CN117049575A - Method for preferentially extracting lithium from waste lithium ion battery anode by two-step roasting method - Google Patents
Method for preferentially extracting lithium from waste lithium ion battery anode by two-step roasting method Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 68
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 57
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 title claims abstract description 20
- 239000007774 positive electrode material Substances 0.000 claims abstract description 32
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 21
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000605 extraction Methods 0.000 claims abstract description 18
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 12
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 11
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007654 immersion Methods 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002893 slag Substances 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-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
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 30
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 2
- 229910000385 transition metal sulfate Inorganic materials 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910018068 Li 2 O Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229940087748 lithium sulfate Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 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 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- -1 oxide Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a method for preferentially extracting lithium from the anode of a waste lithium ion battery by a two-step roasting method, and belongs to the technical field of lithium recovery. A method for preferentially extracting lithium from the positive electrode of a waste lithium ion battery by a two-step roasting method comprises the following steps of; mixing the anode material and ammonium sulfate and roasting to obtain a first roasting product; heating and roasting to obtain a second roasting product; leaching the second roasting product by water, and then filtering, evaporating and crystallizing to obtain a lithium-rich solution and a slag phase; adding a precipitant into the lithium-rich solution, and filtering to obtain lithium carbonate. According to the method, ammonium sulfate is used as a roasting agent, so that part of positive electrode materials are converted into sulfate, transition metal sulfate serving as a heating intermediate product reacts with unreacted positive electrode materials to generate water-soluble lithium sulfate and water-insoluble transition metal oxide, and the preferential extraction of lithium is realized after water immersion. The preparation method is simple, the consumed ammonium sulfate is less, and no pollution gas is generated; the extraction rate and selectivity of lithium are high, and the purity of the obtained lithium carbonate is high.
Description
Technical Field
The invention belongs to the technical field of lithium recovery, and particularly relates to a method for preferentially extracting lithium from the positive electrode of a waste lithium ion battery by a two-step roasting method.
Background
The positive electrode of the waste lithium ion battery refers to a positive electrode material in the battery, and is usually a composite material formed by mixing a lithium compound (such as oxide, phosphate and the like) with other metals (such as cobalt, manganese, nickel and the like). The positive electrode is an important component in the lithium ion battery and is responsible for storing and releasing lithium ions to participate in the charge and discharge process of the battery.
The positive electrode of the discarded lithium ion battery generally contains recoverable valuable metal elements such as lithium, cobalt, nickel, and the like. In the recycling and disposal of waste batteries, the positive electrode is typically separated and disposed of to recover valuable elements and materials therein. Recycling the battery anode material helps to reduce the need for raw materials, save resources, and reduce negative impact on the environment. With proper recovery and disposal, valuable elements in the positive electrode of the discarded lithium-ion battery can be reused for manufacturing new batteries or other applications.
The process of recovering lithium from the positive electrode involves the steps of:
1. collecting waste lithium ion batteries: the discarded lithium ion batteries may be collected from an electronic waste recycling station, a recycling center, or a specialized waste recycling facility.
2. Separating the positive electrode: the waste battery can be separated after pretreatment, and the positive electrode is taken out from the battery. Separation is typically carried out by mechanical disruption, chemical dissolution or heat treatment.
3. Extracting lithium: the separated positive electrode may be treated under corresponding process conditions to extract lithium metal therefrom. Some common extraction methods include leaching, electrolysis, and heat treatment.
4. Purification and reuse of lithium: the extracted lithium metal needs to be subjected to a purification process to remove other impurities. The purified lithium can be used to prepare new lithium ion batteries, or for other lithium-related applications.
The sulfate roasting method is a method commonly used for recovering lithium from lithium ion batteries, and in the prior art, lithium, cobalt, nickel and manganese are often simultaneously converted into lithium sulfate, cobalt sulfate, nickel sulfate and manganese sulfate by adding excessive roasting agents. Leaching lithium, cobalt, nickel and manganese into a solution by adopting a water leaching mode, adding calcium hydroxide or calcium oxide to precipitate cobalt, nickel and manganese ions in the solution, and finally adding sodium carbonate into the solution to synthesize lithium carbonate. Firstly, the method consumes more roasting agent, and can generate polluting gases, ammonia, sulfur dioxide and the like in the roasting process; secondly, lithium ions are inevitably taken away in the process of firstly precipitating cobalt, nickel and manganese ions, so that the extraction rate of the lithium ions is low, and impurity cations are easily mixed in the obtained lithium carbonate, so that the purity of the lithium carbonate is low.
Disclosure of Invention
The invention provides a method for preferentially extracting lithium from the anode of a waste lithium ion battery by a two-step roasting method, which aims to solve the technical problems of complicated lithium recovery operation, gas pollution, low lithium ion extraction rate and low purity in the prior art.
In order to solve the above-mentioned purpose, the technical scheme provided by the invention is as follows:
a method for preferentially extracting lithium from the positive electrode of a waste lithium ion battery by a two-step roasting method comprises the following steps:
s1, mixing a positive electrode material with ammonium sulfate, and then roasting in a first stage to partially convert the positive electrode material into sulfate to obtain a first roasting product;
s2, raising the temperature to enable the first roasting product to be roasted in a second stage, so as to obtain a second roasting product;
s3, leaching the second roasting product, filtering, evaporating and crystallizing to obtain a lithium-rich solution and a slag phase;
and S4, adding a precipitant into the lithium-rich solution to obtain a precipitation reaction solution, and filtering to obtain lithium carbonate.
Preferably, the mass ratio of the positive electrode material to the ammonium sulfate is 1:1.25-1.5. The ratio of the two is too low, too much of the unreacted positive electrode material in the first stage roasting can reduce the extraction rate of lithium, and too high of the positive electrode material can convert cations in the positive electrode material into sulfate, so that the related reaction of the second stage roasting can not be performed. Due to (NH) 4 ) 2 SO 4 The decomposition temperature is lower, and the excess (NH 4) is increased with the temperature 2 SO 4 Will decompose and release SO x And (3) gas. The mass ratio of the positive electrode material to ammonium sulfate must not be excessively high.
Preferably, the temperature of the second stage roasting in S2 is 800-840 ℃ and the time is 100-120min.
Preferably, the temperature of the first stage roasting in S1 is 250-400 ℃ and the time is 90-150min.
Preferably, the positive electrode material in S1 is one or more of lithium cobaltate, lithium nickelate, lithium manganate, and nickel cobalt manganese ternary lithium ion battery.
Preferably, the positive electrode material in S1 is lithium cobaltate, and the first baked product contains lithium sulfate, cobalt sulfate and unreacted lithium cobaltate.
Preferably, the second calcined product in S2 contains lithium sulfate and tricobalt tetraoxide.
Preferably, the solid-to-liquid ratio in the water immersion process in S3 is 200 to 800 g.L -1 The water immersion temperature is 30-90deg.C, and the water immersion time is 10-90min.
Preferably, the precipitant in S4 is Na 2 CO 3 One or two of carbon dioxide.
Preferably, n (CO 3 2- )/n(Li + ) 1.2-1.5.
The invention uses (NH) in the process of roasting at the beginning 4 ) 2 SO 4 As a roasting agent, in the second roasting process, transition metal sulfate is used as the roasting agent to preferentially extract lithium from the waste positive electrode material, and meanwhile, the transition metal oxide is recovered. The specific reaction process of the invention is that firstly, ammonium sulfate is taken as roasting agent to carry out the first stage roasting, the use proportion of the positive electrode material and the ammonium sulfate is strictly controlled in the process, the purpose is to ensure that only part of the positive electrode material participates in the reaction in the first stage roasting process, the ammonium sulfate is completely consumed, and M in the second stage roasting process x (SO 4 ) y (M is cobalt, manganese and nickel) as a roasting agent to react with unreacted cathode materials to generate water-soluble lithium sulfate and water-insoluble M oxide; and directly separating M ions from lithium ions by subsequent water leaching, and then adding carbonate radicals to obtain the battery-grade lithium carbonate.
Compared with the prior art, the technical scheme has at least the following beneficial effects:
according to the scheme, impurity cations are not introduced in the whole roasting process, so that the energy requirement of subsequent evaporation and crystallization is reduced; high lithium selectivity and extraction rate, 98.75% LiCan be selectively extracted at room temperature of 30deg.C by water immersion, and then successfully prepare battery grade Li 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Stringent control (NH) 4 ) 2 SO 4 The amount of the catalyst can effectively reduce the release of polluted gas, and is a relatively environment-friendly and clean process.
Drawings
Fig. 1 is a reaction process diagram of a method for preferentially extracting lithium from a positive electrode of a waste lithium ion battery by a two-step roasting method according to an embodiment of the present invention.
FIG. 2 is a graph showing XRD analysis of the second calcined product of examples 1 and 2 and comparative examples 1 and 2 according to the embodiment of the present invention;
figure 3 is a graph of XRD analysis of the second calcined product of example 1 and comparative examples 3 and 4 in accordance with embodiments of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without creative efforts, based on the described embodiments of the present invention fall within the protection scope of the present invention.
Example 1
A method for preferentially extracting lithium from the positive electrode of a waste lithium ion battery by a two-step roasting method comprises the following steps:
s1, mixing lithium cobaltate and ammonium sulfate, and then roasting in a first stage at the temperature of 350 ℃ for 120min to partially convert the positive electrode material into sulfate to obtain a first roasting product, wherein the mass ratio of the positive electrode material to the ammonium sulfate is 1:1.25, wherein the first roasting product contains lithium sulfate, cobalt sulfate and unreacted lithium cobaltate;
during this step (NH) 4 ) 2 SO 4 Decomposition can occur at lower firing temperatures and the product NH 4 HSO 4 And (NH) 4 ) 2 SO 4 The method has higher thermodynamic spontaneous property in the air atmosphere, and the specific reaction process is as follows;
(NH 4 ) 2 SO 4 ＝NH 4 HSO 4 +NH 3 (g)
NH 4 HSO 4 ＝1/3NH 3 (g)+SO 2 (g)+2H 2 O(g)+1/3N 2 (g)
(NH 4 ) 2 SO 4 +O 2 (g)＝N 2 (g)+4H 2 O(g)+SO 2 (g)
NH 4 HSO 4 +1/4O 2 (g)＝1/2N 2 (g)+5/2H 2 O(g)+SO 2 (g)
at NH 4 HSO 4 And (NH) 4 ) 2 SO 4 Under the promotion effect of (2), the LiCoO is greatly improved 2 The thermodynamic driving force for the decomposition of the positive electrode material continues to raise the temperature, at which the Li and Co oxides and NH react 4 HSO 4 And (NH) 4 ) 2 SO 4 Is negative, indicating Li 2 O and Co 3 O 4 Can be spontaneously converted into CoSO in this step of calcination 4 Li (lithium ion battery) 2 SO 4 The specific reaction formula is as follows,
Li 2 O+NH 4 HSO 4 ＝Li 2 SO 4 +NH 3 (g)+H 2 O(g)
Co 3 O 4 +3NH 4 HSO 4 ＝3CoSO 4 +7/3NH 3 (g)+4H 2 O(g)+1/3N 2 (g)
Li 2 O+(NH 4 ) 2 SO 4 ＝Li 2 SO) 4 +2NH 3 (g)+H 2 O(g)
Co 3 O 4 +3(NH 4 ) 2 SO 4 ＝3CoSO 4 +16/3NH 3 (g)+4H 2 O(g)+1/3N 2 (g)
s2, raising the temperature to enable the first roasting product to be subjected to second-stage roasting, wherein the temperature of the second-stage roasting is 800 ℃ and the time is 110min, so that a second roasting product is obtained, and the second roasting product contains lithium sulfate and cobaltosic oxide; roasting atmosphere: nitrogen, argon, air.
The ammonium sulphate has been consumed by the time this step is entered, the temperature being raised to promote the following reaction,
LiCoO 2 (R)+1/2CoSO 4 ＝1/2Li 2 SO 4 +1/2Co 3 O 4
CoSO generated in the last stage 4 With the rest of LiCoO 2 (R-LCO) reaction to form Li 2 SO 4 While CoSO 4 Then it is converted into Co insoluble in water 3 O 4 。
S3, leaching the second roasting product, and filtering, wherein the solid-liquid ratio in the leaching process is 600 g.L -1 The temperature of water immersion is 60 ℃ and the time is 50min, and a lithium-containing solution and a slag phase are obtained;
s4, adding Na into the lithium-containing solution 2 CO 3 Carbon dioxide to obtain a precipitation reaction solution, wherein n (CO 3 2- )/n(Li + ) 1.3, and filtering to obtain lithium carbonate after precipitation is complete.
The extraction yield of lithium in this example was 98.89%, and the purity of the obtained lithium carbonate was 99.67%.
As shown in fig. 1, the reaction mechanism of the preparation method in this example is as follows: ammonium sulfate gradually decomposes and releases NH 3 SO and SO 2 And (3) gas. At NH 3 ，SO 2 Part of the positive electrode material LCO is decomposed into Li under the promotion effect 2 O and Co 3 O 4 And converted into sulfate Li 2 SO 4 ，CoSO 4 . The main roasting product of the first stage is Li 2 SO 4 ，CoSO 4 And R-LCO, in which case the sulfur element is SO 4 2- Is stored without discharging S0 2 . When the roasting temperature is increased to above 800 ℃, coSO 4 React with the residual LCO (R-LCO) to generate water-soluble Li 2 SO 4 Water insoluble Co 3 O 4 . Li is water-soluble Li 2 SO 4 Exists in the form of CoSO 4 Conversion to Co insoluble in Water 3 O 4 . The selective extraction of Li element is realized through the subsequent simple water leaching process. It is worth mentioning that CoSO at 800 deg.C 4 In a metastable state, thus not decomposing and releasing SO 2 And (3) gas. At the same time, the introduction of cations is avoided, the energy requirement of the subsequent evaporative crystallization is reduced, and the complex unit operation is realized.
The results obtained by replacing lithium cobaltate with lithium nickelate, lithium manganate, nickel cobalt manganese ternary lithium ion battery were similar to those in example 1.
Example 2
A method for preferentially extracting lithium from the positive electrode of a waste lithium ion battery by a two-step roasting method comprises the following steps:
s1, mixing a positive electrode material with ammonium sulfate, and then roasting in a first stage at the temperature of 250 ℃ for 90min to partially convert the positive electrode material into sulfate to obtain a first roasting product, wherein the mass ratio of the positive electrode material to the ammonium sulfate is 1:1.5;
s2, raising the temperature to enable the first roasting product to be subjected to second-stage roasting, wherein the temperature of the second-stage roasting is 810 ℃ and the time is 100min, and a second roasting product is obtained;
s3, soaking the second roasting product in water, and filtering, wherein the solid-liquid ratio in the soaking process is 200 g.L -1 The temperature of water immersion is 30 ℃ and the time is 10min, and a lithium-containing solution and a slag phase are obtained;
s4, adding Na into the lithium-containing solution 2 CO 3 Carbon dioxide to obtain a precipitation reaction solution, wherein n (CO 3 2- )/n(Li + ) 1.2, and after complete precipitation, lithium carbonate was obtained by filtration.
The extraction yield of lithium in this example was 99.12%, and the purity of the obtained lithium carbonate was 99.71%.
Example 3
A method for preferentially extracting lithium from the positive electrode of a waste lithium ion battery by a two-step roasting method comprises the following steps:
s1, mixing a positive electrode material with ammonium sulfate, and then roasting in a first stage at 400 ℃ for 150min to convert part of the positive electrode material into sulfate to obtain a first roasting product, wherein the mass ratio of the positive electrode material to the ammonium sulfate is 1:1.3;
s2, raising the temperature to enable the first roasting product to be roasted in a second stage, wherein the temperature of the second stage roasting is 840 ℃ and the time is 120min, so as to obtain a second roasting product;
s3, leaching the second roasting product, and filtering, wherein the solid-liquid ratio in the leaching process is 800 g.L -1 The temperature of water immersion is 90 ℃ and the time is 90min, and a lithium-containing solution and a slag phase are obtained;
s4, adding Na into the lithium-containing solution 2 CO 3 Obtaining a precipitation reaction liquid, wherein n (CO 3 2- )/n(Li + ) 1.5, and after complete precipitation, lithium carbonate was obtained by filtration.
The extraction yield of lithium in this example was 98.32%, and the purity of the obtained lithium carbonate was 99.73%.
Comparative example 1
This comparative example is similar to example 1, except that the mass ratio of the positive electrode material to ammonium sulfate in this comparative example is 1:1.
the extraction rate of Li in this comparative example was 87.46wt% (NH) 4 ) 2 SO 4 The amount of Li used is small, and Li in LCO is not enough to be completely extracted.
Comparative example 2
This comparative example is similar to example 1, except that the mass ratio of the positive electrode material to ammonium sulfate in this comparative example is 1:0.75.
the extraction yield of Li in this comparative example was smaller than that in comparative example 1.
XRD analysis was performed on the second calcined products of examples 1 and 2 and comparative examples 1 and 2, as shown in FIG. 2, it can be seen that when w (LCO)/w ((NH) 4 ) 2 SO 4 ) At 1:1, LCO diffraction peaks were present, indicating CoSO generated by calcination in the first stage 4 Is insufficient to completely convert the R-LCO to lithium sulfate. When w (LCO)/w ((NH) 4 ) 2 SO 4 ) At 1:0.75, a hybrid peak also occurred. In addition if excessive (NH) 4 ) 2 SO 4 ) Will result in a decrease in Li selectivity only when w (LCO)/w ((NH) 4 ) 2 SO 4 ) The second calcined product obtained when the value of (a) is within the scope of the present invention can only contain lithium sulfate and cobalt oxide, so that the purity of the finally obtained lithium carbonate can be ensured, cobalt can be recovered, and the purity of the recovered cobalt is high.
Comparative example 3
This comparative example is similar to example 1 except that the temperature in this comparative example is 850℃for the second stage firing.
Comparative example 4
This comparative example is similar to example 1 except that the temperature in this comparative example is 750℃for the second stage firing.
XRD analysis of the second calcined product of example 1 and comparative examples 3 and 4 showed, as shown in FIG. 3, that the roasting temperature was 750℃and the water-soluble CoSO content was varied 4 Li (lithium ion battery) 2 Co(SO 4 ) 2 Exists while still leaving a small amount of LCO, indicating that low firing temperatures do not enable CoSO 4 Complete reaction with the R-LCO, which reduces the Li leaching efficiency. Cobalt oxide appeared as the temperature continued to rise to 850 ℃.
The present invention is not limited to the above embodiments, but the scope of the invention is defined by the claims.
Claims (10)
1. The method for preferentially extracting lithium from the positive electrode of the waste lithium ion battery by a two-step roasting method is characterized by comprising the following steps of:
s1, mixing a positive electrode material with ammonium sulfate, and then roasting in a first stage to partially convert the positive electrode material into sulfate to obtain a first roasting product;
s2, raising the temperature to enable the first roasting product to be roasted in a second stage, so as to obtain a second roasting product;
s3, leaching the second roasting product, filtering, evaporating and crystallizing to obtain a lithium-rich solution and a slag phase;
and S4, adding a precipitant into the lithium-rich solution to obtain a precipitation reaction solution, and filtering to obtain lithium carbonate.
2. The method for preferentially extracting lithium from the positive electrode of the waste lithium ion battery according to claim 1, wherein the mass ratio of the positive electrode material to the ammonium sulfate is 1:1.25-1.5.
3. The method for preferentially extracting lithium from the positive electrode of the waste lithium ion battery as claimed in claim 1, wherein the second-stage roasting temperature in the step S2 is 800-840 ℃ for 100-120min.
4. The method for preferential extraction of lithium from the positive electrode of a spent lithium ion battery according to claim 1 or 3, wherein the first stage firing in S1 is performed at a temperature of 250 to 400 ℃ for a time of 90 to 150 minutes.
5. The method for preferentially extracting lithium from the positive electrode of the waste lithium ion battery according to claim 1, wherein the positive electrode material in S1 is one or more of lithium cobaltate, lithium nickelate, lithium manganate and nickel cobalt manganese ternary lithium ion battery.
6. The method for preferential extraction of lithium from a positive electrode of a spent lithium ion battery according to claim 5, wherein the positive electrode material in S1 is lithium cobaltate, and the first calcined product contains lithium sulfate, cobalt sulfate and unreacted lithium cobaltate.
7. The method for preferential extraction of lithium from a positive electrode of a spent lithium ion battery of claim 6 wherein said second calcined product in S2 comprises lithium sulfate and tricobalt tetraoxide.
8. The method for preferentially extracting lithium from the positive electrode of a waste lithium ion battery as claimed in claim 1, wherein the solid-to-liquid ratio in the water leaching process in the S3 is 200-800 g.L -1 The water immersion temperature is 30-90deg.C, and the water immersion time is 10-90min.
9. The method for preferential extraction of lithium from a positive electrode of a spent lithium ion battery according to claim 1, wherein the precipitant in S4 is Na 2 CO 3 One or two of carbon dioxide.
10. The method for preferential extraction of lithium from a positive electrode of a spent lithium ion battery according to claim 9, wherein n (CO 3 2- )/n(Li + ) 1.2-1.5.
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