free of impurities may be prepared in the drying step.
In one embodiment, the present invention may further include the step of heat-treating the mixture of the material consisting of the lithium sulfate powder and carbon in an atmosphere of carbon dioxide or carbon monoxide.
In one embodiment, the material made of carbon includes at least one of carbon powder, graphene, graphite, activated carbon, and carbon black.
In one embodiment, the heat treatment may be performed at a temperature of 700 to 900 ℃.
In one embodiment, lithium carbonate (Li) may be prepared during the heat treatment step 2 CO 3 )。
In one embodiment, the lithium manganese iron phosphate (LiMnFePO) 4 LMFP) the powder may be a powder recovered from a spent lithium ion battery.
Effects of the invention
Unlike the conventional process of leaching all elements contained in lithium manganese iron phosphate into solution by using an excessive and high-concentration inorganic acid and then separating the leached elements, the present invention can control lithium manganese iron phosphate (LiMnFePO) 4 LMFP) and sulfuric acid solution, only selectively leaching and recovering lithium except for impurities, and thus, compared with the existing process, the process is simpler and more efficient, the recovery rate of lithium is also more than 99%, and a high recovery rate can be achieved.
In addition, according to the present invention, lithium sulfate powder containing no impurities can be easily prepared, and lithium carbonate can be prepared from the lithium sulfate powder through a simple dry heat treatment process, thereby having an advantage of process convenience.
Drawings
Fig. 1 is a schematic view of a method of selectively recovering lithium from lithium manganese iron phosphate according to an embodiment of the present invention.
Fig. 2 shows the result of XRD (X-ray Diffraction) analysis of the LMFP powder used in the examples of the present invention.
Fig. 3 shows XRD analysis results of the dry powder prepared by varying the concentration of the sulfuric acid solution according to an embodiment of the present invention.
Fig. 4 shows XRD analysis results of the dry powder prepared by varying the stirring time during the reaction according to an embodiment of the present invention.
Figure 5 shows XRD analysis results of dried powders prepared by varying the solid-to-liquid ratio of the sulfuric acid solution and the LMFP powder according to an embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The present invention may be variously modified and may have various forms, and specific embodiments are illustrated in the drawings and described in detail herein. However, it should be understood that the present invention is not limited to the specific forms disclosed, and includes all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention.
The terminology used in the description is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Where not specifically mentioned in the context, the singular forms include the plural forms. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, steps, acts, components, and/or combinations thereof, but do not preclude the presence or addition of one or more other features, steps, acts, components, and/or combinations thereof.
Unless defined otherwise, all terms used in this specification including technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms defined in commonly used dictionaries should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The invention is directed to the use of lithium manganese iron phosphate (LiMnFePO) 4 LMFP) selective leaching of lithium, controlled lithium manganese iron phosphate (LiMnFePO) 4 LMFP) reaction conditions with sulfuric acid solution. In this case, the present invention is based on lithium manganese iron phosphate (LiMnFePO) 4 LMFP) acid solvent for leaching lithium can adopt 98.08% sulfuric acid (H) 2 SO 4 ) Solution, lithium manganese iron phosphate (LiMnFePO) 4 LMFP), powder recovered from a spent lithium ion battery may be used.
Fig. 1 is a schematic view illustrating a method of selectively recovering lithium from lithium manganese iron phosphate according to an embodiment of the present invention.
Referring to fig. 1, the method for selectively recovering lithium from lithium manganese iron phosphate according to the present invention may include mixing lithium manganese iron phosphate (LiMnFePO) 4 LMFP) powder with a sulfuric acid solution having a concentration of more than 1M and less than 3M, lithium manganese iron phosphate (LiMnFePO) for at least 30 minutes and less than 120 minutes (S100) 4 LMFP), the weight ratio of powder to sulfuric acid solution may be greater than 1.
The step (S100) is a process of leaching only lithium ions from lithium manganese iron phosphate, and in the step (S100), a reaction occurs according to the following reaction formula.
[ REACTION TYPE ]
2LiMnFePO 4 (s)+H 2 SO 4 (aq)＝Li 2 SO 4 (aq)+2FePO 4 (s)+2MnPO 4 (s) +H 2
Specifically, to produce lithium manganese iron phosphate (LiMnFePO) 4 LMFP) powder in which only lithium ions are leached, and lithium manganese iron phosphate (limnffepo) in the step (S100) 4 LMFP) the concentration of the sulfuric acid solution of the powder reaction is preferably greater than 1M and less than 3M, most preferably 2M. When the concentration of the sulfuric acid solution is 1M or less, leaching of Fe, mn, P occurs, resulting in generation of Mn such as Mn in the solution 2+ Fe 3+ 4 (PO 4 ) 3 (OH) 5 When the concentration of the sulfuric acid solution is 3M or more, leaching of Mn occurs, resulting in generation of Mn (C) in the solution, for example 6 H 5 COO) 2 N 2 H 4 And the like.
In addition, to produce lithium manganese iron phosphate (LiMnFePO) 4 LMFP) powder in which only lithium ions are leached, and in the step (S100), lithium manganese iron phosphate (LiMnFePO) 4 LMFP) the reaction time of the powder with the sulfuric acid solution is preferably more than 30 minutes and less than 120 minutes, and, most preferably, 60 minutes. When the reaction time is less than 30 minutes, leaching of Fe, mn, P occurs, resulting in the generation of Li, for example, in the solution 6 P 6 O 18 H 2 O,MnSO 4 ,Fe 2 (SO 4 ) 3 When the reaction time is less than 120 minutes or more, leaching of Fe occurs, resulting in generation of Fe such as Fe in the solution 5 (PO 4 ) 3 (OH) 5 And the like.
On the other hand, to remove lithium manganese iron phosphate (LiMnFePO) 4 LMFP) powder from which only lithium ions are leached, and in the step (S100), lithium manganese iron phosphate (LiMnFePO) 4 LMFP), the weight ratio of powder to sulfuric acid solution is preferably greater than 1. When the weight ratio of LMFP powder to sulfuric acid solution is 1 or less, leaching of Fe, mn, P occurs, resulting in generation of Fe, for example, in the solution 2 PO 5 ,Mn(SO 4 )(H 2 O),Fe 2 (SO 4 ) 4 (H 2 O) 2 When 1 4 (H 2 O), and the like.
As described above, in the present invention, a sulfuric acid solution having a concentration of more than 1M and less than 3M is mixed with lithium manganese iron phosphate powder in a weight ratio of more than 1: a step of reacting 3 to less than 7 of lithium manganese iron phosphate (LiMnFePO 4, LMFP) powder with a sulfuric acid solution for more than 30 minutes and less than 120 minutes, whereby only lithium ions can be selectively leached from the lithium manganese iron phosphate powder. At this time, the step (S100) is preferably performed at normal temperature because when the temperature exceeds normal temperature, leaching of Mn, fe, P occurs, resulting in the generation of, for example, mnSO in the solution 4 ,Fe 2 (SO 4 ) 3 ,Mn 2+ Fe 3+ 4 (PO 4 ) 3 (OH) 5 And the like.
In addition, the step (S100) may include stirring the lithium manganese iron phosphate (LiMnFePO) at a speed of 250 to 350rpm 4 LMFP) a mixture of the powder and a sulfuric acid solution. Therefore, the reaction can be carried out by stirring the mixed solution.
The present invention may further include a step (S200) of performing solid-liquid separation on the reaction solution after the step (S100). In one embodiment, the solid-liquid separation is not particularly limited, and may be performed by a known method, preferably by a filtration method under reduced pressure.
The solution filtered through the step (S200) contains lithium sulfate (Li) 2 SO 4 ) Mn containing no impurities 2+ Fe 3+ 4 (PO 4 ) 3 (OH) 5 ,Mn(C 6 H 5 COO) 2 N 2 H 4 ,Li 6 P 6 O 18 H 2 O,MnSO 4 ,Fe 2 (SO 4 ) 3 , Fe 5 (PO 4 ) 3 (OH) 5 ,Fe 2 PO 5 ,Mn(SO 4 )(H 2 O) and Fe 2 (SO 4 ) 4 (H 2 O) 2 . This is because only lithium ions are leached in the step (S200) to generate lithium sulfate (Li) 2 SO 4 )。
On the other hand, the present invention may further include a step (S300) of drying the filtered solution after the solid-liquid separation. In one embodiment, the step (S300) is preferably performed at a temperature of 350 to 500 ℃ for 22 hours or more and 26 hours or less because since the boiling point of sulfuric acid is 337 ℃, it should be performed at a temperature of 350 to 500 ℃ so that the lithium sulfate powder is prepared by complete drying. Most preferably, step (S300) may be performed at a temperature of 400 ℃ for 24 hours.
In one embodiment, lithium sulfate powder containing no impurities may be prepared in the step (S300).
On the other hand, the present invention may further include a step (S400) of heat-treating the mixture of the materials consisting of lithium sulfate powder and carbon prepared in the step (S300) in a carbon dioxide or carbon monoxide atmosphere.
The step (S400) is a process of preparing lithium carbonate from lithium sulfate powder, mixing the lithium sulfate powder with a carbon material, and injecting carbon dioxide or carbon monoxide to perform a heat treatment to prepare lithium carbonate (Li) 2 CO 3 )。
In one embodiment, the heat treatment may be performed under dry conditions. The drying condition may mean a state without moisture. Therefore, an intermediate product or a byproduct including water, etc. is not generated in the step (S400).
In one embodiment, the carbon dioxide or carbon monoxide may be continuously injected into the reaction vessel during the reaction of the lithium sulfate powder and the carbon material, and a predetermined concentration of the carbon dioxide or carbon monoxide may be maintained to maintain the atmosphere.
In an embodiment, the carbon material and the injected carbon dioxide or carbon monoxide may react with the lithium sulfate powder by heat treatment to generate lithium carbonate. The carbon material may be a material containing carbon, for example, a carbon-containing material such as carbon powder, graphene, graphite, activated carbon, carbon black, and the like may be used without limitation. The carbon material may be mixed in a molar ratio of 1 or more to 1 mole of the lithium sulfate.
In one embodiment, the carbon dioxide may react with the lithium sulfate powder together with the carbon material in the carbon dioxide atmosphere to form lithium carbonate.
In an embodiment, in the carbon dioxide atmosphere, the carbon dioxide may also react with lithium sulfate powder to form lithium carbonate without a carbon material. When the carbon dioxide reacts with the lithium sulfate powder together with the carbon material, lithium sulfate may become lithium carbonate, and thus, there may be no other by-product.
In one embodiment, the heat treatment may be performed in a furnace at about 700 to 900 ℃.
Unlike the conventional process of leaching all elements contained in lithium manganese iron phosphate into solution by using an excessive and high-concentration inorganic acid and then separating the leached elements, the present invention can control lithium manganese iron phosphate (LiMnFePO) 4 LMFP) and sulfuric acid solution, only selectively leaching and recovering lithium except for impurities, and thus, compared with the existing process, the process is simpler and more efficient, the recovery rate of lithium is also more than 99%, and a high recovery rate can be achieved.
In addition, according to the present invention, since lithium sulfate powder containing no impurities can be easily prepared, and lithium carbonate can be prepared from the lithium sulfate powder through a simple dry heat treatment process, there is an advantage in that the process is convenient.
[ examples ]
In this example, a positive electrode active material LMFP (limnffepo) recovered from a used lithium ion battery was used 4 ) And (3) powder. The LMFP powder used in this example was analyzed by XRD (X-ray Diffraction), and the results of the analysis are shown in FIG. 2.
From the XRD analysis result of FIG. 2, it was confirmed that the LMFP powder used in this example was LiMnFePO 4 And (4) phase(s).
On the other hand, 98.08% of H was used for confirmation 2 SO 4 The optimum conditions for the solution to selectively leach lithium (Li) from the LMFP powder were determined by varying the concentration of the sulfuric acid solution, the stirring time, and the solid-to-liquid ratio of the sulfuric acid solution to the LMFP powder.
1) Metal leaching results according to sulfuric acid solution concentration
10g of LMFP powder was added to a beaker containing 50ml of 1M, 2M, and 3M sulfuric acid solution, respectively, and stirred at a stirring speed of 300rpm for 60 minutes. Then, the solid and liquid were separated by filtration under reduced pressure.
Subsequently, the filtered solution was dried at a temperature of 400 ℃ for 24 hours to prepare a lithium sulfate powder. The dry powder was analyzed by XRD for the presence or absence of residual impurities and phase analysis.
Referring to fig. 3 showing the results of XRD analysis, it is shown that only Li is detected in the lithium sulfate powder prepared from the 2M sulfuric acid solution 2 SO 4 Phase, and lithium sulfate powder prepared using 1M, 3M sulfuric acid solution with Mn as impurity 2+ Fe 3+ 4 (PO 4 ) 3 (OH) 5 ,Mn(C 6 H 5 COO) 2 N 2 H 4 Are detected together.
From these results, it was confirmed that a 2M sulfuric acid solution is the optimum condition for selective leaching of lithium free from impurities.
2) Metal leaching results according to agitation time
10g of LMFP powder was added to a beaker containing 50ml of a 2M sulfuric acid solution, which was then stirred at a stirring speed of 300rpm for 30 minutes 60 minutes and 120 minutes, respectively. Then, the solid and liquid were separated by filtration under reduced pressure.
Next, the filtered solution was dried at a temperature of 400 ℃ for 24 hours to prepare a lithium sulfate powder. The dry powder was analyzed by XRD for the presence or absence of residual impurities and phase analysis.
Referring to fig. 4 showing the results of XRD analysis, it is shown that only Li was detected in the lithium sulfate powder prepared by the reaction with the stirring time set to 60 minutes 2 SO 4 Phase, and impurity Li was detected in the lithium sulfate powder prepared with reaction times of 30 minutes and 120 minutes 6 P 6 O 18 H 2 O,MnSO 4 ,Fe 2 (SO 4 ) 3 , Fe 5 (PO 4 ) 3 (OH) 5 The result of (1).
From these results, it was confirmed that when the reaction was carried out with the stirring time set to 60 minutes, only lithium from which impurities were removed was selectively leached out.
3) Metal leaching results based on the solid-to-liquid ratio of sulfuric acid solution to LMFP powder
10g of LMFP powder was added to a beaker containing 30ml, 50ml and 70ml of a 2M sulfuric acid solution, respectively, and stirred at a stirring speed of 300rpm for 60 minutes. Then, the solid and liquid were separated by filtration under reduced pressure.
Subsequently, the filtered solution was dried at a temperature of 400 ℃ for 24 hours to prepare a lithium sulfate powder. The dry powder was analyzed by XRD for the presence or absence of residual impurities and phase analysis.
Referring to fig. 5 showing the results of XRD analysis, only Li was detected in the lithium sulfate powder prepared with a solid-to-liquid ratio of LMFP powder to sulfuric acid solution of 1 2 SO 4 Phase, but Fe impurity was detected together in lithium sulfate powder prepared with solid-to-liquid ratio of 1 2 PO 5 ,Mn(SO 4 )(H 2 O),Fe 2 (SO 4 ) 4 (H 2 O)2, MnSO 4 (H 2 O) of the reaction mixture.
From these results, it was confirmed that only lithium from which impurities were removed was selectively leached when the solid-to-liquid ratio of LMFP powder and sulfuric acid solution was 1.
Although the present invention has been described with reference to the preferred embodiments, those skilled in the art will appreciate that various modifications and changes can be made to the present invention without departing from the spirit and scope of the present invention as set forth in the appended claims.
Claims (16)
1. A method for selectively recovering lithium from lithium manganese iron phosphate comprising; lithium manganese iron phosphate (LiMnFePO) 4 LMFP) powder is reacted with a sulfuric acid solution for at least 30 minutes and less than 120 minutes,
the concentration of the sulfuric acid solution is more than 1M and less than 3M,
the lithium manganese iron phosphate (LiMnFePO) 4 LMFP) the weight ratio of powder to sulfuric acid solution is greater than 1.
2. The method of claim 1, wherein the reacting step is performed at ambient temperature.
3. The method of claim 1, wherein the reacting step comprises reacting the lithium manganese iron phosphate (LiMnFePO) 4 LMFP) a step of stirring a mixture of the powder and the sulfuric acid solution at a speed of 250 to 350 rpm.
4. The method for selectively recovering lithium from lithium manganese iron phosphate according to claim 1, wherein in said reacting step only lithium ions are selectively leached from lithium manganese iron phosphate powder.
5. The method for selectively recovering lithium from lithium manganese iron phosphate according to claim 1, further comprising a step of solid-liquid separating the reaction solution after said reaction step.
6. The method for selectively recovering lithium from lithium manganese iron phosphate according to claim 5, wherein the solution filtered by said step of solid-liquid separation comprises lithium sulfate (Li) 2 SO 4 )。
7. The method for selectively recovering lithium from lithium manganese iron phosphate according to claim 6, wherein said filtered solution does not contain Mn 2+ Fe 3+ 4 (PO 4 ) 3 (OH) 5 ,Mn(C 6 H 5 COO) 2 N 2 H 4 ,Li 6 P 6 O 18 H 2 O,MnSO 4 ,Fe 2 (SO 4 ) 3 ,Fe 5 (PO 4 ) 3 (OH) 5 ,Fe 2 PO 5 ,Mn(SO 4 )(H 2 O) and Fe 2 (SO 4 ) 4 (H 2 O) 2 。
8. The method for selectively recovering lithium from lithium manganese iron phosphate according to claim 5, wherein said solid-liquid separation is performed by a reduced pressure filtration method.
9. The method for selectively recovering lithium from lithium manganese iron phosphate according to claim 5, further comprising the step of drying the filtered solution after said solid-liquid separation.
10. The method for selectively recovering lithium from lithium manganese iron phosphate according to claim 9, wherein said drying step is carried out at a temperature of 350 to 500 ℃ for 22 hours or more and 26 hours or less.
11. The method of claim 9, wherein lithium sulfate powder is prepared during the drying step.
12. The method for selectively recovering lithium from lithium manganese iron phosphate according to claim 11, further comprising the step of heat treating the mixture of materials consisting of said lithium sulfate powder and carbon in an atmosphere of carbon dioxide or carbon monoxide.
13. The method of claim 12, wherein the carbon-derived material comprises at least one of carbon powder, graphene, graphite, activated carbon, and carbon black.
14. The method for selectively recovering lithium from lithium manganese iron phosphate according to claim 12, wherein said heat treatment is performed at a temperature of 700 to 900 ℃.
15. The method for selectively recovering lithium from lithium manganese iron phosphate according to claim 12, characterized in that lithium carbonate (Li) is prepared in said heat treatment step 2 CO 3 )。
16. The method of claim 1, wherein the lithium manganese iron phosphate (LiMnFePO) 4 LMFP) powder was recovered from spent lithium ion batteries.
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