CN112142589B - Method for synthesizing cobalt oxalate dihydrate from leaching solution of waste lithium battery anode active material - Google Patents
Method for synthesizing cobalt oxalate dihydrate from leaching solution of waste lithium battery anode active material Download PDFInfo
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- 238000002386 leaching Methods 0.000 title claims abstract description 67
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- MWHSMSAKVHVSAS-UHFFFAOYSA-L cobalt(2+);oxalate;dihydrate Chemical compound O.O.[Co+2].[O-]C(=O)C([O-])=O MWHSMSAKVHVSAS-UHFFFAOYSA-L 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000006183 anode active material Substances 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 49
- 239000010941 cobalt Substances 0.000 claims abstract description 49
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000007774 positive electrode material Substances 0.000 claims abstract description 39
- 239000011975 tartaric acid Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 26
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 10
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 9
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 abstract description 18
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 abstract description 6
- 235000006408 oxalic acid Nutrition 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 8
- 238000003828 vacuum filtration Methods 0.000 description 8
- 229910001429 cobalt ion Inorganic materials 0.000 description 7
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 239000010926 waste battery Substances 0.000 description 4
- LRRBNLHPFPHVCW-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;hydrogen peroxide Chemical compound OO.OC(=O)C(O)C(O)C(O)=O LRRBNLHPFPHVCW-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the technical field of resource recovery, and particularly relates to a method for synthesizing cobalt oxalate dihydrate from a leaching solution of a waste lithium battery anode active material. The invention provides a method for synthesizing cobalt oxalate dihydrate from a leaching solution of a positive electrode active material of a waste lithium battery, which comprises the following steps: providing a cobalt-containing waste lithium battery positive electrode active material; mixing the cobalt-containing waste lithium battery anode active material with hydrogen peroxide solution of tartaric acid, and carrying out acid leaching to obtain leaching liquid; and mixing the leaching solution with hydrogen peroxide, and performing crystallization reaction to obtain cobalt oxalate dihydrate. The embodiment shows that the method provided by the invention does not need to introduce an external reagent oxalic acid or ammonium oxalate, and has simple process flow; the purity of the obtained cobalt oxalate dihydrate is more than or equal to 98 percent, and the yield is 95-98 percent.
Description
Technical Field
The invention belongs to the technical field of resource recovery, and particularly relates to a method for synthesizing cobalt oxalate dihydrate from a leaching solution of a waste lithium battery anode active material.
Background
The lithium ion battery mainly comprises a shell, a positive electrode (formed by coating a positive electrode active material on an aluminum foil current collector through a binder), a negative electrode (formed by coating a negative electrode active material on a copper foil fluid through a binder), electrolyte and a diaphragm. The positive electrode active material is mainly selected from compounds with high electrochemical potential and capable of reversibly intercalating lithium ions, such as LiCoO with lamellar structure 2 . Natural cobalt resources are low and are mainly present in the ore in the form of intergrowth with other metalsThe content of the stone is only 0.01 to 0.2 percent of the metal content in the ore; the cobalt content in the waste lithium battery is far higher than that in the natural ore, and the lithium cobalt battery is taken as an example, wherein the cobalt content reaches 15-20%. Therefore, the recovery and reuse of cobalt element in the waste lithium battery positive electrode active material has considerable environmental, economic and social benefits.
At present, the regenerated product of cobalt element in the waste lithium battery anode active material is mainly cobalt oxalate dihydrate. The common method is to add oxalic acid or ammonium oxalate into the leaching solution of the positive electrode active material, and react by adjusting the pH value of the solution to obtain cobalt oxalate dihydrate precipitate. However, the process flow needs to introduce an external reagent oxalic acid or ammonium oxalate, and is relatively complex.
Disclosure of Invention
In view of the above, the invention aims to provide a method for synthesizing cobalt oxalate dihydrate from the leaching solution of the positive electrode active material of the waste lithium battery, and the method provided by the invention does not need to introduce an additional reagent oxalic acid or ammonium oxalate, and has a simple process flow.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for synthesizing cobalt oxalate dihydrate from a leaching solution of a positive electrode active material of a waste lithium battery, which comprises the following steps:
providing a cobalt-containing waste lithium battery positive electrode active material;
mixing the cobalt-containing waste lithium battery anode active material with hydrogen peroxide solution of tartaric acid, and carrying out acid leaching to obtain leaching liquid;
and mixing the leaching solution with hydrogen peroxide, and performing crystallization reaction to obtain cobalt oxalate dihydrate.
Preferably, the chemical composition of the positive electrode active material of the cobalt-containing waste lithium battery comprises lithium cobalt oxide and/or lithium nickel cobalt manganese oxide.
Preferably, the method for providing the waste lithium battery positive electrode active material includes the steps of:
disassembling the cobalt-containing waste lithium battery to obtain a positive plate;
and calcining the positive plate to obtain the cobalt-containing waste lithium battery positive active material.
Preferably, the calcination temperature is 450-800 ℃ and the time is 3-6 h.
Preferably, the concentration of tartaric acid in the hydrogen peroxide solution of tartaric acid is 0.1-1.5 mol/L; the mass fraction of hydrogen peroxide of the hydrogen peroxide solution of tartaric acid is less than or equal to 30 percent.
Preferably, the ratio of the volume of the hydrogen peroxide solution of the tartaric acid to the mass of the anode active material of the cobalt-containing waste lithium battery is 1L: (5-100 g).
Preferably, the temperature of the acid leaching is 25-80 ℃ and the time is 1-6 h; the acid leaching is carried out under the condition of stirring; the stirring speed is 100-400 rpm.
Preferably, in the crystallization reaction, the mass fraction of hydrogen peroxide is less than or equal to 30%; the volume ratio of the leaching liquid to the hydrogen peroxide is 1: (1-10).
Preferably, the temperature of the crystallization reaction is 25-80 ℃ and the time is 1-120 h.
The invention provides a method for synthesizing cobalt oxalate dihydrate from a leaching solution of a positive electrode active material of a waste lithium battery, which comprises the following steps: providing a cobalt-containing waste lithium battery positive electrode active material; mixing the cobalt-containing waste lithium battery anode active material with hydrogen peroxide solution of tartaric acid, and carrying out acid leaching to obtain leaching liquid; and mixing the leaching solution with hydrogen peroxide, performing crystallization reaction, and drying a precipitate obtained by the crystallization reaction to obtain cobalt oxalate dihydrate. In the invention, tartaric acid is used as a leaching agent and a complexing agent to extract cobalt from the cobalt-containing waste lithium battery anode active material, and cobalt element reacts with-COOH groups of tartaric acid in a Co (III) form to generate a Co (III) -tartaric acid complex; h 2 O 2 The cobalt oxalate dihydrate has extremely strong reducing power, and the Co (III) -tartaric acid complex is reduced to be Co (II) -tartaric acid complex, wherein the Co (II) -tartaric acid complex is a weak complex and has very low stability constant, and is easy to dissociate to form cobalt oxalate dihydrate precipitate. According to the invention, the cobalt oxalate dihydrate precipitate can be formed in situ without adding oxalic acid or ammonium oxalate into the leaching solution, the reagent system is mild, and the operation is simple.
According to the method provided by the invention, oxalic acid or ammonium oxalate is not required to be added into the leaching solution, so that cobalt oxalate dihydrate can be obtained, and the reagent system is mild and has no secondary pollution; the test result of the embodiment shows that the purity of the obtained cobalt oxalate dihydrate is more than or equal to 98 percent, and the yield is more than or equal to 95 percent.
Drawings
FIG. 1 is a process flow diagram of a method for synthesizing cobalt oxalate dihydrate provided by an embodiment of the invention;
FIG. 2 is a graph showing the ultraviolet-visible spectrum of the leachate and tartaric acid solution obtained in example 1;
FIG. 3 is an XRD pattern of cobalt oxalate dihydrate obtained in example 1;
FIG. 4 is a diagram showing the cobalt oxalate dihydrate obtained in example 1.
Detailed Description
The invention provides a method for synthesizing cobalt oxalate dihydrate from a leaching solution of a positive electrode active material of a waste lithium battery, which comprises the following steps:
providing a cobalt-containing waste lithium battery positive electrode active material;
mixing the cobalt-containing waste lithium battery anode active material with hydrogen peroxide solution of tartaric acid, and carrying out acid leaching to obtain leaching liquid;
and mixing the leaching solution with hydrogen peroxide, and performing crystallization reaction to obtain cobalt oxalate dihydrate.
In the present invention, the components are commercially available products well known to those skilled in the art unless specified otherwise.
Fig. 1 is a process flow chart of a method for synthesizing cobalt oxalate dihydrate from a leaching solution of a positive electrode active material of a waste lithium battery, and the method provided by the invention is specifically described below with reference to fig. 1.
The invention provides a cobalt-containing waste lithium battery positive electrode active material.
In the present invention, the chemical composition of the positive electrode active material of the cobalt-containing waste lithium battery preferably includes lithium cobalt oxide (LiCoO) 2 ) And/or lithium nickel cobalt manganate (LiCo) x Ni y Mn z O 2 )。
In the present invention, the method of providing the waste lithium battery positive electrode active material preferably includes the steps of:
disassembling the cobalt-containing waste lithium battery to obtain a positive plate;
and calcining the positive plate to obtain the cobalt-containing waste lithium battery positive active material.
The invention preferably disassembles the cobalt-containing waste lithium battery to obtain the positive plate. The invention is not particularly limited to the cobalt-containing waste lithium battery, and the cobalt-containing waste lithium battery well known to the person skilled in the art can be adopted, specifically, for example, the cobalt-containing waste lithium battery and/or the nickel cobalt lithium manganate waste battery, and the invention is not particularly limited to the disassembly and can be realized by adopting a disassembly process well known to the person skilled in the art. In the method for separating the positive plate from the positive current collector, the positive part of the cobalt-containing waste lithium battery is preferably soaked in an organic solvent so as to separate the positive current collector from the positive plate; the organic solvent is preferably N-methylpyrrolidone.
After the positive plate is obtained, the positive plate is preferably calcined, so that the cobalt-containing waste lithium battery positive active material is obtained. In the present invention, the temperature of the calcination is preferably 450 to 800 ℃, more preferably 500 to 750 ℃, and most preferably 700 ℃; the time is preferably 3 to 6 hours, more preferably 4 to 5.5 hours, and most preferably 5 hours. In the present invention, the calcination apparatus is preferably a muffle furnace.
After the cobalt-containing waste lithium battery positive electrode active material is obtained, the cobalt-containing waste lithium battery positive electrode active material is mixed with hydrogen peroxide solution of tartaric acid, and acid leaching is carried out to obtain leaching liquid.
In the invention, the hydrogen peroxide solution of tartaric acid is preferably prepared from tartaric acid and hydrogen peroxide; the mass fraction of the hydrogen peroxide is preferably not more than 30%, more preferably 3-20%, and even more preferably 5-10%. In the present invention, the concentration of tartaric acid in the hydrogen peroxide solution of tartaric acid is preferably 0.1 to 1.5mol/L, more preferably 0.5 to 1.5mol/L, and still more preferably 0.8 to 1.5mol/L. In the invention, the ratio of the volume of the hydrogen peroxide solution of the tartaric acid to the mass of the anode active material of the cobalt-containing waste lithium battery is preferably 1L: (5-100 g), more preferably 1L: (5-50 g), more preferably 1L: (5-30 g).
In the present invention, the temperature of the acid leaching is preferably 25 to 80 ℃, more preferably 35 to 80 ℃, still more preferably 40 to 80 ℃; the time is preferably 1 to 6 hours, more preferably 1.5 to 4 hours, and still more preferably 1.5 to 3 hours. In the present invention, the acid leaching is preferably performed under stirring; the stirring speed is preferably 100 to 400rpm, more preferably 100 to 300rpm, and still more preferably 100 to 250rpm.
After acid leaching, the invention preferably carries out solid-liquid separation on a solid-liquid mixed system obtained after acid leaching to obtain a liquid-phase product and a solid-phase product. In the present invention, the solid-liquid separation method is preferably filtration, more preferably vacuum filtration. The vacuum filtration is not particularly limited, and vacuum filtration well known to those skilled in the art may be employed. After solid-liquid separation, the invention obtains a liquid-phase product and a solid-phase product; the filtrate is the leaching solution; the filter residue is a mixture composed of a cobalt-containing waste lithium battery positive electrode active material which is not completely reacted and graphite (the graphite is derived from the cobalt-containing waste lithium battery positive electrode material).
After the leaching solution is obtained, the leaching solution is mixed with hydrogen peroxide and then subjected to crystallization reaction, so that cobalt oxalate dihydrate is obtained.
In the invention, the volume ratio of the leaching solution to the hydrogen peroxide is preferably 1: (1 to 10), more preferably 1: (2-5). In the present invention, the mass fraction of the hydrogen peroxide is preferably not more than 30%, more preferably 3 to 30%, and even more preferably 5 to 30%.
In the invention, hydrogen peroxide is beneficial to release more cobalt ions from lithium cobalt oxide during acid leaching; in the crystallization reaction, hydrogen peroxide is advantageous in promoting the conversion of Co (III) to Co (II). In the invention, if the system of acid leaching and crystallization reaction does not contain hydrogen peroxide, cobalt oxalate dihydrate is not generated; when the acid leaching is carried out, hydrogen peroxide is not contained, the concentration of cobalt ions in the leaching solution can be lower, and although hydrogen peroxide is contained in the crystallization reaction, cobalt oxalate dihydrate can be generated, but the total amount of generated cobalt oxalate dihydrate is smaller; the acid leaching contains hydrogen peroxide, and the crystallization reaction does not contain hydrogen peroxide, so that cobalt oxalate dihydrate can be generated, but the generation rate of the cobalt oxalate dihydrate is very slow.
In the present invention, the temperature of the crystallization reaction is preferably 25 to 80 ℃, more preferably 40 to 80 ℃, still more preferably 60 to 80 ℃; the time is preferably 1 to 120 hours, more preferably 3 to 72 hours, and still more preferably 3 to 48 hours. In the present invention, the crystallization is preferably performed under a standing or stirring condition; the stirring rate is preferably 100 to 300rpm, more preferably 150 to 250rpm.
Taking the lithium cobalt oxide as an example of the positive electrode active material of the waste lithium battery containing cobalt, the total reaction in the method for synthesizing cobalt oxalate dihydrate from the leaching solution of the positive electrode active material of the waste lithium battery is shown as the reaction in the formula I:
2LiCoO 2 +2C 4 H 6 O 6 +4H 2 O 2 →2CoC 2 O 4 ·2H 2 O↓+C 4 H 4 O 6 Li 2 +4H 2 O+O 2 ∈formula I.
The reaction is mainly carried out in two steps, wherein in the first step, tartaric acid and lithium cobalt oxide react to generate a solution containing cobalt ions, and hydrogen peroxide promotes more cobalt ions to be released from the lithium cobalt oxide; and secondly, mixing the leaching solution with hydrogen peroxide, wherein the hydrogen peroxide is beneficial to reducing more Co (III) -tartaric acid complex in the solution into Co (II) -tartaric acid complex, and the Co (II) -tartaric acid complex is unstable and is easy to dissociate to generate cobalt oxalate dihydrate. Because no other precipitate is generated, the purity of the cobalt oxalate dihydrate in the product obtained by the invention is high (more than or equal to 98%).
After the crystallization reaction, the invention preferably further comprises filtering the crystallization reaction system; the filtration is not particularly limited in the present invention, and filtration known to those skilled in the art may be employed, and in particular, vacuum filtration may be employed. In the invention, the filter residue obtained by filtration is the precipitated cobalt oxalate dihydrate obtained by crystallization reaction.
After filtration, the present invention preferably further comprises drying the resulting filter residue. In the present invention, the drying temperature is preferably 80 to 100 ℃, more preferably 85 to 100 ℃, still more preferably 90 to 100 ℃; the time is preferably 8 to 12 hours, more preferably 8 to 11 hours, and still more preferably 8 to 10 hours.
In the invention, the purity of the obtained cobalt oxalate dihydrate is preferably more than or equal to 98%; the yield is preferably not less than 95%, more preferably 95 to 98%. Description: in the invention, the yield refers to the ratio of cobalt element in the leaching solution to cobalt oxalate dihydrate.
In order to further illustrate the present invention, a method for synthesizing cobalt oxalate dihydrate from a leaching solution of a positive electrode active material of a waste lithium battery is provided in the present invention with reference to the following examples, which should not be construed as limiting the scope of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Disassembling the lithium cobaltate waste battery, wherein the positive electrode part is arranged in N-methyl pyrrolidone so as to separate a positive electrode current collector from positive electrode powder to obtain the positive electrode powder; calcining the positive electrode powder at 700 ℃ for 5 hours to obtain a cobalt-containing waste lithium battery positive electrode active material;
mixing 2g of the cobalt-containing waste lithium battery positive electrode active material and 400mL of tartaric acid hydrogen peroxide solution with the concentration of 0.8mol/L (prepared by 5% hydrogen peroxide by mass fraction), carrying out acid leaching for 2h at the temperature of 80 ℃ and the stirring speed of 100rpm, carrying out vacuum suction filtration on the acid leached system, obtaining filtrate which is leaching solution, and detecting to obtain the cobalt ion mass concentration in the leaching solution of 4.24g/L;
mixing the leaching solution and 30% hydrogen peroxide according to a volume ratio of 2:1, carrying out crystallization reaction for 24 hours at 60 ℃ and stirring speed of 200rpm, carrying out vacuum filtration on a system after the crystallization reaction, and drying a pink precipitate obtained after the vacuum filtration at 100 ℃ for 8 hours to obtain 5g of cobalt oxalate dihydrate.
The leachate and tartaric acid solution obtained in example 1 were subjected to ultraviolet-visible light analysis, and the obtained ultraviolet-visible spectrum is shown in fig. 2. As can be seen from FIG. 2, the ultraviolet-visible spectrum of the leachate obtained by the invention shows three absorption peaks respectively at 240nm, 300nm and 510nm, and comparing the ultraviolet-visible spectrum of tartaric acid solution shows that the absorption peak at 240nm is generated by tartaric acid, the absorption peak at 510nm is generated by Co (III) -tartaric acid complex, and the absorption peak at about 300nm is generated by Co (II) -tartaric acid complex.
The obtained cobalt oxalate dihydrate product was subjected to an X-ray diffraction test, and the obtained XRD pattern was shown in fig. 3. As can be seen from FIG. 3, the spectrum is consistent with the standard spectrum of cobalt oxalate dihydrate, and has no impurity peak, which indicates that the product obtained in this example is high-purity cobalt oxalate dihydrate.
And (4) observing the real object of the obtained cobalt oxalate dihydrate product, wherein the obtained real object diagram is shown in fig. 4. As can be seen from FIG. 4, the cobalt oxalate dihydrate obtained by the invention is pink powder with good crystallinity.
Testing the obtained cobalt oxalate dihydrate to obtain the purity of the cobalt oxalate dihydrate of 100%; the yield of cobalt oxalate dihydrate is 95%.
Example 2
Disassembling the lithium cobaltate waste battery, wherein the positive electrode part is arranged in N-methyl pyrrolidone so as to separate a positive electrode current collector from positive electrode powder to obtain the positive electrode powder; calcining the positive electrode powder at 700 ℃ for 5 hours to obtain a cobalt-containing waste lithium battery positive electrode active material;
mixing 6g of the cobalt-containing waste lithium battery anode active material and 250mL of tartaric acid hydrogen peroxide solution with the concentration of 1.5mol/L (prepared by 10% hydrogen peroxide by mass fraction), carrying out acid leaching for 2h at 40 ℃ under the condition of the stirring speed of 200rpm, carrying out vacuum suction filtration on the acid leached system, obtaining filtrate which is leaching solution, and detecting to obtain the cobalt ion mass concentration in the leaching solution of 3.98g/L;
mixing the leaching solution and 30% hydrogen peroxide according to a volume ratio of 4:1, carrying out crystallization reaction for 6h at 80 ℃ and stirring speed of 200rpm, carrying out vacuum suction filtration on a system after the crystallization reaction, and drying the pink precipitate obtained after the vacuum suction filtration at 100 ℃ for 8h to obtain 2.96g of cobalt oxalate dihydrate.
Testing the obtained cobalt oxalate dihydrate to obtain the purity of the cobalt oxalate dihydrate of 100%; the yield of cobalt oxalate dihydrate is 96%.
Example 3
Disassembling the lithium cobaltate waste battery, wherein the positive electrode part is arranged in N-methyl pyrrolidone so as to separate a positive electrode current collector from positive electrode powder to obtain the positive electrode powder; calcining the positive electrode powder at 700 ℃ for 5 hours to obtain a cobalt-containing waste lithium battery positive electrode active material;
mixing 5g of the cobalt-containing waste lithium battery anode active material and 1000mL of tartaric acid hydrogen peroxide solution with the concentration of 0.8mol/L (prepared by using 10% hydrogen peroxide by mass fraction), carrying out acid leaching for 1.5h at the temperature of 80 ℃ and the stirring speed of 200rpm, carrying out vacuum suction filtration on the acid leached system, obtaining filtrate which is leaching solution, and detecting to obtain the cobalt ion mass concentration in the leaching solution of 4.6g/L;
mixing the leaching solution and 30% hydrogen peroxide according to a volume ratio of 4:1, carrying out crystallization reaction for 10 hours at 80 ℃ and stirring speed of 200rpm, carrying out vacuum filtration on a system after the crystallization reaction, and drying a pink precipitate obtained after the vacuum filtration at 100 ℃ for 8 hours to obtain 13.97g of cobalt oxalate dihydrate.
Testing the obtained cobalt oxalate dihydrate to obtain the purity of the cobalt oxalate dihydrate of 100%; the yield of cobalt oxalate dihydrate is 98%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. A method for synthesizing cobalt oxalate dihydrate from a leaching solution of a positive electrode active material of a waste lithium battery comprises the following steps:
providing a cobalt-containing waste lithium battery positive electrode active material;
mixing the cobalt-containing waste lithium battery anode active material with hydrogen peroxide solution of tartaric acid, and carrying out acid leaching to obtain leaching liquid;
and mixing the leaching solution with hydrogen peroxide, and performing crystallization reaction to obtain cobalt oxalate dihydrate.
2. The method of claim 1, wherein the chemical composition of the cobalt-containing spent lithium battery positive electrode active material comprises lithium cobalt oxide and/or lithium nickel cobalt manganese oxide.
3. The method of claim 1, wherein the method of providing the spent lithium battery positive electrode active material comprises the steps of:
disassembling the cobalt-containing waste lithium battery to obtain a positive plate;
and calcining the positive plate to obtain the cobalt-containing waste lithium battery positive active material.
4. A method according to claim 3, wherein the calcination is carried out at a temperature of 450 to 800 ℃ for a period of 3 to 6 hours.
5. The method according to claim 1, wherein the concentration of tartaric acid in the hydrogen peroxide solution of tartaric acid is 0.1-1.5 mol/L; the mass fraction of hydrogen peroxide of the hydrogen peroxide solution of tartaric acid is less than or equal to 30 percent.
6. The method according to claim 5, wherein the ratio of the volume of the hydrogen peroxide solution of tartaric acid to the mass of the cobalt-containing waste lithium battery positive electrode active material is 1L: (5-100 g).
7. The method according to claim 1 or 6, wherein the acid leaching is carried out at a temperature of 25-80 ℃ for a time of 1-6 hours; the acid leaching is carried out under the condition of stirring; the stirring speed is 100-400 rpm.
8. The method according to claim 1, wherein in the crystallization reaction, the mass fraction of hydrogen peroxide is less than or equal to 30%; the volume ratio of the leaching liquid to the hydrogen peroxide is 1: (1-10).
9. The method according to claim 1 or 8, wherein the crystallization reaction is carried out at a temperature of 25 to 80 ℃ for a time of 1 to 120 hours.
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| KR20120128913A (en) * | 2011-05-18 | 2012-11-28 | 한국생산기술연구원 | Leaching solution for recovering valuable metal from wastes and leaching method using the same |
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| CN110615486A (en) * | 2019-09-18 | 2019-12-27 | 陕西科技大学 | Process for selectively extracting valuable metals from waste power lithium batteries and preparing ternary cathode material |
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| KR20120128913A (en) * | 2011-05-18 | 2012-11-28 | 한국생산기술연구원 | Leaching solution for recovering valuable metal from wastes and leaching method using the same |
| CN106450559A (en) * | 2016-12-07 | 2017-02-22 | 天津华庆百胜能源有限公司 | Method for preparing new electrodes through recovering of waste ion batteries |
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