CN114597526A - Method for extracting lithium salt by reducing and roasting ternary lithium battery positive electrode waste - Google Patents
Method for extracting lithium salt by reducing and roasting ternary lithium battery positive electrode waste Download PDFInfo
- Publication number
- CN114597526A CN114597526A CN202011407894.8A CN202011407894A CN114597526A CN 114597526 A CN114597526 A CN 114597526A CN 202011407894 A CN202011407894 A CN 202011407894A CN 114597526 A CN114597526 A CN 114597526A
- Authority
- CN
- China
- Prior art keywords
- ternary
- lithium
- positive electrode
- roasting
- reduction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 70
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002699 waste material Substances 0.000 title claims abstract description 23
- 229910003002 lithium salt Inorganic materials 0.000 title claims abstract description 20
- 159000000002 lithium salts Chemical class 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000002386 leaching Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 26
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 26
- 229910001868 water Inorganic materials 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 21
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000012216 screening Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000007670 refining Methods 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000003345 natural gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 238000004537 pulping Methods 0.000 abstract description 3
- 238000011027 product recovery Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 32
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- 229910017703 Ni Co Mn Al Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application provides a method for extracting lithium salt from a waste material of a positive electrode of a reduction roasting ternary lithium battery, which comprises the steps of disassembling a scrapped lithium battery to obtain a ternary positive electrode plate, and crushing and screening the ternary positive electrode plate to obtain ternary positive electrode powder; placing the ternary positive electrode powder into a reducing atmosphere roasting furnace for reducing roasting to obtain a roasted ternary material; placing the roasted ternary material into a ball mill for slurrying and ball milling to obtain a ball-milled ternary material; transferring the ball-milled ternary material into a reaction kettle, adding water for leaching, performing solid-liquid separation to obtain a lithium-rich solution, and refining the lithium-rich solution to remove impurities through residues to obtain a refined lithium-rich solution; introducing carbon dioxide into the refined lithium-rich solution to obtain lithium carbonate precipitate; and pulping and washing the lithium carbonate precipitate, centrifugally dewatering and drying to obtain the battery-grade lithium carbonate. The method has the characteristics of low cost, simple process, high product purity and high product recovery rate.
Description
Technical Field
The invention belongs to the technical field of lithium battery recovery, and particularly relates to a method for extracting lithium salt from a ternary lithium battery anode waste material through reduction roasting.
Background
Since its birth, lithium ion batteries have been widely used in the fields of battery products such as mobile phones, notebooks, and charge pads because of their characteristics of high energy density, fast charge and discharge, and particularly, their application has been greatly promoted with the rise of new energy vehicles. The service life of the lithium battery is generally 3-5 years, waste lithium batteries are scrapped along with the large-scale application of the lithium battery, the scrapped lithium batteries contain a large amount of organic matters, fluorides and heavy metals which are harmful to the environment and human bodies, and serious environmental pollution is caused if the waste lithium batteries cannot be properly treated. Therefore, the development of a simple and effective recovery process of the scrapped lithium battery is urgently needed.
Disclosure of Invention
The embodiment of the invention provides a method for extracting lithium salt by reducing and roasting positive electrode waste of a ternary lithium battery, which is used for solving the technical problem that the discarded lithium battery pollutes the environment.
Provided is a method for extracting lithium salt from reduction roasting ternary lithium battery positive electrode waste, comprising the following steps:
disassembling a scrapped lithium battery to obtain a ternary positive plate, and crushing and screening the ternary positive plate to obtain ternary positive powder;
placing the ternary positive electrode powder into a reducing atmosphere roasting furnace for reducing roasting to obtain a roasted ternary material;
placing the roasted ternary material into a ball mill for slurrying and ball milling to obtain a ball-milled ternary material;
transferring the ball-milled ternary material into a reaction kettle, adding water for leaching, and performing solid-liquid separation to obtain a lithium-rich solution and residues;
refining the lithium-rich solution to remove impurities to obtain a refined lithium-rich solution;
introducing carbon dioxide into the refined lithium-rich solution to obtain lithium carbonate precipitate;
and performing slurrying washing, centrifugal dehydration and drying on the lithium carbonate precipitate to obtain the battery-grade lithium carbonate.
Preferably, the granularity of the ternary cathode powder is 50-500 meshes.
Preferably, the reducing atmosphere in the reducing roasting atmosphere is one or more of carbon monoxide, nitrogen and natural gas, the concentration of the reducing atmosphere is 60-70%, the roasting temperature is 200-700 ℃, and the roasting time is 1-6 h.
Preferably, the granularity of the ball-milling ternary material is 50-500 meshes.
Preferably, the solid-to-solid ratio of the water leaching solution for water leaching is 1: 1-6: 1, the reaction temperature of the water leaching reaction is 50-90 ℃, and the reaction time is 1-5 hours.
Preferably, the lithium-rich solution is refined and purified by adopting resin for removing impurities.
Preferably, the method further comprises the steps of carrying out strong acid dissolution, precipitation reaction, extraction impurity removal and crystallization on the residue to obtain the product.
According to the technical scheme, the method for extracting the lithium salt from the waste material of the positive electrode of the reduction roasting ternary lithium battery, provided by the embodiment of the invention, comprises the steps of disassembling a scrapped lithium battery to obtain a ternary positive electrode plate, and crushing and screening the ternary positive electrode plate to obtain ternary positive electrode powder; placing the ternary positive electrode powder into a reducing atmosphere roasting furnace for reducing roasting to obtain a roasted ternary material; placing the roasted ternary material into a ball mill for slurrying and ball milling to obtain a ball-milled ternary material; transferring the ball-milled ternary material into a reaction kettle, adding water for leaching, and performing solid-liquid separation to obtain a lithium-rich solution and residues; refining the lithium-rich solution to remove impurities to obtain a refined lithium-rich solution; introducing carbon dioxide into the refined lithium-rich solution to obtain lithium carbonate precipitate; and pulping and washing the lithium carbonate precipitate, centrifugally dewatering and drying to obtain the battery-grade lithium carbonate. Under the condition of no need of adding other additives, the reduction roasting is carried out in the reduction furnace by using the oxidizing atmosphere, the lithium can be selectively and preferentially extracted by utilizing the replacement action of the reducing atmosphere and the decomposition reaction of a replacement product, most of lithium is dissolved in an aqueous solution (the leaching rate of the lithium is more than 99 percent) through water leaching, the leaching of other metals such as nickel, cobalt, manganese and the like is avoided, the recovery rate of the lithium metal is improved, the recovery process of the lithium is reduced, and the production cost can be greatly reduced. Creatively utilizes the characteristic of water extract (lithium hydroxide solution), the lithium hydroxide solution is refined and purified, and pure CO is introduced2Gas reaction is carried out to obtain pure lithium carbonate precipitate, and the high-purity lithium carbonate product (carbon) is obtained through the working procedures of slurrying, washing, centrifugal dehydration, drying and the likeThe purity of lithium oxide can reach more than 99.9 percent).
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is a flow chart of a method for extracting lithium salt from the waste material of the positive electrode of a reduction-calcined ternary lithium battery according to an embodiment of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Fig. 1 is a flow chart of a method for extracting lithium salt from reduction-calcined ternary lithium battery positive electrode waste provided by an embodiment of the present invention, and the method for extracting lithium salt from reduction-calcined ternary lithium battery positive electrode waste provided by the present application is described in detail below with reference to the accompanying drawings.
As shown in FIG. 1, the method for extracting lithium salt from the waste cathode material of the reduction-calcined ternary lithium battery specifically comprises the following steps.
S1: and disassembling the scrapped lithium battery to obtain a ternary positive plate, and crushing and screening the ternary positive plate to obtain ternary positive powder.
The scrapped lithium battery in retired service is disassembled to obtain a ternary positive plate, the ternary positive plate is crushed and sieved to obtain ternary positive powder, and the granularity of the ternary positive powder is 50-500 meshes.
S2: and (3) placing the ternary positive electrode powder into a reducing atmosphere roasting furnace for reducing roasting to obtain a roasted ternary material.
The ternary positive electrode powder is placed into a reducing atmosphere roasting furnace for reducing roasting, the reducing atmosphere roasting furnace is a steel belt conveying furnace, the reducing atmosphere in the reducing roasting atmosphere is one or more of carbon monoxide, nitrogen and natural gas, the concentration of the reducing atmosphere is 60-70%, the roasting temperature is 200-700 ℃, the roasting time of the ternary positive electrode powder in the reducing furnace is controlled to be 1-6 hours, a roasted ternary material is finally obtained, and the roasted ternary material lithium is converted into a compound capable of reacting with water to produce water-soluble compounds.
S3: and placing the roasted ternary material into a ball mill for slurrying and ball milling to obtain a ball-milled ternary material.
The roasted ternary material has certain agglomeration, the material needs to be put into a ball mill for slurrying and ball milling to obtain a ball-milled ternary material, and the granularity of the ball-milled material is controlled to be 50-500 meshes.
S4: and transferring the ball-milled ternary material into a reaction kettle, adding water for leaching, and performing solid-liquid separation to obtain a lithium-rich solution and residues.
Performing water leaching reaction on the ball-milled materials in a reaction kettle, leaching Li in the materials into a solution, wherein the solid-to-solid ratio of the water leaching solution is 1: 1-6: 1, the reaction temperature of the water leaching reaction is controlled to be 50-90 ℃, and the water leaching reaction time is controlled to be 1-5 h. Then, lithium-rich solution and residue are obtained through solid-liquid separation.
S5: and refining the lithium-rich solution to remove impurities to obtain the refined lithium-rich solution.
And after the water leaching reaction, the lithium-rich solution is a crude lithium hydroxide solution, the concentration of Li is 10-20 g/L, and the alkalinity is 1-2.5N. The crude lithium hydroxide solution is refined to remove impurities to obtain a refined lithium-rich solution. The special resin is used for removing impurities.
S6: and introducing carbon dioxide into the refined lithium-rich solution to obtain lithium carbonate precipitate.
And (3) refining the lithium-rich solution, namely the refined lithium hydroxide solution, carrying out carbon dioxide introduction lithium precipitation reaction, wherein the reaction temperature in the lithium precipitation process is controlled to be 80-85 ℃, and the precipitation time is controlled to be 1-2h, so as to obtain lithium carbonate precipitate. The carbon dioxide introduced is composed of CO2The pure gas produced by the generator. Carbon dioxide is introduced into the reaction kettle, a special aeration head is needed, the dissolving and absorbing rate of the carbon dioxide is greatly improved, and the lithium salt precipitation efficiency is improved.
S7: and pulping and washing the lithium carbonate precipitate, centrifugally dewatering and drying to obtain the battery-grade lithium carbonate.
And washing lithium salt generated by precipitation by using primary slurrying deionized water, centrifugally dewatering and drying to obtain the battery-grade lithium carbonate.
S8: and carrying out strong acid dissolution, precipitation reaction, extraction impurity removal and crystallization on the residue to obtain the product.
Dissolving the water leaching reaction residues by using sulfuric acid and hydrogen peroxide or sulfur dioxide or sodium sulfite, filtering out insoluble substances, removing iron and aluminum impurities by a chemical precipitation method, extracting and separating to obtain a cobalt sulfate solution, a nickel sulfate solution and a manganese sulfate solution, and obtaining a cobalt sulfate, nickel sulfate and manganese sulfate mixed product by evaporative crystallization.
Examples of the experiments
Taking the ternary positive plate waste material, wherein the main components of the ternary positive plate waste material are shown in the table 1.
TABLE 1 Main Components of ternary Positive plate waste
| Element(s) | Li | Ni | Co | Mn | Al |
| Wt% | 6 | 10.94 | 14.68 | 13.45 | 8.9 |
Crushing and screening the ternary positive plate, controlling the granularity of the screened ternary powder to be 100 meshes, then carrying out reduction roasting treatment, controlling the reduction roasting temperature to be 600 ℃, controlling the roasting time in a reduction atmosphere to be 4 hours, enabling the roasted material to be agglomerated, carrying out slurrying ball milling by using a ball mill, controlling the liquid-solid ratio of the slurrying ball milling to be 1:1, controlling the ball milling time to be 2 hours, and controlling the granularity of the ball-milled material to be 200 meshes.
The main components of the 100-mesh ternary cathode powder after crushing and screening are shown in table 2.
TABLE 2 ternary cathode powder main Components
| Element(s) | Li | Ni | Co | Mn | Al |
| Wt% | 6 | 10.94 | 14.68 | 13.45 | 0.3 |
And (3) placing the ternary positive electrode powder into a reducing atmosphere roasting furnace for reducing roasting, wherein the reducing atmosphere in the reducing roasting atmosphere is a mixed gas of carbon monoxide, nitrogen and natural gas, the concentration of the reducing atmosphere is 60%, the roasting temperature is 200 ℃, and the roasting time of the ternary positive electrode powder in the roasting furnace is controlled to be 3 hours, so that the roasted ternary material is obtained.
And placing the roasted ternary material into a ball mill for slurrying and ball milling to obtain a ball-milled ternary material with the granularity of 100 meshes.
Transferring the ball-milled slurried material to a water leaching reaction tank for water leaching reaction, controlling the liquid-solid ratio of the water leaching reaction liquid to be 4:1, controlling the reaction temperature to be 60 ℃, and filtering and separating the leached slurry to obtain leachate and leached residues.
The leachate composition is given in Table 3.
TABLE 3 composition of the leach liquors
| Element(s) | Li | Ni | Co | Mn | Al | Alkalinity of |
| g/L | 16 | 0.0001 | 0.0001 | 0.0001 | 0.3 | 2,1N |
The leaching residue is washed and dried, and the components of the leaching residue are detected as shown in the table 4.
TABLE 4 composition of residue
| Element(s) | Li | Ni | Co | Mn | Al |
| Wt% | 0.05 | 11.2 | 15.3 | 14.6 | 0.2 |
In the water leaching process, the Li leaching rate reaches more than 99.5 percent.
Leaching residue is subjected to acid leaching, precipitation for impurity removal, extraction separation and evaporation crystallization to obtain salt crystals containing nickel, cobalt and manganese respectively, which are not described in detail herein.
The lithium water extract is purified and refined by special resin to obtain refined solution, and the components are shown in Table 5.
TABLE 5 refined liquid composition
| Element(s) | Li | Ni | Co | Mn | Al | Alkalinity of |
| g/L | 16 | 0.0001 | 0.0001 | 0.0001 | 0.0001 | 2,1N |
Introducing purified CO2 into the refined lithium liquid to perform lithium precipitation reaction, controlling the reaction temperature to be 80-85 ℃ in the lithium precipitation process, controlling the precipitation time to be 1h, slurrying and washing the precipitated lithium carbonate for 1 time, centrifugally dewatering and drying to obtain dried lithium carbonate, wherein the components of the dried lithium carbonate are shown in Table 6.
TABLE 6 lithium carbonate composition after drying
| Index (I) | Unit of | Battery level control index | Measured value |
| Li2CO3 | % | ≥99.5 | 99.95 |
| H2O | % | ≤0.25 | 0.15 |
| Fe | ppm | ≤10 | 3 |
| Mg | ppm | ≤80 | 6 |
| Ca | ppm | ≤50 | 8 |
| Na | ppm | ≤250 | 15 |
| K | ppm | ≤10 | 2 |
| Zn | ppm | ≤3 | 0 |
| Pb | ppm | ≤3 | 0 |
| Cu | ppm | ≤3 | 0 |
| Al | ppm | ≤10 | 2 |
| Mn | ppm | ≤3 | 2 |
| Si | ppm | ≤30 | 3 |
| SO42- | ppm | ≤800 | 50 |
The lithium carbonate component meets the standard of battery grade lithium carbonate.
The embodiments in this specification are described in a progressive manner. The same and similar parts among the various embodiments can be mutually referred, and each embodiment focuses on the differences from the other embodiments.
It should be noted that, unless otherwise specified and limited, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a circuit structure, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such article or apparatus. Without further limitation, the presence of an element identified by the phrase "comprising an … …" does not exclude the presence of additional like elements in the article or device comprising the element. In addition, as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It will be understood that the invention is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (7)
1. A method for extracting lithium salt from waste materials of a positive electrode of a reduction-calcined ternary lithium battery, which is characterized by comprising the following steps:
disassembling a scrapped lithium battery to obtain a ternary positive plate, and crushing and screening the ternary positive plate to obtain ternary positive powder;
placing the ternary positive electrode powder into a reducing atmosphere roasting furnace for reducing roasting to obtain a roasted ternary material;
placing the roasted ternary material into a ball mill for slurrying and ball milling to obtain a ball-milled ternary material;
transferring the ball-milled ternary material into a reaction kettle, adding water for leaching, and performing solid-liquid separation to obtain a lithium-rich solution and residues;
refining the lithium-rich solution to remove impurities to obtain a refined lithium-rich solution;
introducing carbon dioxide into the refined lithium-rich solution to obtain lithium carbonate precipitate;
and performing slurrying washing, centrifugal dehydration and drying on the lithium carbonate precipitate to obtain the battery-grade lithium carbonate.
2. The method for extracting lithium salt from the reduction-calcined ternary lithium battery positive electrode waste material as claimed in claim 1, wherein the granularity of the ternary positive electrode powder is 50-500 meshes.
3. The method for extracting lithium salt from the reduction roasting ternary lithium battery positive electrode waste material as claimed in claim 1, wherein the reduction atmosphere in the reduction roasting atmosphere is one or more of carbon monoxide, nitrogen and natural gas, the concentration of the reduction atmosphere is 60-70%, the roasting temperature is 200-700 ℃, and the roasting time is 1-6 h.
4. The method for extracting lithium salt from the reduction-calcined ternary lithium battery positive electrode waste material as claimed in claim 1, wherein the particle size of the ball-milled ternary material is 50-500 meshes.
5. The method for extracting lithium salt from the reduction-roasted ternary lithium battery positive electrode waste material as claimed in claim 1, wherein the water leaching solution solid-to-solid ratio of the water leaching is 1: 1-6: 1, the reaction temperature of the water leaching reaction is 50-90 ℃, and the reaction time is 1-5 hours.
6. The method for extracting lithium salt from the reduction-calcined ternary lithium battery positive electrode waste material as claimed in claim 1, wherein the lithium-rich solution is refined and purified by resin.
7. The method for extracting lithium salt from the reduction-calcined ternary lithium battery positive electrode waste material as claimed in claim 1, further comprising the steps of performing strong acid dissolution, precipitation reaction, extraction impurity removal and crystallization on the residue to obtain a product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011407894.8A CN114597526A (en) | 2020-12-05 | 2020-12-05 | Method for extracting lithium salt by reducing and roasting ternary lithium battery positive electrode waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011407894.8A CN114597526A (en) | 2020-12-05 | 2020-12-05 | Method for extracting lithium salt by reducing and roasting ternary lithium battery positive electrode waste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114597526A true CN114597526A (en) | 2022-06-07 |
Family
ID=81802312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011407894.8A Pending CN114597526A (en) | 2020-12-05 | 2020-12-05 | Method for extracting lithium salt by reducing and roasting ternary lithium battery positive electrode waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114597526A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115947357A (en) * | 2023-02-03 | 2023-04-11 | 上海电气集团股份有限公司 | Method for extracting lithium carbonate |
-
2020
- 2020-12-05 CN CN202011407894.8A patent/CN114597526A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115947357A (en) * | 2023-02-03 | 2023-04-11 | 上海电气集团股份有限公司 | Method for extracting lithium carbonate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107017443B (en) | A method for comprehensive recovery of valuable metals from waste lithium-ion batteries | |
| CA3058572C (en) | Lithium ion battery scrap treatment method | |
| US20210079495A1 (en) | Process for the recovery of cobalt, lithium, and other metals from spent lithium-based batteries and other feeds | |
| CN108075203B (en) | A method for recovering valuable metal components in waste lithium-ion battery materials | |
| JP4865745B2 (en) | Method for recovering valuable metals from lithium batteries containing Co, Ni, Mn | |
| US11981976B2 (en) | Method for purifying nickel-cobalt-manganese leaching solution | |
| WO2017145099A1 (en) | Process for recovery of pure cobalt oxide from spent lithium ion batteries with high manganese content | |
| JP6070898B2 (en) | Method and facility for recovering valuable components from waste dry batteries | |
| KR102724564B1 (en) | Method for recovering valuable metals from spent lithium-ion batteries | |
| US20230193422A1 (en) | Method for producing mixed metal solution and method for producing mixed metal salt | |
| CN109097581A (en) | The recovery method of valuable metal in waste and old nickel cobalt manganese lithium ion battery | |
| CN112111650B (en) | Method for recovering valuable metals of waste lithium ion batteries by selective reduction | |
| JP2023063319A (en) | Method for treating lithium-ion battery waste and method for producing sulfate | |
| CN102994747A (en) | Technology for recovering metallic copper from high-lead copper matte | |
| KR102737366B1 (en) | Method for recovering manganese from waste batteries and recovery facility | |
| WO2023010969A1 (en) | Method for recycling spent lithium-ion batteries | |
| CN109004307A (en) | The recyclable device of valuable metal in waste and old nickel cobalt manganese lithium ion battery | |
| JP6314730B2 (en) | Method for recovering valuable metals from waste nickel metal hydride batteries | |
| CN114597526A (en) | Method for extracting lithium salt by reducing and roasting ternary lithium battery positive electrode waste | |
| CN101195869A (en) | Solvent extraction method for materials after nickelous oxide mine chloridization oxidation treatment | |
| KR100820163B1 (en) | Separation and Extraction Method of Cobalt from Lithium Battery Cathode Active Material | |
| JP6943141B2 (en) | Leaching method of mixed sulfide containing nickel and cobalt | |
| US8974754B2 (en) | Method for producing nickel-containing acid solution | |
| CN114006067B (en) | Method and system for recycling anode and cathode mixed powder of waste ternary lithium ion battery | |
| CN111100991A (en) | Treatment method of nickel wet refining tailings based on high-temperature oxygen pressure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20220607 |