CN116002725A - Method for efficiently separating lithium element in waste lithium ion battery anode material - Google Patents
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000010405 anode material Substances 0.000 title claims description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 26
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims description 60
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 50
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 45
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000012065 filter cake Substances 0.000 claims description 32
- 230000009467 reduction Effects 0.000 claims description 30
- 238000010521 absorption reaction Methods 0.000 claims description 28
- 239000001569 carbon dioxide Substances 0.000 claims description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 239000011812 mixed powder Substances 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000571 coke Substances 0.000 claims description 7
- 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 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 36
- 229910052759 nickel Inorganic materials 0.000 abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 abstract description 8
- 239000010941 cobalt Substances 0.000 abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 16
- 239000012535 impurity Substances 0.000 description 11
- 238000002479 acid--base titration Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 229910017703 Ni Co Mn Al Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 6
- 229910017709 Ni Co Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000001941 electron spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- -1 lithium (Li) Chemical class 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- 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
Abstract
The invention relates to the field of solid waste recycling, in particular to a method for efficiently separating lithium elements in a waste lithium ion battery positive electrode material. The recovery process is simple, high-purity lithium elements are efficiently separated, no pollutant is discharged, and efficient closed-loop green recovery of lithium elements is realized. The lithium residue in the metal oxide obtained after the lithium element is separated is less, and convenience is brought to the subsequent recycling of metals or metal elements such as nickel, cobalt, manganese, iron and the like.
Description
Technical Field
The invention relates to the field of solid waste recycling, in particular to a method for efficiently separating lithium elements in a positive electrode material of a waste lithium ion battery.
Background
As atmospheric environmental pollution worsens, new energy automobile industry is promoted in various countries in the world, global electric automobiles (including pure electric and plug-in hybrid electric automobiles) are exponentially increased, and estimated by international energy institutions, the cumulative sales of the global electric automobiles reaches 2150 ten thousand by 2030. With the rapid development of electric automobiles, the demand of lithium ion batteries is also increasing, so that a large number of waste lithium ion batteries are also generated. Waste lithium ion batteries contain many valuable metals such as lithium (Li), cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), copper (Cu), aluminum (Al), and the like. Compared with mineral resources, the waste lithium ion battery has higher metal resource content, and if the metal elements in the waste lithium ion battery can be efficiently recovered, the consumption of the mineral resources can be reduced, and on the other hand, the waste lithium ion battery is directly discarded under the condition of no proper treatment, and the metal substances contained in the waste lithium ion battery pollute soil and underground water. The waste lithium ion battery material is efficiently recycled, so that the pollution to the natural environment and the harm to the human health can be avoided, valuable metal resources can be reused, and the sustainable development is promoted.
At present, 35% of the global extracted lithium elements are mainly applied to lithium ion batteries, and the dependence of China on foreign lithium resources is extremely high, so that the lithium elements need to be efficiently recovered. At present, research on recycling of lithium elements in waste lithium ion batteries has been advanced to a certain extent, and reported methods of fractional precipitation after acid leaching or water dissolution after carbothermic reduction are adopted. The method of fractional precipitation after acid leaching can generate a lot of waste water, so that the method is difficult to popularize in the actual engineering process. After carbothermal reduction in the positive electrode material of the lithium ion battery, a mixture of lithium carbonate and metal oxide is produced, and researchers separate the mixture of lithium carbonate and metal oxide by using the dissolution of lithium carbonate in water. For example, chinese patent publication No. CN113921931A, CN113213544a adopts a method of directly dissolving lithium carbonate with water after carbothermic reduction. However, lithium carbonate has a low solubility in water, and a solubility of only 1.33g/100g of water at 20 ℃ (hydrodynamics 103 (2010) 12-18), which makes the separation efficiency extremely low, and brings many obstacles to mass production.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for efficiently separating lithium elements in the anode material of the waste lithium ion battery, which has high yield of separating lithium elements and high separation efficiency, and the obtained lithium carbonate has high purity.
The aim of the invention is realized by adopting the following technical scheme:
a method for efficiently separating lithium elements in a waste lithium ion battery anode material comprises the following steps:
(1) Mechanically and uniformly mixing the anode material of the waste lithium ion battery with coke;
(2) Carrying out carbothermic reduction treatment on the mixed powder obtained in the step (1) under an anoxic atmosphere;
(3) Mixing the mixed powder obtained after carbothermic reduction obtained in the step (2) with water, and mechanically stirring to obtain a suspension;
(4) Introducing the suspension obtained in the step (3) into a reaction absorption tower, and then gradually flowing through a tower plate, an overflow weir, a downcomer and the like until the bottom of the tower flows out;
(5) Introducing carbon dioxide from the bottom of the reaction tower in the step (4), and passing through holes of each tower plate step by step and suspension flowing through the tower plates until the carbon dioxide flows out from the top of the tower;
(6) Filtering and washing the suspension flowing out of the bottom of the step (4) for multiple times, and separating to obtain filtrate and a filter cake, wherein the filter cake is a metal or metal oxide mixture;
(7) And (3) evaporating the filtrate obtained in the step (6) to dryness to obtain the high-purity lithium carbonate.
Preferably, in the step (1), the positive electrode material of the waste lithium ion battery comprises at least one of nickel cobalt lithium manganate, lithium cobaltate, lithium manganate and lithium iron phosphate.
Preferably, in the step (1), the mass ratio of the anode material of the waste lithium ion battery to the coke is 8:2.
preferably, in the step (2), the reaction temperature of the carbothermic reduction treatment is 650 ℃, the reaction time is 3 hours, and the carbothermic reduction treatment is ground into powder after being cooled to room temperature.
Preferably, in the step (3), the mixed powder obtained after carbothermic reduction is mixed with water for mechanical stirring for 0.5-6h.
Preferably, in the step (3), the concentration of the suspension solid-phase substance obtained by mixing the mixed powder obtained after carbothermic reduction with water is 1-60wt%.
Preferably, in the step (4), the operation pressure of the reaction absorption tower is 0.1-10MPa.
Preferably, in step (4), the reaction absorber operates at a temperature of 1-65 ℃.
Preferably, in the step (4), the flow rate of the suspension is 10-180m/min.
Preferably, in the step (5), the flow rate of the carbon dioxide is 0.2-20m/s.
Preferably, in the step (6), the filtration is performed 3 to 5 times of water washing.
The beneficial effects of the invention are as follows:
1. the invention adopts waste lithium ion battery anode materials to generate lithium carbonate and metals or metal oxides such as nickel, cobalt, manganese, iron and the like through carbothermal reduction, and lithium carbonate which is difficult to dissolve in water reacts with carbon dioxide in aqueous solution to generate lithium bicarbonate which is easy to dissolve in water, and then the lithium bicarbonate is separated from metals or metal oxides such as nickel, cobalt, manganese, iron and the like which are not dissolved in water. The recovery process is simple, high-purity lithium elements are efficiently separated, no pollutant is discharged, and efficient closed-loop green recovery of lithium elements is realized.
2. The lithium residue in the metal oxide obtained after the lithium element is separated is less, and convenience is brought to the subsequent recycling of metals or metal elements such as nickel, cobalt, manganese, iron and the like.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is an X-ray diffraction chart of a mixture obtained after carbothermic reduction of a nickel-cobalt-manganese ternary cathode material of a waste lithium ion battery in example 1 of the invention;
fig. 2 is an electron spectrum analysis of a mixture obtained after carbothermic reduction of the nickel-cobalt-manganese ternary cathode material of the waste lithium ion battery in example 1 of the present invention.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
The method comprises the steps of adopting a waste lithium ion battery anode material for carbothermic reduction treatment, uniformly mixing a mixture obtained by carbothermic treatment with water, introducing carbon dioxide to react with lithium carbonate to generate lithium bicarbonate, dissolving the lithium bicarbonate in the water easily, filtering and separating insoluble matters such as lithium bicarbonate, metal or metal oxide and the like, evaporating and crystallizing a lithium bicarbonate filtrate to obtain the lithium carbonate, wherein a filter cake is metal or metal oxide. The method is suitable for the common waste lithium ion battery anode material, carbon dioxide and water used in the reaction process can be collected and reused, no other pollutant is discharged, green closed-loop recovery is realized, the operation is simple and convenient, the requirement on equipment is low, and the method can be industrially popularized on a large scale.
The method for calculating the yield of the lithium element comprises the following steps:
the starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention will be further described with reference to the following examples.
Example 1
A method for efficiently separating lithium elements in a waste lithium ion battery anode material comprises the following steps:
(1) And (3) grinding the waste lithium ion battery nickel cobalt lithium manganate ternary anode material (NCM 811) and coke (the mass ratio is 8:2) uniformly, mechanically mixing for 2 hours by using a ball mill, then placing the mixture in a nitrogen atmosphere furnace for carbothermic reduction treatment, wherein the reaction temperature is 650 ℃, the heating time is 3 hours, and grinding the mixture into powder after cooling to room temperature. The resulting powder was subjected to X-ray diffraction analysis (XRD) as shown in fig. 1. According to the analysis of the X-ray diffraction peak, the powder is a mixture of lithium carbonate, nickel oxide, manganese oxide and metallic nickel. The XRD pattern does not have a diffraction peak of cobalt element, probably because the Co element compound has a low crystallinity or is in an amorphous state. The electron spectroscopy analysis of the mixture obtained after carbothermic reduction shown in fig. 2 shows that elements such as oxygen, carbon, fluorine, silicon, aluminum and the like are also present in addition to the nickel, cobalt and manganese elements.
(2) And mixing the mixed powder obtained in the previous carbothermal reduction step with water, and mechanically stirring for 1h to obtain a uniform suspension with the solid content of 15wt%.
(3) Introducing the suspension obtained in the last step into a reaction absorption tower at a flow rate of 20m/min, and enabling the suspension to gradually flow through a column plate, an overflow weir, a downcomer and the like until the suspension flows out of the bottom of the tower; introducing carbon dioxide into the bottom of the reaction absorption tower at a flow rate of 10m/s, and passing through holes of each tower plate step by step and the suspension flowing through the tower plates until the carbon dioxide flows out of the tower top; the reaction absorption tower has an operating pressure of 0.1MPa and an operating temperature of 20 ℃.
(4) Filtering the suspension flowing out from the bottom of the tower in the last step, washing with water for 3 times, and separating to obtain filtrate and filter cake. The content of Ni, co, mn, li metal element in the filter cake obtained by inductively coupled plasma emission spectrometer (icp-oes) was tested as shown in Table 1. Evaporating the obtained filtrate to obtain high-purity lithium carbonate, and determining Li in the obtained high-purity lithium carbonate by acid-base titration (GB/T11064.1-2013) 2 CO 3 The content was 99.81%, and the yield of lithium element was 95%. The content of Ni, co, mn, al, si and other impurity metal elements in lithium carbonate obtained by using an inductively coupled plasma emission spectrometer (icp-oes) is shown in Table 2.
TABLE 1 content of Ni, co, mn, li metallic elements in Filter cake
| Species of element | Ni | Co | Mn | Li |
| Content of | 23.52wt％ | 9.05wt％ | 18.24wt％ | 42ppm |
TABLE 2 content of Ni, co, mn, al, si metallic element in lithium carbonate
| Species of element | Ni | Co | Mn | Al | Si |
| Content of | 4ppm | 3ppm | 3ppm | 1ppm | 1ppm |
Example 2
A method for efficiently separating lithium elements in a waste lithium ion battery anode material comprises the following steps:
(1) The same as in example 1.
(2) And mixing the mixed powder obtained in the last step of carbothermic reduction with water, and mechanically stirring for 1h to obtain a uniform suspension with the solid content of 30wt%.
(3) Introducing the suspension obtained in the last step into a reaction absorption tower at a flow rate of 20m/min, and enabling the suspension to gradually flow through a column plate, an overflow weir, a downcomer and the like until the suspension flows out of the bottom of the tower; introducing carbon dioxide into the bottom of the reaction absorption tower at a flow rate of 10m/s, and passing through holes of each tower plate step by step and the suspension flowing through the tower plates until the carbon dioxide flows out of the tower top; the reaction absorption tower has an operating pressure of 0.1MPa and an operating temperature of 20 ℃.
(4) Filtering the suspension flowing out from the bottom of the tower in the last step, washing with water for 3 times, and separating to obtain filtrate and filter cake. The content of Ni, co, mn, li metal element in the filter cake obtained by inductively coupled plasma emission spectrometer (icp-oes) was tested as shown in Table 3. Evaporating the obtained filtrate to obtain high-purity lithium carbonate, and determining Li in the obtained high-purity lithium carbonate by acid-base titration (GB/T11064.1-2013) 2 CO 3 The content was 99.91%, and the yield of lithium element was 93%. The content of Ni, co, mn, al, si and other impurity metal elements in lithium carbonate obtained by using an inductively coupled plasma emission spectrometer (icp-oes) is shown in Table 4.
TABLE 3 content of Ni, co, mn, li metallic elements in Filter cake
| Species of element | Ni | Co | Mn | Li |
| Content of | 23.51wt％ | 9.08wt％ | 18.25wt％ | 92ppm |
TABLE 4 content of Ni, co, mn, al, si metallic elements in lithium carbonate
| Species of element | Ni | Co | Mn | Al | Si |
| Content of | 4ppm | 3ppm | 2ppm | 1ppm | 1ppm |
Example 3
A method for efficiently separating lithium elements in a waste lithium ion battery anode material comprises the following steps:
(1) The same as in example 1.
(2) And mixing the mixed powder obtained in the last step of carbothermic reduction with water, and mechanically stirring for 1h to obtain a uniform suspension with the solid content of 30wt%.
(3) Introducing the suspension obtained in the last step into a reaction absorption tower at a flow rate of 20m/min, and enabling the suspension to gradually flow through a column plate, an overflow weir, a downcomer and the like until the suspension flows out of the bottom of the tower; introducing carbon dioxide into the bottom of the reaction absorption tower at a flow rate of 10m/s, and passing through holes of each tower plate step by step and the suspension flowing through the tower plates until the carbon dioxide flows out of the tower top; the reaction absorption tower has an operating pressure of 1MPa and an operating temperature of 20 ℃.
(4) Filtering the suspension flowing out from the bottom of the tower in the last step, washing with water for 3 times, and separating to obtain filtrate and filter cake. The content of Ni, co, mn, li metal element in the filter cake obtained by inductively coupled plasma emission spectrometer (icp-oes) was tested as shown in Table 5. Evaporating the obtained filtrate to obtain high-purity lithium carbonate, and determining Li in the obtained high-purity lithium carbonate by acid-base titration (GB/T11064.1-2013) 2 CO 3 The content was 99.93%, and the yield of lithium element was 96%. The content of Ni, co, mn, al, si and other impurity metal elements in lithium carbonate obtained by using an inductively coupled plasma emission spectrometer (icp-oes) is shown in Table 6.
TABLE 5 content of Ni, co, mn, li metallic elements in Filter cake
| Species of element | Ni | Co | Mn | Li |
| Content of | 23.52wt％ | 9.07wt％ | 18.23wt％ | 22ppm |
TABLE 6 content of Ni, co, mn, al, si metallic element in lithium carbonate
| Species of element | Ni | Co | Mn | Al | Si |
| Content of | 6ppm | 5ppm | 4ppm | 2ppm | 1ppm |
Example 4
A method for efficiently separating lithium elements in a waste lithium ion battery anode material comprises the following steps:
(1) The same as in example 1.
(2) And mixing the mixed powder obtained in the last step of carbothermic reduction with water, and mechanically stirring for 1h to obtain a uniform suspension with the solid content of 30wt%.
(3) Introducing the suspension obtained in the last step into a reaction absorption tower at a flow rate of 20m/min, and enabling the suspension to gradually flow through a column plate, an overflow weir, a downcomer and the like until the suspension flows out of the bottom of the tower; introducing carbon dioxide into the bottom of the reaction absorption tower at a flow rate of 10m/s, and passing through holes of each tower plate step by step and the suspension flowing through the tower plates until the carbon dioxide flows out of the tower top; the reaction absorption tower has an operating pressure of 1MPa and an operating temperature of 50 ℃.
(4) Filtering the suspension flowing out from the bottom of the tower in the last step, washing with water for 3 times, and separating to obtain filtrate and filter cake. The content of Ni, co, mn, li metal element in the filter cake obtained by inductively coupled plasma emission spectrometer (icp-oes) was tested as shown in Table 7. Evaporating the obtained filtrate to obtain high-purity lithium carbonate, and determining Li in the obtained high-purity lithium carbonate by acid-base titration (GB/T11064.1-2013) 2 CO 3 The content was 99.95%, and the yield of lithium element was 91%. The content of Ni, co, mn, al, si and other impurity metal elements in lithium carbonate obtained by using an inductively coupled plasma emission spectrometer (icp-oes) is shown in Table 8.
TABLE 7 content of Ni, co, mn, li metallic elements in Filter cake
| Species of element | Ni | Co | Mn | Li |
| Content of | 23.51wt％ | 9.04wt％ | 18.23wt％ | 112ppm |
TABLE 8 content of Ni, co, mn, al, si metallic element in lithium carbonate
| Species of element | Ni | Co | Mn | Al | Si |
| Content of | 4ppm | 2ppm | 2ppm | 1ppm | 1ppm |
Example 5
A method for efficiently separating lithium elements in a waste lithium ion battery anode material comprises the following steps:
(1) The same elements as in example 1.
(2) And mixing the mixed powder obtained in the last step of carbothermic reduction with water, and mechanically stirring for 1h to obtain a uniform suspension with the solid content of 30wt%.
(3) Introducing the suspension obtained in the last step into a reaction absorption tower at a flow rate of 100m/min, and enabling the suspension to gradually flow through a column plate, an overflow weir, a downcomer and the like until the suspension flows out of the bottom of the tower; introducing carbon dioxide into the bottom of the reaction absorption tower at a flow rate of 20m/s, and passing through holes of each tower plate step by step and the suspension flowing through the tower plates until the carbon dioxide flows out of the tower top; the reaction absorption tower has an operating pressure of 1MPa and an operating temperature of 50 ℃.
(4) Filtering the suspension flowing out from the bottom of the tower in the last step, washing with water for 3 times, and separating to obtain filtrate and filter cake. The content of Ni, co, mn, li metal element in the filter cake obtained by inductively coupled plasma emission spectrometer (icp-oes) was tested as shown in Table 9. Evaporating the obtained filtrate to obtain high-purity lithium carbonate, and determining Li in the obtained high-purity lithium carbonate by acid-base titration (GB/T11064.1-2013) 2 CO 3 The content was 99.92%, and the yield of lithium element was 83%. The content of Ni, co, mn, al, si and other impurity metal elements in lithium carbonate obtained by using an inductively coupled plasma emission spectrometer (icp-oes) is shown in Table 10.
TABLE 9 content of Ni, co, mn, li metallic elements in Filter cake
| Species of element | Ni | Co | Mn | Li |
| Content of | 23.55wt％ | 9.07wt％ | 18.25wt％ | 115ppm |
Table 10 content of Ni, co, mn, al, si Metal element in lithium carbonate
| Species of element | Ni | Co | Mn | Al | Si |
| Content of | 4ppm | 2ppm | 3ppm | 1ppm | 1ppm |
Example 6
A method for efficiently separating lithium elements in a waste lithium ion battery anode material comprises the following steps:
(1) And (3) grinding the lithium cobalt oxide anode material of the waste lithium ion battery and coke (the mass ratio is 8:2) uniformly, mechanically mixing for 2 hours by using a ball mill, then placing the mixture in a nitrogen atmosphere furnace for carbothermic reduction treatment, cooling to room temperature for 2 hours at the reaction temperature of 550 ℃, and grinding into powder.
(2) And mixing the mixed powder obtained in the last step of carbothermic reduction with water, and mechanically stirring for 1h to obtain a uniform suspension with the solid content of 20wt%.
(3) Introducing the suspension obtained in the last step into a reaction absorption tower at a flow rate of 25m/min, and enabling the suspension to gradually flow through a column plate, an overflow weir, a downcomer and the like until the suspension flows out of the bottom of the tower; introducing carbon dioxide into the bottom of the reaction absorption tower at a flow rate of 2m/s, and passing through holes of each tower plate step by step and the suspension flowing through the tower plates until the carbon dioxide flows out of the tower top; the reaction absorption tower has an operating pressure of 0.5MPa and an operating temperature of 25 ℃.
(4) Filtering the suspension flowing out from the bottom of the tower in the last step, washing with water for 5 times, and separating to obtain filtrate and filter cake. The filter cake is a mixture of cobalt and cobalt oxide, and the content of metal elements in the filter cake obtained by adopting an inductively coupled plasma emission spectrometer (icp-oes) is shown in table 11; evaporating the obtained filtrate to obtain high-purity lithium carbonate, and determining Li in the obtained high-purity lithium carbonate by acid-base titration (GB/T11064.1-2013) 2 CO 3 The content was 99.74%, and the yield of lithium element was 93%. The content of metal impurity elements in lithium carbonate obtained by using an inductively coupled plasma emission spectrometer (icp-oes) is shown in Table 12.
TABLE 11 Co, li Metal element content in Filter cake
| Species of element | Co | Li |
| Content of | 41.57wt％ | 21ppm |
Table 12 content of impurity metal element such as Ni, co, mn, al, si in lithium carbonate
| Species of element | Ni | Co | Mn | Al | Si |
| Content of | — | 4ppm | — | 1ppm | — |
Example 7
A method for efficiently separating lithium elements in a waste lithium ion battery anode material comprises the following steps:
(1) Grinding the lithium manganate positive electrode material of the waste lithium ion battery and coke (the mass ratio is 8:2) uniformly, mechanically mixing for 2 hours by using a ball mill, then placing the mixture in a nitrogen atmosphere furnace for carbothermic reduction treatment, cooling to room temperature for 2 hours at the reaction temperature of 650 ℃, and grinding into powder.
(2) And mixing the mixed powder obtained in the last step of carbothermic reduction with water, and mechanically stirring for 1h to obtain a uniform suspension with the solid content of 20wt%.
(3) Introducing the suspension obtained in the last step into a reaction absorption tower at a flow rate of 40m/min, and enabling the suspension to gradually flow through a column plate, an overflow weir, a downcomer and the like until the suspension flows out of the bottom of the tower; introducing carbon dioxide into the bottom of the reaction absorption tower at a flow rate of 10m/s, and passing through holes of each tower plate step by step and the suspension flowing through the tower plates until the carbon dioxide flows out of the tower top; the reaction absorption tower has an operating pressure of 1.5Mpa and an operating temperature of 25 ℃.
(4) Filtering the suspension flowing out from the bottom of the tower in the last step, washing for 4 times, and separating to obtain filtrate and filter cake. The filter cake is a mixture of manganese and manganese oxide, and the content of metal elements in the filter cake is obtained by adopting an inductively coupled plasma emission spectrometer (icp-oes) as shown in table 13; evaporating the obtained filtrate to obtain high-purity lithium carbonate, and determining Li in the obtained high-purity lithium carbonate by acid-base titration (GB/T11064.1-2013) 2 CO 3 The content was 99.79%, and the yield of lithium element was 97%. The content of metal impurity elements in lithium carbonate obtained by using an inductively coupled plasma emission spectrometer (icp-oes) is shown in Table 14.
TABLE 13 Mn, li Metal element content in Filter cake
| Species of element | Mn | Li |
| Content of | 44.52wt％ | 25ppm |
Table 14 content of impurity metal element such as Ni, co, mn, al, si in lithium carbonate
| Species of element | Ni | Co | Mn | Al | Si |
| Content of | — | — | 9ppm | 1ppm | — |
Example 8
A method for efficiently separating lithium elements in a waste lithium ion battery anode material comprises the following steps:
(1) Grinding the waste lithium ion battery lithium iron phosphate anode material and coke (the mass ratio is 8:2) uniformly, mechanically mixing for 2 hours by using a ball mill, then placing the mixture in a nitrogen atmosphere furnace for carbothermic reduction treatment, cooling to room temperature for 2 hours at the reaction temperature of 700 ℃, and grinding into powder.
(2) And mixing the mixed powder obtained in the last step of carbothermic reduction with water, and mechanically stirring for 1h to obtain a uniform suspension with the solid content of 20wt%.
(3) Introducing the suspension obtained in the last step into a reaction absorption tower at a flow rate of 10m/min, and enabling the suspension to gradually flow through a column plate, an overflow weir, a downcomer and the like until the suspension flows out of the bottom of the tower; introducing carbon dioxide into the bottom of the reaction absorption tower at a flow rate of 10m/s, and passing through holes of each tower plate step by step and the suspension flowing through the tower plates until the carbon dioxide flows out of the tower top; the reaction absorption tower has an operating pressure of 1MPa and an operating temperature of 25 ℃.
(4) Filtering the suspension flowing out from the bottom of the tower in the last step, washing with water for 3 times, and separating to obtain filtrate and filter cake. The filter cake is a mixture of ferric oxide and ferric phosphide, and the content of metal elements in the filter cake obtained by adopting an inductively coupled plasma emission spectrometer (icp-oes) is shown in table 15; evaporating the obtained filtrate to obtain high-purity lithium carbonate, and determining Li in the obtained high-purity lithium carbonate by acid-base titration (GB/T11064.1-2013) 2 CO 3 The content was 99.81%, and the yield of lithium element was 95%. The content of metal impurity elements in lithium carbonate obtained by using an inductively coupled plasma emission spectrometer (icp-oes) is shown in Table 16.
TABLE 15 Fe, li Metal element content in Filter cake
| Species of element | Fe | Li |
| Content of | 25.24wt％ | 34ppm |
TABLE 16 content of impurity Metal elements such as Fe, al in lithium carbonate
| Species of element | Fe | Al |
| Content of | 4ppm | 1ppm |
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. A method for efficiently separating lithium elements in a waste lithium ion battery anode material is characterized by comprising the following steps:
(1) Mechanically and uniformly mixing the anode material of the waste lithium ion battery with coke;
(2) Carrying out carbothermic reduction treatment on the mixed powder obtained in the step (1) under an anoxic atmosphere;
(3) Mixing the mixed powder obtained after carbothermic reduction obtained in the step (2) with water, and mechanically stirring to obtain a suspension;
(4) Introducing the suspension obtained in the step (3) into a reaction absorption tower, and then gradually flowing through a tower plate, an overflow weir, a downcomer and the like until the bottom of the tower flows out;
(5) Introducing carbon dioxide from the bottom of the reaction tower in the step (4), and passing through holes of each tower plate step by step and suspension flowing through the tower plates until the carbon dioxide flows out from the top of the tower;
(6) Filtering and washing the suspension flowing out of the bottom of the step (4) for multiple times, and separating to obtain filtrate and a filter cake, wherein the filter cake is a metal or metal oxide mixture;
(7) And (3) evaporating the filtrate obtained in the step (6) to dryness to obtain the high-purity lithium carbonate.
2. The method for efficiently separating lithium elements from the waste lithium ion battery positive electrode material according to claim 1, wherein in the step (1), the waste lithium ion battery positive electrode material comprises at least one of nickel cobalt lithium manganate, lithium cobaltate, lithium manganate and lithium iron phosphate.
3. The method for efficiently separating lithium elements from the anode material of the waste lithium ion battery according to claim 1, wherein in the step (3), the mixed powder obtained after carbothermic reduction is mixed with water for mechanical stirring for 0.5-6h.
4. The method for efficiently separating lithium elements from the anode material of the waste lithium ion battery according to claim 1, wherein in the step (3), the concentration of the suspension solid phase substance obtained by mixing the mixed powder obtained by carbothermic reduction with water is 1-60wt%.
5. The method for efficiently separating lithium elements from the anode material of the waste lithium ion battery according to claim 1, wherein in the step (4), the operation pressure of the reaction absorption tower is 0.1-10MPa, and the operation temperature is 1-65 ℃.
6. The method for efficiently separating lithium elements from the anode material of the waste lithium ion battery according to claim 1, wherein in the step (4), the flow rate of the suspension is 10-180m/min.
7. The method for efficiently separating lithium elements from the anode material of the waste lithium ion battery according to claim 1, wherein in the step (5), the flow rate of the carbon dioxide is 0.2-20m/s.
8. The method for efficiently separating lithium element from the anode material of the waste lithium ion battery according to claim 1, wherein in the step (6), the filtering is performed for 3-5 times.
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| CN106129511A (en) * | 2016-06-27 | 2016-11-16 | 北京科技大学 | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material |
| CN111825110A (en) * | 2020-05-12 | 2020-10-27 | 宁夏百川新材料有限公司 | Recycling method of waste lithium ion battery anode material |
| CN113213544A (en) * | 2021-03-29 | 2021-08-06 | 中南大学 | Method for regenerating electrode by using waste lithium battery and leaching residues |
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| CN106129511A (en) * | 2016-06-27 | 2016-11-16 | 北京科技大学 | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material |
| CN111825110A (en) * | 2020-05-12 | 2020-10-27 | 宁夏百川新材料有限公司 | Recycling method of waste lithium ion battery anode material |
| CN113213544A (en) * | 2021-03-29 | 2021-08-06 | 中南大学 | Method for regenerating electrode by using waste lithium battery and leaching residues |
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