CN115432722A - Lithium circulation system and preparation method of positive electrode material precursor - Google Patents
Lithium circulation system and preparation method of positive electrode material precursor Download PDFInfo
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- CN115432722A CN115432722A CN202211051947.6A CN202211051947A CN115432722A CN 115432722 A CN115432722 A CN 115432722A CN 202211051947 A CN202211051947 A CN 202211051947A CN 115432722 A CN115432722 A CN 115432722A
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- 239000002243 precursor Substances 0.000 title claims abstract description 135
- 238000002360 preparation method Methods 0.000 title claims abstract description 114
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 74
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 31
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 291
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 118
- 150000003624 transition metals Chemical class 0.000 claims abstract description 105
- 238000001179 sorption measurement Methods 0.000 claims abstract description 66
- 239000007788 liquid Substances 0.000 claims abstract description 52
- 239000002699 waste material Substances 0.000 claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 238000003860 storage Methods 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 76
- 229910021529 ammonia Inorganic materials 0.000 claims description 38
- 238000004821 distillation Methods 0.000 claims description 28
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 238000000975 co-precipitation Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000008139 complexing agent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 229920000178 Acrylic resin Polymers 0.000 claims description 13
- 239000004925 Acrylic resin Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 150000005837 radical ions Chemical class 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 229920001890 Novodur Polymers 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 230000001351 cycling effect Effects 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 69
- 230000000052 comparative effect Effects 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 239000010406 cathode material Substances 0.000 description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 7
- 230000000536 complexating effect Effects 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910001428 transition metal ion Inorganic materials 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 230000009615 deamination Effects 0.000 description 4
- 238000006481 deamination reaction Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052642 spodumene Inorganic materials 0.000 description 3
- -1 transition metal salt Chemical class 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009993 causticizing Methods 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
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 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 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- FDGBQHCDMSYZRC-UHFFFAOYSA-N 2-hydroxy-2-oxo-1,3,2$l^{5}-dioxaphosphinan-4-amine Chemical compound NC1CCOP(O)(=O)O1 FDGBQHCDMSYZRC-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- MQNVHUZWFZKETG-UHFFFAOYSA-N P1(OCCCCCO1)=O.NCCNCCN Chemical compound P1(OCCCCCO1)=O.NCCNCCN MQNVHUZWFZKETG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- XOJITQHBMRQMRX-UHFFFAOYSA-M sodium;ethane-1,2-diamine;2-oxido-1,3,2$l^{5}-dioxaphosphepane 2-oxide Chemical compound [Na+].NCCN.[O-]P1(=O)OCCCCO1 XOJITQHBMRQMRX-UHFFFAOYSA-M 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
Images
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
- C01D15/02—Oxides; Hydroxides
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a lithium circulation system and a preparation method of a precursor of a positive electrode material. The lithium cycle system of the present invention includes: the device comprises a precursor preparation unit, a transition metal removal unit and an adsorption unit; an outlet of the precursor preparation unit and/or an outlet of the lithium-containing waste liquid storage unit are/is communicated with an inlet of the transition metal removal unit, a first solution obtained by removing transition metal elements is communicated with an inlet of the adsorption unit through a first outlet of the transition metal removal unit, and after adsorption, the first solution is communicated with an inlet of the precursor preparation unit and/or an inlet of the transition metal removal unit through an outlet of the adsorption unit; the remover of the transition metal removing unit is lithium hydroxide. The system can extract high-purity lithium hydroxide from the production waste liquid of the precursor of the anode material, and the extracted lithium hydroxide can return to the precursor preparation unit and/or the transition metal removal unit, thereby being beneficial to saving the production cost.
Description
Technical Field
The invention relates to a lithium circulation system and a preparation method of a precursor of a positive electrode material, belonging to the technical field of new energy.
Background
In recent years, batteries are being developed toward high energy density, long cycle life, and high safety performance. The positive electrode material is the key to determine the energy density of the battery.
In the prior art, sodium hydroxide is usually used as a precipitant, a ternary precursor is obtained by a coprecipitation method, and then the ternary precursor and a lithium source are calcined at a high temperature to synthesize the cathode material. However, in the high-temperature calcination process of the ternary precursor obtained by the method, a lithium source is difficult to be uniformly embedded into the ternary precursor, so that the electrochemical performance of the finally obtained cathode material is influenced; and because the method uses sodium hydroxide as a precipitating agent, not only does the comprehensive consideration of Na need to be considered + The impurity removal process increases the production cost, and Na + Is easy to be introduced into the finally formed cathode material, thereby reducing the electrochemical performance of the cathode material in the later period.
In order to solve the above problems, a method of preparing a positive electrode precursor using lithium hydroxide as a precipitant has been developed, but lithium hydroxide is expensive and increases the production cost of a positive electrode material precursor.
Disclosure of Invention
The invention provides a lithium circulation system, which can extract high-purity lithium hydroxide from lithium-containing waste liquid, and the extracted lithium hydroxide can be returned to a precursor preparation unit and/or a transition metal removal unit, thereby being beneficial to saving the production cost.
The invention provides a preparation method of a precursor of a positive electrode material, which can recycle lithium hydroxide in lithium-containing waste liquid and is beneficial to saving production cost.
The invention provides a lithium cycle system, which comprises: the device comprises a precursor preparation unit, a transition metal removal unit and an adsorption unit;
an outlet of the precursor preparation unit and/or an outlet of the lithium-containing waste liquid storage unit are/is communicated with an inlet of the transition metal removal unit, a first solution obtained by removing transition metal elements is communicated with an inlet of the adsorption unit through a first outlet of the transition metal removal unit, and the first solution is communicated with an inlet of the precursor preparation unit and/or an inlet of the transition metal removal unit through an outlet of the adsorption unit after being adsorbed;
the remover of the transition metal removing unit is lithium hydroxide.
The system as described above, further comprising a crystallization drying unit and a lithium hydroxide dissolution unit, wherein the outlet of the adsorption unit is communicated with the inlet of the precursor preparation unit through the crystallization drying unit and the lithium hydroxide dissolution unit;
the outlet of the adsorption unit is communicated with the inlet of the crystallization drying unit, the outlet of the crystallization drying unit is communicated with the inlet of the lithium hydroxide dissolving unit, and the outlet of the lithium hydroxide dissolving unit is communicated with the inlet of the precursor preparation unit.
The system as described above, further comprising an ammonia distillation unit;
the first outlet of the transition metal removal unit is communicated with the inlet of the adsorption unit through the ammonia distillation unit;
and a first outlet of the transition metal removal unit is communicated with an inlet of the ammonia distillation unit, and a first outlet of the ammonia distillation unit is communicated with an inlet of the adsorption unit.
The system as described above, wherein the second outlet of the ammonia still unit is in communication with the inlet of the precursor preparation unit.
The system as described above, wherein the second outlet of the transition metal removal unit is communicated with the inlet of the precursor preparation unit, and the transition metal removed by the transition metal removal unit is output through the second outlet of the transition metal removal unit and enters the precursor preparation unit through the inlet of the precursor preparation unit.
The system of above, wherein the adsorption unit comprises a styrenic resin and/or an acrylic resin.
The invention also provides a preparation method of the precursor of the cathode material, wherein the preparation method is carried out by using the system, and comprises the following steps:
carrying out coprecipitation reaction on a precursor preparation raw material of a mixed salt system at least comprising nickel salt and cobalt salt and lithium hydroxide in a precursor preparation unit to obtain a coprecipitation system, wherein the coprecipitation system comprises lithium-containing waste liquid and a positive electrode material precursor;
the lithium-containing waste liquid is output through an outlet of the precursor preparation unit and enters the transition metal removal unit through an inlet of the transition metal removal unit to be subjected to transition metal removal treatment, so that the first solution is obtained, and a removal agent of the transition metal removal unit is lithium hydroxide;
the first solution is output through a first outlet of the transition metal removal unit and enters an adsorption unit through an inlet of the adsorption unit, and acid radical ions in the solution and the styrene resin and/or acrylic resin are subjected to exchange reaction to remove the acid radical ions in the solution, so that a lithium hydroxide solution is obtained;
the lithium hydroxide solution is output through an outlet of the adsorption unit and enters the precursor preparation unit through an inlet of the precursor preparation unit; and/or the presence of a gas in the gas,
and the lithium hydroxide solution is output through an outlet of the adsorption unit and enters the transition metal removal unit through an inlet of the transition metal removal unit.
The preparation method as described above, wherein the precursor preparation raw material further includes a complexing agent;
the complexing agent in the first solution is removed by an exchange reaction with the styrene resin and/or the acrylic resin.
The production method as described above, wherein the precursor preparation raw material further includes a lithium precipitant;
the lithium precipitating agent is at least one selected from sodium carbonate, sodium bicarbonate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and phosphoric acid.
The production method as described above, wherein, in the transition metal removal unit, the pH is 11 to 12.
The invention provides a lithium circulating system, which uses lithium hydroxide as a remover and does not introduce other cations (Na) into lithium-containing waste liquid + ) Not only the subsequent step of removing other cations is omitted, the production cost is saved, but also the high-purity lithium hydroxide without other cations can be obtained with high recovery rate (the recovery rate of the lithium hydroxide is more than 99 percent, and Na does not exist in the obtained lithium hydroxide + ) (ii) a Meanwhile, the system can also recycle the extracted lithium hydroxide, so that the extracted lithium hydroxide participates in the coprecipitation reaction to obtain the precursor of the cathode material with excellent electrochemical performance, and the system has excellent economic benefit.
The invention provides a preparation method of a precursor of a positive electrode material, which can recycle lithium hydroxide in lithium-containing waste liquid and is beneficial to saving production cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the related art, the drawings used in the description of the embodiments of the present invention or the related art are briefly introduced below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a lithium cycle system in a first embodiment of the invention;
FIG. 2 is a lithium cycle system in a second embodiment of the present invention;
fig. 3 is a lithium cycle system in a third embodiment of the present invention;
fig. 4 shows a lithium cycle system according to a fourth embodiment of the present invention.
Description of reference numerals:
1: a precursor preparation unit;
2: a lithium-containing waste liquid storage unit;
3: a transition metal removal unit;
4: an adsorption unit;
5: a crystallization drying unit;
6: a lithium hydroxide dissolution unit;
7: and an ammonia distillation unit.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 shows a lithium cycle system according to a first embodiment of the present invention. As shown in fig. 1, a first aspect of the present invention provides a lithium cycle system, comprising: a precursor preparation unit 1, a transition metal removal unit 3 and an adsorption unit 4;
an outlet of the precursor preparation unit 1 and/or an outlet of the lithium-containing waste liquid storage unit 2 is/are communicated with an inlet of the transition metal removal unit 3, a first solution obtained by removing transition metal elements is communicated with an inlet of the adsorption unit 4 through a first outlet of the transition metal removal unit 3, and the first solution is communicated with an inlet of the precursor preparation unit 1 and/or an inlet of the transition metal removal unit 3 through an outlet of the adsorption unit 4 after being adsorbed;
the removing agent of the transition metal removing unit 3 is lithium hydroxide.
The lithium circulating system is used for extracting lithium hydroxide from the lithium-containing waste liquid and recycling the extracted lithium hydroxide. In the present invention, the lithium-containing waste liquid is not particularly limited, as long as the waste liquid containing lithium ions falls within the scope of protection of the present application, and in some embodiments, the lithium-containing waste liquid is a production waste liquid of a precursor of a positive electrode material.
It is understood that the production waste liquid of the positive electrode material precursor includes at least: li + Transition metal ions, and anions. In some embodiments, the production waste of the positive electrode material precursor further includes a complexing group.
The complexing group is not particularly limited, and is formed after coprecipitation reaction of a complexing agent, lithium hydroxide and a transition metal salt. In some embodiments of the present invention, the complexing agent may be selected from at least one of ammonia, ammonium sulfate, ammonium nitrate, ammonium acetate, ammonium chloride, glycine, diethanolamine, triethanolamine, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, sodium ethylenediamine tetramethylene phosphate (EDTMPS), diethylenetriamine pentamethylene phosphonate (DETPMPS), amine trimetaphosphate, aminotrimethylene phosphate, polyacrylic acid, sodium pyrophosphate, tartaric acid, citric acid, ammonium citrate, sodium citrate, oxalic acid, sodium oxalate, acetic acid, maleic acid, succinic acid, malonic acid, and crown ether.
The specific operation mode of the lithium cycle system of the present invention includes: leading the lithium-containing waste liquid to be output through an outlet of the precursor preparation unit 1 and/or an outlet of the lithium-containing waste liquid storage unit 2, leading the lithium-containing waste liquid to enter the transition metal removal unit 3 through an inlet of the transition metal removal unit 3, wherein in the transition metal removal unit 3, the pH of the lithium-containing waste liquid can be adjusted by lithium hydroxide serving as a removal agent, the pH of the lithium-containing waste liquid is 11-12, transition metal elements (nickel, cobalt, manganese and the like) in the lithium-containing waste liquid form transition metal precipitates under the action of the lithium hydroxide serving as the removal agent, lithium ions cannot be precipitated, in the transition metal removal unit 3, the transition metal elements in the lithium-containing waste liquid are removed, and the lithium-containing waste liquid without the transition metal elements is called as a first solution;
the first solution is output through a first outlet of the transition metal removing unit 3, enters the adsorption unit 4 through an inlet of the adsorption unit 4, and anions (NO) in the first solution in the adsorption unit 4 3 2- 、SO 4 2- Etc.) and/or the complexing group will be adsorbed, forming a lithium hydroxide solution;
the lithium hydroxide solution can be output through an outlet of the adsorption unit 4 and enter the precursor preparation unit 1 through an inlet of the precursor preparation unit 1 to be used for preparing a precursor; the lithium hydroxide can also be output through the outlet of the adsorption unit 4, and enter the transition metal removal unit 3 through the inlet of the transition metal removal unit 3 to be used as a removal agent of the transition metal removal unit 3 for removing transition metal elements in the lithium-containing waste liquid.
The present invention is not particularly limited as long as the adsorption unit 4 can achieve the above-described functions.
The system of the invention does not introduce other cations (Na) into the lithium-containing waste liquid because lithium hydroxide is used as a remover + ) The subsequent step of removing other cations is omitted, the production cost is saved, and high-purity lithium hydroxide without other cations can be obtained; meanwhile, the system can also recycle the extracted lithium hydroxide, and has excellent economic benefit.
Fig. 2 is a lithium cycle system according to a second embodiment of the present invention. As shown in fig. 2, in some embodiments of the present invention, further comprising a crystallization drying unit 5 and a lithium hydroxide dissolving unit 6, an outlet of the adsorption unit 4 is communicated with an inlet of the precursor preparation unit 1 through the crystallization drying unit 5 and the lithium hydroxide dissolving unit 6;
the outlet of the adsorption unit 4 is communicated with the inlet of the crystallization drying unit 5, the outlet of the crystallization drying unit 5 is communicated with the inlet of the lithium hydroxide dissolution unit 6, and the outlet of the lithium hydroxide dissolution unit 6 is communicated with the inlet of the precursor preparation unit 1.
Specifically, the lithium hydroxide solution is output through an outlet of the adsorption unit 4, enters the crystallization drying unit 5 through an inlet of the crystallization drying unit 5, the lithium hydroxide solution is evaporated, crystallized and dried in the crystallization drying unit 5 to form lithium hydroxide, the lithium hydroxide is output through an outlet of the crystallization drying unit 5, enters the lithium hydroxide dissolving unit 6 through an inlet of the lithium hydroxide dissolving unit 6, the lithium hydroxide with the target concentration can be dissolved in the lithium hydroxide dissolving unit 6, and the lithium hydroxide solution with the target concentration is output through an outlet of the lithium hydroxide dissolving unit 6, enters the precursor preparation unit 1 through an inlet of the precursor preparation unit 1, and participates in the preparation of the precursor. In some embodiments, the evaporated liquid in the lithium hydroxide solution can be recovered, and the recovered liquid can be reused.
In a particular embodiment, the temperature of the crystallization drying unit 5 is 80 to 100 ℃.
The specific structures of the crystallization drying unit 5 and the lithium hydroxide dissolving unit 6 in the present invention are not particularly limited as long as the above functions can be achieved.
The outlet of the adsorption unit 4 is communicated with the inlet of the precursor preparation unit 1 through the crystallization drying unit 5 and the lithium hydroxide dissolution unit 6, so that the concentration of lithium hydroxide can be adjusted as required, and the utilization efficiency of lithium hydroxide can be improved.
Fig. 3 is a lithium cycle system in a third embodiment of the present invention. As shown in fig. 3, in some embodiments of the invention, the system further comprises an ammonia still unit 7;
a first outlet of the transition metal removal unit 3 is communicated with a liquid phase inlet of the adsorption unit 4 through an ammonia distillation unit 7;
the first outlet of the transition metal removal unit 3 is communicated with the inlet of the ammonia distillation unit 7, and the first outlet of the ammonia distillation unit 7 is communicated with the inlet of the adsorption unit 4.
It can be understood that if the lithium-containing waste liquid contains a complexing group (including NH) formed by the complexing agent ammonia water 3 、NH 3 ·H 2 O、H 2 O、NH 4 + And OH - At least one of (1), the lithium cycle system of the present invention further comprises an ammonia distillation unit 7.
In a specific operation process, the lithium-containing waste liquid enters the transition metal removing unit 3 through an inlet of the transition metal removing unit 3, and a first solution is formed after transition metal elements are removed through the transition metal removing unit 3;
the first solution is output through a first outlet of the transition metal removal unit 3, enters an ammonia distillation unit 7 through an inlet of the ammonia distillation unit 7, and is subjected to ammonia distillation treatment to remove ammonia components in the first solution to form a second solution;
the second solution is output through a first outlet of the ammonia distillation unit 7, enters the adsorption unit 4 through an inlet of the adsorption unit 4, and is subjected to anion removal and/or complexing group removal (the complexing group which is not removed completely by the ammonia distillation unit) through the adsorption unit 4 to form a lithium hydroxide solution.
In a specific operation process, the residence time of the first solution in the ammonia distillation unit 7 is 0.5-1h.
The present invention is not particularly limited to the specific structure of the ammonia distillation unit 7 as long as the function of the ammonia distillation unit 7 described above can be achieved.
In some embodiments, ammonia distillation unit 7 comprises a deamination rectifier. Specifically, the first solution enters a deamination rectifying tower, and ammonium ions in the first solution are treated by the deamination rectifying tower to form ammonia water so as to be removed to form a second solution.
Fig. 4 shows a lithium cycle system according to a third embodiment of the present invention, as shown in fig. 4, in some embodiments of the present invention, the second outlet of the ammonia still unit 7 is in communication with the inlet of the precursor preparation unit 1.
In the invention, the ammonia water formed by the treatment of the ammonia distillation unit 7 can be output through the second outlet of the ammonia distillation unit 7, and enters the precursor preparation unit 1 through the inlet of the precursor preparation unit 1 to be used as a complexing agent to participate in the preparation of the precursor. It can be understood that, in a specific embodiment, the system further includes an ammonia water storage unit, and the ammonia water generated by the ammonia evaporation unit 7 can be output through the second outlet of the ammonia evaporation unit 7 and enter the ammonia water storage unit, and then the ammonia water in the ammonia water storage unit is input into the precursor preparation unit through the liquid phase inlet of the precursor preparation unit 1. According to the invention, the concentration of the ammonia water can be regulated and controlled in the ammonia water storage unit, so that the content of the complexing agent in the precursor preparation process is controlled.
The system of the invention can also reuse the treatment product of the ammonia distillation unit 7, which is beneficial to saving cost.
As shown in fig. 4, in some embodiments of the present invention, the second outlet of the transition metal removal unit 3 is communicated with the inlet of the precursor preparation unit 1, and the transition metal removed by the transition metal removal unit 3 is output through the second outlet of the transition metal removal unit 3 and enters the precursor preparation unit 1 through the inlet of the precursor preparation unit 1.
In the present invention, the transition metal precipitate generated by the transition metal removal unit 3 may be output through the second outlet of the transition metal removal unit 3, and enter the precursor preparation unit 1 through the inlet of the precursor preparation unit 1, so as to provide transition metal ions for the precursor preparation unit 1. It is understood that, in a specific embodiment, the precursor preparation unit 1 has a dissolving subunit, and the transition metal ions can be dissolved by the dissolving subunit to form a transition metal salt solution, and the transition metal ion content in the precursor preparation process is controlled by regulating the concentration of the transition metal salt solution.
In the invention, the transition metal precipitate generated by the transition metal removing unit 3 enters the precursor preparation unit 1, so that the recycling of transition metal ions can be realized, and the production cost can be saved.
In some embodiments of the invention, the resin of the adsorption unit 4 is a styrenic resin and/or an acrylic resin.
Further, the resin may be at least one of a styrene resin a400, a macroporous strong base styrene resin a510, a strong base acrylic resin a870, a macroporous weak base styrene resin a100, a macroporous weak base styrene resin a105, and a macroporous weak acid acrylic resin a 830.
In a specific embodiment, the adsorption unit 4 comprises 2 to 4 ion exchange columns having a height of 4 to 6m, and the height of the resin in the ion exchange columns is 2 to 3m.
A second aspect of the present invention provides a method of preparing a precursor of a positive electrode material, wherein the method is performed using the system described above, and comprises the following steps:
carrying out coprecipitation reaction on a precursor preparation raw material of a mixed salt system at least comprising nickel salt and cobalt salt and lithium hydroxide in a precursor preparation unit 1 to obtain a coprecipitation system, wherein the coprecipitation system comprises lithium-containing waste liquid and a positive electrode material precursor;
the lithium-containing waste liquid is output through an outlet of the precursor preparation unit 1, enters the transition metal removal unit 3 through an inlet of the transition metal removal unit 3, and is subjected to transition metal removal treatment to obtain a first solution, and a removal agent of the transition metal removal unit 3 is lithium hydroxide;
the first solution is output through a first outlet of the transition metal removal unit 3, enters the adsorption unit through an inlet of the adsorption unit 4, and is subjected to exchange reaction with styrene resin and/or acrylic resin to remove acid ions in the solution, so that a lithium hydroxide solution is obtained;
the lithium hydroxide solution is output through an outlet of the adsorption unit 4 and enters the precursor preparation unit 1 through an inlet of the precursor preparation unit 1; and/or the presence of a gas in the atmosphere,
the lithium hydroxide solution is output through an outlet of the adsorption unit 4 and enters the transition metal removal unit 3 through an inlet of the transition metal removal unit 3.
The preparation method of the precursor of the cathode material specifically comprises the following steps: carrying out coprecipitation reaction on precursor preparation raw materials at least comprising lithium hydroxide, nickel salt and cobalt salt in a precursor preparation unit 1 to obtain a coprecipitation system containing lithium-containing waste liquid and a precursor of a positive electrode material;
outputting the lithium-containing waste liquid through an outlet of the precursor preparation unit 1, and entering the transition metal removal unit 3 through an inlet of the transition metal removal unit 3 for transition metal removal treatment, wherein the lithium-containing waste liquid forms a first solution after removing transition metal elements;
the first solution is output through a first outlet of the transition metal removing unit 3, enters the adsorption unit 4 through an inlet of the adsorption unit 4 for adsorption treatment, and acid radical ions (NO) in the first solution 3 2- 、SO 4 2- Etc.) will be removed by exchange reaction with styrene resin and/or acrylic resin to form lithium hydroxide solution;
the lithium hydroxide solution is output through an outlet of the adsorption unit 4, enters the precursor preparation unit 1 through an inlet of the precursor preparation unit 1, and participates in the preparation of the precursor of the anode material; and/or the presence of a gas in the gas,
the lithium hydroxide solution is output through an outlet of the adsorption unit 4, enters the transition metal removal unit 3 through an inlet of the transition metal removal unit 3, and is used as a removal agent for removing transition metal elements in the transition metal removal unit 3.
According to the preparation method of the precursor of the cathode material, disclosed by the invention, the cathode material is prepared by utilizing the high-purity lithium hydroxide extracted from the lithium-containing waste liquid, so that the production cost is favorably saved.
In some embodiments of the invention, the precursor preparation feedstock further comprises a complexing agent;
the complexing agent in the first solution is removed by an exchange reaction with the styrenic resin and/or the acrylic resin.
Specifically, a precursor preparation raw material comprising lithium hydroxide, a nickel salt, a cobalt salt and a complexing agent is subjected to a coprecipitation reaction in a precursor preparation unit to obtain a coprecipitation system comprising a lithium-containing waste liquid and a positive electrode material precursor;
the lithium-containing waste liquid is output through an outlet of the precursor preparation unit 1, enters the transition metal removal unit 3 through an inlet of the transition metal removal unit 3 for transition metal removal treatment, and forms a first solution after the lithium-containing waste liquid is subjected to transition metal element removal;
the first solution is output through a first outlet of the transition metal removing unit 3, enters the adsorption unit 4 through an inlet of the adsorption unit 4 for adsorption treatment, and acid radical ions (NO) in the first solution 3 2- 、SO 4 2- Etc.) and the complexing groups are removed by exchange reaction with the styrene resin and/or acrylic resin to form a lithium hydroxide solution.
In the invention, the precursor preparation raw material also comprises a complexing agent, and the complexing agent can promote the coprecipitation reaction and is beneficial to improving the performance of the precursor of the anode material.
In some embodiments of the invention, the precursor preparation feedstock further comprises a lithium precipitating agent;
the lithium precipitating agent is at least one selected from sodium carbonate, sodium bicarbonate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and phosphoric acid.
According to the invention, the precursor preparation raw material also comprises a lithium precipitator, so that the lithium-rich anode material precursor can be obtained, the lithium removal and insertion performance of the anode material can be improved, and the comprehensive performance of the battery can be further improved.
The invention is further illustrated by the following specific examples in which all parts, percentages, and ratios recited in the following examples are by weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and used as such without further treatment, and the equipment used in the examples is commercially available.
Example 1
The preparation method of the precursor of the cathode material of the embodiment includes the following steps:
1) Carrying out coprecipitation reaction on 5mol/L LiOH solution, 1.5mol/L nickel-cobalt-manganese mixed nitrate solution and 4.5g/L triethanolamine solution to obtain a precipitation system, carrying out aging treatment on the precipitation system, then filtering to obtain a filter cake and filtrate, washing the filter cake to obtain a positive electrode material precursor and washing liquid, and collecting the filtrate and the washing liquid to form lithium-containing waste liquid;
wherein, in the nickel-cobalt-manganese mixed nitrate solution, the molar ratio of nickel element, cobalt element and manganese element is 8; the temperature of the coprecipitation reaction is 55 ℃, and the time of the aging treatment is 2h; the washing treatment time is 30min, and the temperature is 50 ℃;
2) The lithium-containing waste liquid is output through an outlet of the precursor preparation unit, enters the transition metal removal unit through an inlet of the transition metal removal unit, is subjected to transition metal removal treatment, and obtains a first solution and a transition metal precipitate, and the transition metal precipitate is output through a second outlet of the transition metal removal unit, enters the precursor preparation unit through an inlet of the precursor preparation unit, and provides transition metal ions for the precursor preparation unit;
wherein the remover of the transition metal removing unit is 5mol/L LiOH aqueous solution; and the LiOH originates from a crystallization drying unit.
3) The first solution is output through a first outlet of the transition metal removal unit and enters the adsorption unit through an inlet of the adsorption unit for adsorption treatment, so that a lithium hydroxide solution is obtained;
wherein, the adsorption unit comprises 3 ion exchange columns with the height of 6m, the height of resin in the ion exchange columns is 3m, and the resin is A400.
4) The lithium hydroxide solution is output through an outlet of the adsorption unit, enters the crystallization drying unit through an inlet of the crystallization drying unit, is subjected to crystallization drying treatment to obtain lithium hydroxide, the lithium hydroxide is output through an outlet of the crystallization drying unit, enters the lithium hydroxide dissolving unit through an inlet of the lithium hydroxide dissolving unit, is dissolved to obtain a lithium hydroxide solution with the concentration of 5mol/L, the lithium hydroxide solution with the concentration of 5mol/L is output through an outlet of the lithium hydroxide dissolving unit, enters the precursor preparation unit through an inlet of the precursor preparation unit, and liquid evaporated by the crystallization drying unit returns to the precursor preparation unit as condensed water for washing filter cakes;
the temperature of the crystallization drying treatment was 90 ℃.
Example 2
The preparation method of the precursor of the positive electrode material of the present example is substantially the same as that of example 1, except that:
in the step 1), EDTA is used for replacing triethanolamine; the nickel-cobalt-manganese mixed nitrate solution is replaced by the nickel-cobalt-manganese mixed sulfate solution.
Example 3
The preparation method of the precursor of the positive electrode material of the present example is substantially the same as that of example 2, except that:
in step 1), EDTA was not contained.
Example 4
The preparation method of the precursor of the positive electrode material of the present example is substantially the same as that of example 2, except that:
extraction was performed using the system of example 2, in step 1) EDTA was replaced with ammonia;
step 2) also comprises pretreatment, namely performing ammonia distillation treatment on the first solution by using an ammonia distillation unit;
the ammonia distillation unit comprises a deamination rectifying tower, and the ammonia distillation time is 1h.
Comparative example 1
The preparation method of the positive electrode material precursor of this comparative example was substantially the same as that of example 2 except that:
also includes a spodumene ore calcination process, which specifically comprises: calcining spodumene ore, adding sulfuric acid for acidification, then calcining, adding water into a calcined product for leaching, filtering to obtain a solid phase, adding sodium hydroxide for removing impurities from the solid phase, and filtering to obtain a lithium sulfate solution;
mixing a lithium sulfate solution with the lithium-containing waste liquid obtained in the step 1) to obtain a mixed solution;
the remover of the transition metal removing unit in the step 2) is 5mol/L sodium hydroxide aqueous solution;
and 3) outputting the first solution through a liquid phase outlet of the transition metal removal unit in the step 3), and entering a causticizing freezing unit through a liquid phase inlet of the causticizing freezing unit to separate sulfate ions and sodium ions to obtain a lithium hydroxide solution.
Comparative example 2
The preparation method of the precursor of the positive electrode material of the present comparative example is substantially the same as that of comparative example 1 except that:
a spodumene calcination process is not included.
Comparative example 3
The preparation method of the precursor of the positive electrode material of the present comparative example is substantially the same as that of comparative example 2 except that:
in step 1), triethanolamine is used to replace EDTA.
Comparative example 4
The preparation method of the precursor of the positive electrode material of the present comparative example is substantially the same as that of comparative example 2 except that:
in step 1), glycine is used to replace triethanolamine.
Comparative example 5
The preparation method of the precursor of the positive electrode material of the present comparative example is substantially the same as that of comparative example 2 except that:
in step 1), polyacrylic acid is used to replace triethanolamine.
Comparative example 6
The preparation method of the precursor of the positive electrode material of the present comparative example is substantially the same as that of comparative example 2 except that:
in step 1), citric acid is used to replace triethanolamine.
Comparative example 7
The preparation method of the positive electrode material precursor of this comparative example was substantially the same as that of comparative example 2, except that:
in the step 1), lithium metaaluminate solution is used to replace manganese sulfate solution.
Comparative example 8
The preparation method of the precursor of the positive electrode material of the present comparative example is substantially the same as that of comparative example 2 except that:
in step 1), EDTA was not contained.
Performance testing
Li in the lithium-containing waste liquid in the examples and comparative examples was tested separately + Content of (b), content of lithium hydroxide extracted in the example and comparative example, respectively, was measured according to Li in lithium-containing waste liquid + And the content of extracted lithium hydroxide to calculate Li + The results are shown in Table 1;
the purity of the extracted lithium hydroxide was checked and the test results are shown in table 1.
TABLE 1
As can be seen from table 1, the method for extracting lithium hydroxide from the production waste liquid of the precursor of the positive electrode material, li, according to the example of the present invention + The yield of (A) is high, and the purity of the lithium hydroxide obtained by recovery is high.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments. The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A lithium cycling system, comprising: the device comprises a precursor preparation unit, a transition metal removal unit and an adsorption unit;
an outlet of the precursor preparation unit and/or an outlet of the lithium-containing waste liquid storage unit are/is communicated with an inlet of the transition metal removal unit, a first solution obtained by removing transition metal elements is communicated with an inlet of the adsorption unit through a first outlet of the transition metal removal unit, and the first solution is communicated with an inlet of the precursor preparation unit and/or an inlet of the transition metal removal unit through an outlet of the adsorption unit after being adsorbed;
the remover of the transition metal removing unit is lithium hydroxide.
2. The system of claim 1, further comprising a crystallization drying unit and a lithium hydroxide dissolution unit, wherein an outlet of the adsorption unit is in communication with an inlet of the precursor preparation unit through the crystallization drying unit and the lithium hydroxide dissolution unit;
the outlet of the adsorption unit is communicated with the inlet of the crystallization drying unit, the outlet of the crystallization drying unit is communicated with the inlet of the lithium hydroxide dissolving unit, and the outlet of the lithium hydroxide dissolving unit is communicated with the inlet of the precursor preparation unit.
3. The system of claim 1 or 2, further comprising an ammonia still unit;
the first outlet of the transition metal removal unit is communicated with the inlet of the adsorption unit through the ammonia distillation unit;
and a first outlet of the transition metal removal unit is communicated with an inlet of the ammonia distillation unit, and a first outlet of the ammonia distillation unit is communicated with an inlet of the adsorption unit.
4. The system of claim 3, wherein the second outlet of the ammonia still unit is in communication with an inlet of the precursor preparation unit.
5. The system according to any one of claims 1 to 4, wherein the second outlet of the transition metal removal unit is in communication with the inlet of the precursor preparation unit, and the transition metal removed by the transition metal removal unit is output through the second outlet of the transition metal removal unit and enters the precursor preparation unit through the inlet of the precursor preparation unit.
6. The system of any one of claims 1-5, wherein the adsorption unit comprises a styrenic resin and/or an acrylic resin.
7. A method for preparing a precursor of a positive electrode material, characterized by using the system of any one of claims 1 to 6, comprising the steps of:
carrying out coprecipitation reaction on a precursor preparation raw material of a mixed salt system at least comprising nickel salt and cobalt salt and lithium hydroxide in a precursor preparation unit to obtain a coprecipitation system, wherein the coprecipitation system comprises lithium-containing waste liquid and a positive electrode material precursor;
the lithium-containing waste liquid is output through an outlet of the precursor preparation unit and enters the transition metal removal unit through an inlet of the transition metal removal unit to be subjected to transition metal removal treatment, so that the first solution is obtained, and a removal agent of the transition metal removal unit is lithium hydroxide;
the first solution is output through a first outlet of the transition metal removal unit and enters the adsorption unit through an inlet of the adsorption unit, and acid radical ions in the solution and styrene resin and/or acrylic resin are subjected to exchange reaction to remove the acid radical ions in the solution, so that a lithium hydroxide solution is obtained;
the lithium hydroxide solution is output through an outlet of the adsorption unit and enters the precursor preparation unit through an inlet of the precursor preparation unit; and/or the presence of a gas in the atmosphere,
and the lithium hydroxide solution is output through an outlet of the adsorption unit and enters the transition metal removal unit through an inlet of the transition metal removal unit.
8. The production method according to claim 7, wherein the precursor preparation raw material further comprises a complexing agent;
the complexing agent in the first solution is removed by an exchange reaction with the styrene resin and/or the acrylic resin.
9. The production method according to claim 7 or 8, characterized in that the precursor preparation raw material further comprises a lithium precipitant;
the lithium precipitating agent is at least one selected from sodium carbonate, sodium bicarbonate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and phosphoric acid.
10. The production method according to any one of claims 7 to 9, characterized in that, in the transition metal removal unit, the pH is 11 to 12.
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