CN117210687A - Alkaline leaching recovery method for waste oxide battery anode material - Google Patents
Alkaline leaching recovery method for waste oxide battery anode material Download PDFInfo
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- 238000002386 leaching Methods 0.000 title claims abstract description 109
- 239000002699 waste material Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000010405 anode material Substances 0.000 title claims abstract description 23
- 238000011084 recovery Methods 0.000 title claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 35
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002585 base Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000004471 Glycine Substances 0.000 claims abstract description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 229940039748 oxalate Drugs 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000010406 cathode material Substances 0.000 claims description 9
- 229960002089 ferrous chloride Drugs 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 5
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 5
- 229940039790 sodium oxalate Drugs 0.000 claims description 5
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 18
- 239000002184 metal Substances 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 13
- 150000002739 metals Chemical class 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 2
- -1 iron ions Chemical class 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000002893 slag Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910004493 Li(Ni1/3Co1/3Mn1/3)O2 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910003900 Li(Ni0.5Co0.2Mn0.3)O2 Inorganic materials 0.000 description 2
- 229910002999 Li(Ni0.8Co0.1Mn0.1)O2 Inorganic materials 0.000 description 2
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The application provides an alkaline leaching recovery method of a waste oxide battery anode material, which comprises the following steps: and (3) taking a mixed aqueous solution of glycine, alkali and oxalate as an alkaline leaching base solution, adding a waste oxide battery anode material and soluble ferrous salt into the alkaline leaching base solution, and carrying out leaching reaction. The method can realize the reduction of high-valence metal in the anode material of the oxide waste lithium ion battery by utilizing the reducibility of ferrous ions, can effectively improve the leaching efficiency of the valuable metal, shortens the alkaline leaching time, and simultaneously obtains higher metal leaching rate. The leaching method can effectively avoid a series of problems of difficult separation of subsequent valuable metals and the like caused by the fact that iron ions enter a liquid phase in the leaching process, and has the advantages of simple reagents, simple and easy control of method conditions, low energy consumption, high efficiency and considerable industrial application prospect.
Description
Technical Field
The application belongs to the technical field of lithium ion battery recovery, and particularly relates to an alkaline leaching recovery method of a waste oxide battery anode material.
Background
In recent years, new energy automobiles in China show blowout type growth. Accordingly, a large number of power batteries face retirement, and how to recycle the waste power batteries has important practical significance. At present, methods for recovering valuable metals in lithium ion batteries mainly comprise a pyrogenic process and a wet process. The pyrogenic process is simpler, but has the disadvantages of high energy consumption and large exhaust emission. Wet processes mainly include acid leaching and alkaline leaching. Acid leaching, which generally adopts hydrochloric acid, sulfuric acid, nitric acid and the like as leaching solvents, can generate toxic and harmful gases (sulfur dioxide, nitrogen dioxide and the like), is difficult to treat acid waste liquid, and is not friendly to the environment; meanwhile, various impurities are easily introduced into the acid leaching, so that the subsequent valuable metal recycling process becomes more complicated. Alkaline leaching generally adopts ammonia water as a leaching solvent, has the advantage of selective leaching of metals, but has the defect of slow leaching rate; meanwhile, the ammonia water is large in use amount, is extremely volatile under the heating condition, and has higher requirements on the sealing performance of equipment and devices.
Chinese patent CN107017443A realizes the recovery of valuable metals in waste lithium ion batteries through a plurality of procedures such as battery crushing, pre-roasting, reduction roasting, water leaching, ammonia oxide leaching, extraction, back extraction, acid oxidation leaching, extraction purification and the like. The extraction system of the method is very complex, and the process flow is very lengthy.
Chinese patent CN109193057A realizes the recovery of lithium, nickel and cobalt by pressurized ammonia leaching when recovering valuable metals in waste ternary lithium batteries. The method comprises the steps of carrying out leaching reaction in a high-pressure reaction kettle under a preset pressure (0.6-1.5 MPa); meanwhile, the ammonia consumption is relatively large (5-12 mol/L).
Disclosure of Invention
Aiming at the technical problems, the application aims to provide an alkaline leaching recovery method for a waste oxide battery anode material.
Aiming at the technical problems existing in the prior art, the inventor finds that the mixed solution of glycine-alkali-oxalate is used as leaching base solution, ferrous salt is used as reducing agent, and higher leaching rate can be obtained under mild reaction conditions and short flow.
To achieve the above object, the present application proposes the following solution:
an alkaline leaching recovery method of a waste oxide battery positive electrode material comprises the following steps: taking a mixed aqueous solution of glycine, alkali and oxalate as an alkaline leaching base solution, adding a waste oxide battery anode material and soluble ferrous salt into the alkaline leaching base solution, and carrying out leaching reaction; the alkali is sodium hydroxide and/or potassium hydroxide.
Preferably, the method further comprises the step of carrying out solid-liquid separation on the materials obtained by the leaching reaction to obtain leaching liquid and leaching slag.
Preferably, in the alkaline leaching base solution, the concentration of alkali is 0.01-0.3 mol/L; the concentration of glycine is 0.05-1 mol/L.
Preferably, the pH of the alkaline leaching base solution is controlled to be 8-12.
Preferably, the oxalate is one or more of potassium oxalate, sodium oxalate and ammonium oxalate; in the alkaline leaching solution, the concentration of oxalate is 0.01-0.5 mol/L.
Preferably, the temperature of the leaching reaction is 30-90 ℃; the leaching reaction time is 1-10 h; the leaching reaction is carried out under the stirring action; the stirring speed is 100-500 r/min.
Preferably, the soluble ferrous salt is selected from one or two of ferrous chloride and ferrous nitrate; the molar ratio of iron in the soluble ferrous salt to the waste oxide positive electrode powder material is 1:1-4:1.
Preferably, the waste oxide battery positive electrode material is selected from Li 1+a (Ni x Co y M 1-x-y )O 2 、Na 1+a (Ni x Co y M 1-x-y )O 2 、Li(Ni p Mn q Co 2-p-q-r M r )O 4 、Na(Ni p Mn q Co 2-p-q-r M r )O 4 And one or more of them; wherein a is more than or equal to 0 and less than or equal to 0.3, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and x+y is more than 0 and less than or equal to 1; p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 0 and less than or equal to 2, p+q is more than or equal to 0 and less than or equal to 2, and r is more than or equal to 0 and less than or equal to 2; m is selected from one or more of Fe, ni, co, mn, al, V.
Preferably, the anode material of the waste oxide battery is added into alkaline leaching base solution according to the solid-liquid ratio controlled between 1 g/L and 50 g/L.
Compared with the prior art, the application has the following beneficial effects:
in the leaching method, the reduction of high-valence metal in the anode material of the oxide waste lithium ion battery can be realized by taking a special alkaline system as a leaching base solution and utilizing the reducibility of ferrous ions, so that the leaching efficiency of the valuable metal is effectively improved, the alkaline leaching time is shortened, and meanwhile, the higher metal leaching rate is obtained. The leaching method can effectively avoid a series of problems of difficult separation of subsequent valuable metals and the like caused by the fact that iron ions enter a liquid phase in the leaching process, and has the advantages of simple reagents, simple and easy control of method conditions, low energy consumption, high efficiency and considerable industrial application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram of a waste ternary cathode material Li (Ni) 1/3 Co 1/3 Mn 1/3 )O 2 Scanning electron microscope images of (2);
FIG. 2 is a scanning electron microscope image of the leached residue obtained in example 2 of the present application.
Detailed Description
The application provides an alkaline leaching recovery method of a waste oxide battery anode material, which comprises the following steps: taking a mixed aqueous solution of glycine, alkali and oxalate as an alkaline leaching base solution, adding a waste oxide battery anode material and soluble ferrous salt into the alkaline leaching base solution, and carrying out leaching reaction; the alkali is sodium hydroxide and/or potassium hydroxide.
In some embodiments, the method further comprises solid-liquid separation of the leached material to obtain a leachate and leached residues.
In some preferred embodiments, the concentration of the alkali in the alkaline leaching base solution is 0.01 to 0.3 mol/L, for example, 0.05 mol/L, 0.1 mol/L, 0.15 mol/L, 0.2 mol/L, 0.25 mol/L, etc.
In some preferred embodiments, the concentration of glycine is 0.05 to 1 mol/L, for example 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, 0.4 mol/L, 0.5 mol/L, 0.6 mol/L, 0.7 mol/L, 0.8 mol/L, 0.9 mol/L, etc.
In some preferred embodiments, the pH of the alkaline leaching base solution is controlled to be between 8 and 12, for example 8.5, 9, 9.5, 10, 10.5, 11, 11.5, etc.
In some embodiments, the oxalate is one or more of potassium oxalate, sodium oxalate, and ammonium oxalate.
In some preferred embodiments, the concentration of oxalate in the alkaline leaching solution is 0.01 to 0.5 mol/L, for example, 0.05 mol/L, 0.1 mol/L, 0.15 mol/L, 0.2 mol/L, 0.25 mol/L, 0.3 mol/L, 0.35 mol/L, 0.4 mol/L, 0.45 mol/L, etc.
In some preferred embodiments, the temperature of the leaching reaction is 30-90 ℃, for example 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, etc.; the leaching reaction time is 1-10 h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h and the like; the leaching reaction is carried out under the stirring action; the stirring speed is 100-500 r/min, such as 200-r/min, 300-r/min, 400-r/min, 450-r/min, and the like.
In some preferred embodiments, the soluble ferrous salt is selected from one or more of ferrous chloride, ferrous nitrate; the molar ratio of iron in the soluble ferrous salt to the waste oxide positive electrode powder material is 1:1-4:1, for example, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1 and the like.
Various oxide positive electrode materials, including lithium ion battery oxide positive electrode materials and sodium ion battery oxide positive electrode materials, can be used as the treatment object, and in some preferred embodiments, the waste oxide battery positive electrode materials are selected from Li 1+a (Ni x Co y M 1-x-y )O 2 、Na 1+a (Ni x Co y M 1-x-y )O 2 、Li(Ni p Mn q Co 2-p-q-r M r )O 4 、Na(Ni p Mn q Co 2-p-q-r M r )O 4 And one or more of them; wherein a is more than or equal to 0 and less than or equal to 0.3, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and x+y is more than 0 and less than or equal to 1; p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 0 and less than or equal to 2, p+q is more than or equal to 0 and less than or equal to 2, and r is more than or equal to 0 and less than or equal to 2; m is selected from one or more of Fe, ni, co, mn, al, V.
In some preferred embodiments, the anode material of the waste oxide battery is added into the alkaline leaching base solution according to the solid-to-liquid ratio controlled to be 1-50 g/L, for example, 5 g/L, 10 g/L, 15 g/L, 20 g/L, 25 g/L, 30 g/L, 35 g/L, 40 g/L, 45 g/L and the like.
The application will be described more fully hereinafter with reference to the accompanying drawings and preferred embodiments in order to facilitate an understanding of the application, but the scope of the application is not limited to the following specific embodiments.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present application.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
Example 1
(1) Waste NCM523 (Li (Ni 0.5 Co 0.2 Mn 0.3 )O 2 ) And discharging the ternary lithium battery, then manually disassembling, separating out an anode aluminum foil, and then stripping to obtain an anode material (waste ternary anode material).
(2) Adding 1.1260 g glycine, 0.1200. 0.1200 g sodium hydroxide and 3.8136 g potassium oxalate into 300 ml distilled water to prepare 300 mL mixed solution;
(3) Heating the mixed solution to 80 ℃, stirring in the whole process, and controlling the rotating speed to 300 r/min;
(4) Adding 2g waste ternary cathode material Li (Ni 0.5 Co 0.2 Mn 0.3 )O 2 Adding 2.6237 g ferrous chloride, stopping stirring and heating after reacting for 3 hours;
(5) The separation of the leaching solution and the leaching slag is realized by adopting a vacuum suction filtration device, wherein the leaching solution is diluted by 100 times and then is used for ICP detection, and the basic morphology of the leaching slag is observed by utilizing a scanning electron microscope.
ICP results prove that the leaching rates of the metals respectively reach: 99.5% of Li, 99.6% of Ni, 89.1% of Co and 52.3% of Mn, while Fe, al and Cu do not enter the filtrate.
Example 2
(1) Waste NCM111 (Li (Ni 1/3 Co 1/3 Mn 1/3 )O 2 ) And discharging the ternary lithium battery, then manually disassembling, separating out an anode aluminum foil, and then stripping to obtain an anode material (waste ternary anode material).
(2) Adding 0.7507 g glycine, 0.1600 g sodium hydroxide and 1.3936 g sodium oxalate into 200 ml distilled water to prepare 200 mL mixed solution;
(3) Heating the mixed solution to 80 ℃ and preserving heat, stirring in the whole process, and controlling the rotating speed to be 250 r/min;
(4) Adding 1 g waste ternary cathode material Li (Ni 1/3 Co 1/3 Mn 1/3 )O 2 1.31 is added again48 g, ferrous chloride reacts at 80 ℃, and stirring and heating are stopped after the reaction is carried out for 2 hours;
(5) The separation of the leaching solution and the leaching slag is realized by adopting a vacuum suction filtration device, wherein the leaching solution is diluted by 100 times and then is used for ICP detection, and the basic morphology of the leaching slag is observed by utilizing a scanning electron microscope.
ICP results prove that the leaching rates of the metals respectively reach: 99.9% of Li, 99.9% of Ni, 92.4% of Co and 55.6% of Mn, while Fe, al and Cu do not enter the filtrate.
By scanning electron microscopy, FIG. 1 and FIG. 2 respectively represent the waste ternary cathode material Li (Ni 1/ 3 Co 1/3 Mn 1/3 )O 2 And the appearance of the leached slag after the reaction is finished, and the substances with the secondary sphere particle structure can be completely disappeared. FIG. 1 shows a waste ternary cathode material Li (Ni 1/3 Co 1/3 Mn 1/3 )O 2 The SEM image of (2) shows that the secondary sphere particle structure is in an irregular spherical structure, the particle sizes are different, and the particle size distribution is 2-20 microns. Fig. 2 is an SEM image of the leached residue obtained after the reaction, and it can be found that the substances of the secondary sphere particle structure completely disappear, indicating that the leaching is more thorough.
Example 3
(1) Waste NCM811 (Li (Ni 0.8 Co 0.1 Mn 0.1 )O 2 ) And discharging the ternary lithium battery, then manually disassembling, separating out an anode aluminum foil, and then stripping to obtain an anode material (waste ternary anode material).
(2) Adding 3.0026 g glycine, 0.4800 g sodium hydroxide and 3.8222 g ammonium oxalate into 400 ml distilled water to prepare 400 mL mixed solution;
(3) Heating the mixed solution to 60 ℃, stirring in the whole process, and controlling the rotating speed to be 350 r/min;
(4) Adding 3 g waste ternary cathode material Li (Ni 0.8 Co 0.1 Mn 0.1 )O 2 Adding 5.8559 g ferrous chloride, reacting at 60 ℃, stopping stirring and heating after reacting for 4 hours;
(5) The separation of the leaching solution and the leaching slag is realized by adopting a vacuum suction filtration device, wherein the leaching solution is diluted by 100 times and then is used for ICP detection, and the basic morphology of the leaching slag is observed by utilizing a scanning electron microscope.
ICP results prove that the leaching rates of the metals respectively reach: 98.2% of Li, 99.8% of Ni, 85.9% of Co and 51.5% of Mn, while Fe, al and Cu do not enter the filtrate.
Example 4
(1) Waste NCM111 (Li (Ni 1/3 Co 1/3 Mn 1/3 )O 2 ) And discharging the ternary lithium battery, then manually disassembling, separating out an anode aluminum foil, and then stripping to obtain an anode material (waste ternary anode material).
(2) Adding 15.014 g glycine, 1.6000 g sodium hydroxide and 5.360 g sodium oxalate into 200 ml distilled water to prepare 200 mL mixed solution;
(3) Heating the mixed solution to 50 ℃ and preserving heat, and mechanically stirring in the whole process and controlling the rotating speed to be 500 r/min;
(4) 10 g waste ternary cathode material Li (Ni) is added 1/3 Co 1/3 Mn 1/3 )O 2 Adding 19.013 g ferrous chloride, reacting at 50deg.C, stopping stirring and heating after reacting for 9 hr;
(5) The separation of the leaching solution and the leaching slag is realized by adopting a vacuum suction filtration device, wherein the leaching solution is diluted by 100 times and then is used for ICP detection, and the basic morphology of the leaching slag is observed by utilizing a scanning electron microscope.
ICP results prove that the leaching rates of the metals respectively reach: 97.7% of Li, 96.9% of Ni, 83.1% of Co and 49.3% of Mn, while Fe, al and Cu do not enter the filtrate.
Example 5
(1) 13.5128 g glycine, 3.1680 g sodium hydroxide and 19.8972g of potassium oxalate are put into 300 ml distilled water to prepare 300 mL mixed solution;
(2) Heating the mixed solution to 50 ℃, mechanically stirring in the whole process, and controlling the rotating speed to 300 r/min;
(3) 8g of waste ternary cathode material Li (Ni) is added 1/3 Co 1/3 Mn 1/3 )O 2 Adding 10.14 and g ferrous chloride, reacting at 50deg.C, stopping stirring after reacting for 8 hrMixing and heating;
(4) The separation of the leaching solution and the leaching slag is realized by adopting a vacuum suction filtration device, wherein the leaching solution is diluted by 100 times and then is used for ICP detection, and the basic morphology of the leaching slag is observed by utilizing a scanning electron microscope.
ICP results prove that the leaching rates of the metals respectively reach: 98.3% of Li, 97.5% of Ni, 85.1% of Co and 49.6% of Mn, while Fe, al and Cu do not enter the filtrate.
The foregoing is merely a preferred embodiment of the present application 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 application, which are intended to be comprehended within the scope of the present application.
Claims (9)
1. The alkaline leaching recovery method of the waste oxide battery anode material is characterized by comprising the following steps of: taking a mixed aqueous solution of glycine, alkali and oxalate as an alkaline leaching base solution, adding a waste oxide battery anode material and soluble ferrous salt into the alkaline leaching base solution, and carrying out leaching reaction; the alkali is sodium hydroxide and/or potassium hydroxide.
2. The alkaline leaching recovery method of the waste oxide battery cathode material according to claim 1, further comprising the step of carrying out solid-liquid separation on the material obtained by the leaching reaction to obtain a leaching solution and leaching residues.
3. The alkaline leaching recovery method of the waste oxide battery positive electrode material according to claim 1 or 2, wherein the concentration of alkali in the alkaline leaching base solution is 0.01-0.3 mol/L; the concentration of glycine is 0.05-1 mol/L.
4. The alkaline leaching recovery method of the waste oxide battery positive electrode material according to claim 1 or 2, wherein the pH of the alkaline leaching base solution is controlled to be 8-12.
5. The alkaline leaching recovery method of the waste oxide battery positive electrode material according to claim 1 or 2, wherein the oxalate is one or more of potassium oxalate, sodium oxalate and ammonium oxalate; in the alkaline leaching base solution, the concentration of oxalate is 0.01-0.5 mol/L.
6. The alkaline leaching recovery method of the waste oxide battery positive electrode material according to claim 1 or 2, wherein the temperature of the leaching reaction is 30-90 ℃; the leaching reaction time is 1-10 h; the leaching reaction is carried out under the stirring action; the stirring speed is 100-500 r/min.
7. The alkaline leaching recovery method of the waste oxide battery positive electrode material according to claim 1 or 2, wherein the soluble ferrous salt is selected from one or two of ferrous chloride and ferrous nitrate; the molar ratio of iron in the soluble ferrous salt to the waste oxide positive electrode powder material is 1:1-4:1.
8. The alkaline leaching recovery method of a waste oxide battery positive electrode material according to claim 1 or 2, wherein the waste oxide battery positive electrode material is selected from the group consisting of Li 1+a (Ni x Co y M 1-x-y )O 2 、Na 1+a (Ni x Co y M 1-x-y )O 2 、Li(Ni p Mn q Co 2-p-q-r M r )O 4 、Na(Ni p Mn q Co 2-p-q-r M r )O 4 One or more of the following; wherein a is more than or equal to 0 and less than or equal to 0.3, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, and x+y is more than 0 and less than or equal to 1; p is more than or equal to 0 and less than or equal to 2, q is more than or equal to 0 and less than or equal to 2, p+q is more than or equal to 0 and less than or equal to 2, and r is more than or equal to 0 and less than or equal to 2; m is selected from one or more of Fe, ni, co, mn, al, V.
9. The alkaline leaching recovery method of the waste oxide battery positive electrode material according to claim 1 or 2, wherein the waste oxide battery positive electrode material is added into alkaline leaching base solution according to a solid-to-liquid ratio controlled to be 1-50 g/L.
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| CN117230312B (en) * | 2023-11-13 | 2024-03-19 | 帕瓦(长沙)新能源科技有限公司 | Alkaline leaching process of waste lithium ion battery anode material |
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