CN115432722B - Lithium circulating system and preparation method of positive electrode material precursor - Google Patents
Lithium circulating system and preparation method of positive electrode material precursor Download PDFInfo
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- CN115432722B CN115432722B CN202211051947.6A CN202211051947A CN115432722B CN 115432722 B CN115432722 B CN 115432722B CN 202211051947 A CN202211051947 A CN 202211051947A CN 115432722 B CN115432722 B CN 115432722B
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- 239000002243 precursor Substances 0.000 title claims abstract description 137
- 238000002360 preparation method Methods 0.000 title claims abstract description 108
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 73
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 46
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 288
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 115
- 150000003624 transition metals Chemical class 0.000 claims abstract description 103
- 238000001179 sorption measurement Methods 0.000 claims abstract description 58
- 239000007788 liquid Substances 0.000 claims abstract description 51
- 239000002699 waste material Substances 0.000 claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000003860 storage Methods 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 79
- 229910021529 ammonia Inorganic materials 0.000 claims description 38
- 238000004821 distillation Methods 0.000 claims description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 238000002425 crystallisation Methods 0.000 claims description 28
- 230000008025 crystallization Effects 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 238000000975 co-precipitation Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000008139 complexing agent Substances 0.000 claims description 14
- 229920000178 Acrylic resin Polymers 0.000 claims description 12
- 239000004925 Acrylic resin Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 230000000536 complexating effect Effects 0.000 claims description 8
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 7
- 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
- 239000002253 acid Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 150000005837 radical ions Chemical class 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 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
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 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
- 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
- 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
- 238000004090 dissolution Methods 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
- 238000004891 communication 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
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal 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
- 239000012065 filter cake Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910052642 spodumene Inorganic materials 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
- 239000000706 filtrate Substances 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 238000003837 high-temperature calcination 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
- 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
- -1 transition metal salt Chemical class 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
- 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
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 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
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 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
- 239000010406 cathode material Substances 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
- 238000009831 deintercalation Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical group [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
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
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
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 circulating system and a preparation method of a positive electrode material precursor. The lithium circulating system of the present invention includes: a precursor preparation unit, a transition metal removal unit and an adsorption unit; the outlet of the precursor preparation unit and/or the outlet of the lithium-containing waste liquid storage unit are/is communicated with the inlet of the transition metal removal unit, a first solution obtained by removing transition metal elements is communicated with the inlet of the adsorption unit through the first outlet of the transition metal removal unit, and after the first solution is adsorbed, the first solution is communicated with the inlet of the precursor preparation unit and/or the inlet of the transition metal removal unit through the outlet of the adsorption unit; the removing agent of the transition metal removing unit is lithium hydroxide. The system can extract high-purity lithium hydroxide from the production waste liquid of the positive electrode material precursor, 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 circulating system and a preparation method of a positive electrode material precursor, and belongs to the technical field of new energy.
Background
In recent years, batteries are evolving toward high energy density, long cycle life, and high safety performance. The positive electrode material is critical in determining the energy density of the battery.
In the prior art, sodium hydroxide is generally used as a precipitant, a ternary precursor is obtained by a coprecipitation method, and then the ternary precursor and a lithium source are subjected to high-temperature calcination 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 uniformly embed into the ternary precursor, so that the electrochemical performance of the finally obtained positive electrode material is influenced; in addition, as sodium hydroxide is used as a precipitant in the method, not only is the impurity removal process of Na + and the like comprehensively considered, the production cost is increased, but also Na + is easily introduced into the finally formed positive electrode material, and the electrochemical performance of the later positive electrode material is further reduced.
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, which increases the production cost of the positive electrode material precursor.
Disclosure of Invention
The invention provides a lithium circulating system, which can extract high-purity lithium hydroxide from lithium-containing waste liquid, and the extracted lithium hydroxide can return to a precursor preparation unit and/or a transition metal removal unit, thereby being beneficial to saving production cost.
The invention provides a preparation method of a positive electrode material precursor, which can recycle lithium hydroxide in lithium-containing waste liquid and is beneficial to saving production cost.
The present invention provides a lithium circulating system, which includes: a precursor preparation unit, a transition metal removal unit and an adsorption unit;
The outlet of the precursor preparation unit and/or the outlet of the lithium-containing waste liquid storage unit are/is communicated with the inlet of the transition metal removal unit, a first solution obtained by removing transition metal elements is communicated with the inlet of the adsorption unit through the first outlet of the transition metal removal unit, and after the first solution is adsorbed, the first solution is communicated with the inlet of the precursor preparation unit and/or the inlet of the transition metal removal unit through the outlet of the adsorption unit;
The removing agent of the transition metal removing unit is lithium hydroxide.
The system comprises a precursor preparation unit, a crystallization drying unit, a lithium hydroxide dissolution unit, 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 removing unit is communicated with the inlet of the adsorption unit through the ammonia distillation unit;
The first outlet of the transition metal removing unit is communicated with the inlet of the ammonia distilling unit, and the first outlet of the ammonia distilling unit is communicated with the inlet of the adsorption unit.
The system as described above, wherein the second outlet of the ammonia distillation 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 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.
The system as described above, wherein the adsorption unit comprises a styrenic resin and/or an acrylic resin.
The invention also provides a preparation method of the positive electrode material precursor, which is carried out by using the system, and comprises the following steps:
Carrying out coprecipitation reaction on precursor preparation raw materials of a mixed salt system comprising lithium hydroxide and at least nickel salt and cobalt salt 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, enters the transition metal removal unit through an inlet of the transition metal removal unit to be subjected to transition metal removal treatment, so as to obtain the first solution, and the removal agent of the transition metal removal unit is lithium hydroxide;
The first solution is output through a first outlet of the transition metal removing unit, enters the adsorption unit through an inlet of the adsorption unit, and undergoes an exchange reaction with the styrene resin and/or the acrylic resin to remove 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 number of the groups of groups,
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 comprises the steps that the precursor preparation raw material further comprises a complexing agent;
the complexing agent in the first solution is removed by exchange reaction with the styrene-based resin and/or acrylic resin.
The preparation method comprises the steps that the precursor preparation raw material further comprises a lithium precipitant;
the lithium precipitant is at least one selected from sodium carbonate, sodium bicarbonate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and phosphoric acid.
The preparation method as described above, wherein, in the transition metal removing unit, the pH is 11 to 12.
The invention provides a lithium circulating system, which uses lithium hydroxide as a removing agent, does not introduce other cations (Na +) into lithium-containing waste liquid, omits the subsequent step of removing other cations, saves the production cost, and can obtain lithium hydroxide which does not contain other cations and has high purity (the recovery rate of the lithium hydroxide is more than 99 percent, and Na + does not exist in the obtained lithium hydroxide) with high recovery rate; meanwhile, the system can also recycle the extracted lithium hydroxide, so that the extracted lithium hydroxide participates in the coprecipitation reaction, and the positive electrode material precursor with excellent electrochemical performance is obtained, and the system has excellent economic benefit.
The invention provides a preparation method of a positive electrode material precursor, 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 that are required to be used in the description of the embodiments of the present invention or the related technologies are briefly described below. It is evident that the drawings in the following description are only some embodiments of the present invention and that other drawings may be obtained from these drawings without inventive effort for a person of ordinary skill in the art.
Fig. 1 is a lithium cycle system in a first embodiment of the present invention;
fig. 2 is a lithium cycle system in a second embodiment of the present invention;
fig. 3 is a lithium circulating system in a third embodiment of the present invention;
Fig. 4 is a lithium circulating system in a fourth embodiment of the present invention.
Reference numerals illustrate:
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 following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Fig. 1 is a lithium circulating system in a first embodiment of the present invention. As shown in fig. 1, a first aspect of the present invention provides a lithium circulating system, including: a precursor preparation unit 1, a transition metal removal unit 3 and an adsorption unit 4;
The outlet of the precursor preparation unit 1 and/or the outlet of the lithium-containing waste liquid storage unit 2 are/is communicated with the inlet of the transition metal removal unit 3, the first solution obtained by removing the transition metal element is communicated with the inlet of the adsorption unit 4 through the first outlet of the transition metal removal unit 3, and after the first solution is adsorbed, the first solution is communicated with the inlet of the precursor preparation unit 1 and/or the inlet of the transition metal removal unit 3 through the outlet of the adsorption unit 4;
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. The present application is not particularly limited as long as the lithium ion-containing waste liquid falls within the scope of the present application, and in some embodiments, the lithium-containing waste liquid is a production waste liquid of a positive electrode material precursor.
It will be appreciated that the production waste 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 by 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 tetraacetate, ethylenediamine tetramethylene sodium phosphate (EDTMPS), diethylenetriamine pentamethylene phosphonate (DETPMPS), amine trimethophosphate, amino trimethophosphoric acid, 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 circulating system comprises the following steps: the lithium-containing waste liquid is output through an outlet of the precursor preparation unit 1 and/or an outlet of the lithium-containing waste liquid storage unit 2, enters the transition metal removal unit 3 through an inlet of the transition metal removal unit 3, the pH of the lithium-containing waste liquid is adjusted by the removal agent lithium hydroxide in the transition metal removal unit 3, 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 removal agent lithium hydroxide, lithium ions cannot be precipitated, the transition metal elements in the lithium-containing waste liquid are removed in the transition metal removal unit 3, and the lithium-containing waste liquid from which the transition metal elements are removed is called as a first solution;
The first solution is output through a first outlet of the metal removing unit 3, enters the adsorbing unit 4 through an inlet of the adsorbing unit 4, and anions (NO 3 2-、SO4 2- and the like) and/or complexing groups in the first solution are adsorbed in the adsorbing unit 4 to form a lithium hydroxide solution;
The lithium hydroxide solution can be output through the outlet of the adsorption unit 4, enters the precursor preparation unit 1 through the inlet of the precursor preparation unit 1, and is used for preparing the precursor; lithium hydroxide can also be output through the outlet of the adsorption unit 4, enters the transition metal removal unit 3 through the inlet of the transition metal removal unit 3, and is used as a removal agent of the transition metal removal unit 3 for removing transition metal elements in lithium-containing waste liquid.
The specific structure of the adsorption unit 4 is not particularly limited as long as the above-described functions can be achieved.
In the system, as the lithium hydroxide is used as the removing agent, other cations (Na +) are not introduced into the lithium-containing waste liquid, so that the subsequent step of removing other cations is omitted, the production cost is saved, and the lithium hydroxide which does not contain other cations and has high purity can be obtained; meanwhile, the system can also recycle the extracted lithium hydroxide, and has excellent economic benefit.
Fig. 2 is a lithium circulating system in a second embodiment of the present invention. As shown in fig. 2, in some embodiments of the present invention, a crystallization drying unit 5 and a lithium hydroxide dissolving unit 6 are further included, and an outlet of the adsorption unit 4 is communicated with an inlet of the precursor preparing 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 dissolving unit 6, and the outlet of the lithium hydroxide dissolving unit 6 is communicated with the inlet of the precursor preparation unit 1.
Specifically, the lithium hydroxide solution is output through the outlet of the adsorption unit 4, enters the crystallization drying unit 5 through the inlet of the crystallization drying unit 5, is evaporated and crystallized in the crystallization drying unit 5, and is dried to form lithium hydroxide, the lithium hydroxide is output through the outlet of the crystallization drying unit 5, enters the lithium hydroxide dissolving unit 6 through the inlet of the lithium hydroxide dissolving unit 6, lithium hydroxide can be dissolved into a lithium hydroxide solution with a target concentration in the lithium hydroxide dissolving unit 6, the lithium hydroxide solution with the target concentration is output through the outlet of the lithium hydroxide dissolving unit 6, enters the precursor preparation unit 1 through the 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 may be recovered and the recovered liquid may be reused.
In a specific embodiment, the temperature of the crystallization drying unit 5 is 80-100 ℃.
The specific structures of the crystallization drying unit 5 and the lithium hydroxide dissolving unit 6 are not particularly limited as long as the above functions can be achieved.
The invention is beneficial to adjusting the concentration of lithium hydroxide according to the requirement and improving the utilization efficiency of the lithium hydroxide by communicating the outlet of the adsorption unit 4 with the inlet of the precursor preparation unit 1 through the crystallization drying unit 5 and the lithium hydroxide dissolving unit 6.
Fig. 3 is a lithium circulating 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 distillation unit 7;
The first outlet of the transition metal removing unit 3 is communicated with the 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 will be appreciated that if the lithium-containing waste liquid includes a complexing group (including at least one of NH 3、NH3·H2O、H2O、NH4 + and OH -) formed by the complexing agent aqueous ammonia, the lithium circulation system of the present invention further includes 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 forms a first solution after the transition metal removing unit 3 removes transition metal elements;
The first solution is output through a first outlet of the metal removing unit 3, enters the ammonia distilling unit 7 through an inlet of the ammonia distilling unit 7, is subjected to ammonia distilling treatment, and removes 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 removes anions and/or complexing groups (complexing groups which are not removed by the ammonia distillation unit) through the adsorption unit 4 to form a lithium hydroxide solution.
In a specific operation, the residence time of the first solution in the ammonia distillation unit 7 is 0.5-1h.
The specific structure of the ammonia distillation unit 7 is not particularly limited in the present invention, as long as the functions of the ammonia distillation unit 7 described above can be achieved.
In some embodiments, ammonia distillation unit 7 comprises a deamination rectification column. 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, so that a second solution is formed.
Fig. 4 shows a lithium recycling system according to a third embodiment of the present invention, as shown in fig. 4, in which the second outlet of the ammonia distillation unit 7 is in communication with the inlet of the precursor preparation unit 1.
In the invention, the ammonia water processed by the ammonia distillation unit 7 can be output through the second outlet of the ammonia distillation unit 7, enter the precursor preparation unit 1 through the inlet of the precursor preparation unit 1, and serve as a complexing agent to participate in the preparation of the precursor. It will be appreciated that in a specific embodiment, the system further includes an ammonia water storage unit, and the ammonia water generated by the ammonia distillation unit 7 may be output through the second outlet of the ammonia distillation unit 7, enter the ammonia water storage unit, and then input the ammonia water of the ammonia water storage unit into the precursor preparation unit through the liquid phase inlet of the precursor preparation unit 1. In 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 also enables recycling of the treated product of the ammonia distillation unit 7, which is advantageous for saving costs.
As shown in fig. 4, in some embodiments of the present invention, the second outlet of the transition metal removal unit 3 is in communication 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 invention, the transition metal precipitate generated by the transition metal removing unit 3 can be output through the second outlet of the transition metal removing unit 3, enter the precursor preparing unit 1 through the inlet of the precursor preparing unit 1, and provide transition metal ions for the precursor preparing unit 1. It will be appreciated that in a specific embodiment, the precursor preparation unit 1 has a dissolution subunit, and the transition metal ions can be dissolved by the dissolution subunit to form a transition metal salt solution, and the concentration of the transition metal salt solution is controlled to control the content of the transition metal ions in the precursor preparation process.
In the invention, the transition metal precipitate generated by the transition metal removing unit 3 enters the precursor preparing unit 1, so that the reutilization of transition metal ions can be realized, and the production cost can be saved.
In some embodiments of the present invention, the resin of the adsorption unit 4 is a styrene-based resin and/or an acrylic-based resin.
Further, the resin may be at least one of a styrene-based resin a400, a macroporous strongly basic styrene-based resin a510, a strongly basic acrylic resin a870, a macroporous weakly basic styrene-based resin a100, a macroporous weakly basic styrene-based resin a105, and a macroporous weakly acidic acrylic resin a 830.
In a specific embodiment, the adsorption unit 4 comprises 2-4 ion exchange columns with a height of 4-6m, and the height of the resin in the ion exchange columns is 2-3m.
A second aspect of the present invention provides a method for preparing a positive electrode material precursor, wherein the method is performed by using the system, and the method comprises the following steps:
carrying out coprecipitation reaction on precursor preparation raw materials of a mixed salt system comprising lithium hydroxide and at least nickel salt and cobalt salt 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 from the outlet of the precursor preparation unit 1, enters the transition metal removal unit 3 through the inlet of the transition metal removal unit 3 to be subjected to transition metal removal treatment to obtain a first solution, and the removal agent of the transition metal removal unit 3 is lithium hydroxide;
the first solution is output through a first outlet of the metal removing unit 3, enters the adsorption unit through an inlet of the adsorption unit 4, and undergoes an exchange reaction with styrene resin and/or acrylic resin to remove acid radical ions in the solution, so as to obtain lithium hydroxide solution;
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 number of the groups of groups,
The lithium hydroxide solution is output through the outlet of the adsorption unit 4 and enters the transition metal removal unit 3 through the inlet of the transition metal removal unit 3.
The preparation method of the positive electrode material precursor specifically comprises the following steps: performing 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 positive electrode material precursor;
outputting lithium-containing waste liquid through an outlet of the precursor preparation unit 1, entering the transition metal removal unit 3 through an inlet of the transition metal removal unit 3 for transition metal removal treatment, and forming a first solution after removing transition metal elements from the lithium-containing waste liquid;
The first solution is output through a first outlet of the transition metal removing unit 3, enters the adsorbing unit 4 through an inlet of the adsorbing unit 4 for adsorption treatment, and acid radical ions (NO 3 2-、SO4 2- and the like) in the first solution are 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 positive electrode material; and/or the number of the groups of groups,
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 the transition metal element in the transition metal removal unit 3.
According to the preparation method of the precursor of the positive electrode material, the high-purity lithium hydroxide extracted from the lithium-containing waste liquid is utilized to prepare the positive electrode material, so that the production cost is 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 exchange reaction with the styrene resin and/or the acrylic resin.
Specifically, a precursor preparation raw material comprising lithium hydroxide, nickel salt, cobalt salt and a complexing agent is subjected to coprecipitation reaction in a precursor preparation unit to obtain a coprecipitation system containing lithium-containing waste liquid and a positive electrode material precursor;
The lithium-containing waste liquid is output from the outlet of the precursor preparation unit 1, enters the transition metal removal unit 3 through the 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 removal;
The first solution is output through a first outlet of the transition metal removing unit 3, enters the adsorbing unit 4 through an inlet of the adsorbing unit 4 for adsorption treatment, and acid radical ions (NO 3 2-、SO4 2- and the like) and complexing groups in the first solution are removed through exchange reaction with styrene resin and/or acrylic resin to form 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, thereby being beneficial to improving the performance of the positive electrode material precursor.
In some embodiments of the invention, the precursor preparation feedstock further comprises a lithium precipitant;
The lithium precipitant is at least one selected from sodium carbonate, sodium bicarbonate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and phosphoric acid.
In the invention, the precursor preparation raw material also comprises a lithium precipitant, so that the positive electrode material precursor rich in lithium elements can be obtained, the lithium intercalation and deintercalation performance of the positive electrode material can be improved, and the comprehensive performance of the battery can be improved.
The technical solutions of the present invention will be further described below with reference to specific examples, all parts, percentages, and ratios recited in the following examples are by weight, and all reagents used in the examples are commercially available or are synthesized according to conventional methods and can be used directly without further treatment, and the instruments used in the examples are commercially available.
Example 1
The preparation method of the positive electrode material precursor of the embodiment comprises the following steps:
1) Performing 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, aging the precipitation system, filtering to obtain a filter cake and filtrate, washing the filter cake to obtain a positive electrode material precursor and a 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 to cobalt element to manganese element is 8:1:1; the temperature of the coprecipitation reaction is 55 ℃, and the aging treatment time is 2 hours; 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 to be subjected to transition metal removal treatment, so as to obtain 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 removing agent of the transition metal removing unit is LiOH aqueous solution with the concentration of 5 mol/L; and the LiOH originates from a crystallization drying unit.
3) The first solution is output through a first outlet of the metal removing unit, enters the adsorption unit through an inlet of the adsorption unit and is subjected to adsorption treatment to obtain lithium hydroxide solution;
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 to be subjected to crystallization drying treatment to obtain 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 to be dissolved to obtain 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 is returned to the precursor preparation unit as condensed water to be used for washing filter cakes;
the temperature of the crystallization drying treatment was 90 ℃.
Example 2
The preparation method of the positive electrode material precursor of this example is basically the same as that of example 1, except that:
in step 1), EDTA is used to replace triethanolamine; and replacing the nickel-cobalt-manganese mixed nitrate solution with the nickel-cobalt-manganese mixed sulfate solution.
Example 3
The preparation method of the positive electrode material precursor of this example is basically the same as that of example 2, except that:
in step 1), EDTA was not included.
Example 4
The preparation method of the positive electrode material precursor of this example is basically the same as that of example 2, except that:
extraction was performed using the system of example 2, and in step 1), EDTA was replaced with ammonia;
Step 2) further comprises pretreatment, wherein ammonia distillation is carried out on the first solution by using an ammonia distillation unit;
The ammonia distillation unit comprises a deamination rectifying tower, and the ammonia distillation treatment time is 1h.
Comparative example 1
The preparation method of the positive electrode material precursor of this comparative example is substantially the same as in example 2, except that:
The method also comprises a spodumene ore calcination process, and specifically comprises the following steps: calcining spodumene ore, adding sulfuric acid for acidification, then calcining, adding water into a calcined product for leaching, then filtering to obtain a solid phase, adding sodium hydroxide for impurity removal of the solid phase, and then filtering to obtain a lithium sulfate solution;
Mixing the lithium sulfate solution with the lithium-containing waste liquid in the step 1) to obtain a mixed solution;
The removing agent 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 removing unit in the step 3), and entering the causticizing freezing unit through a liquid phase inlet of the causticizing freezing unit to separate sulfate ions and sodium ions so as to obtain lithium hydroxide solution.
Comparative example 2
The preparation method of the positive electrode material precursor of this comparative example is substantially the same as comparative example 1, except that:
The spodumene calcination process was not included.
Comparative example 3
The preparation method of the positive electrode material precursor of this comparative example is substantially the same as comparative example 2, except that:
in step 1), triethanolamine was used instead of EDTA.
Comparative example 4
The preparation method of the positive electrode material precursor of this comparative example is substantially the same as comparative example 2, except that:
in step 1), glycine is used instead of triethanolamine.
Comparative example 5
The preparation method of the positive electrode material precursor of this comparative example is substantially the same as comparative example 2, except that:
in step 1), polyacrylic acid is used instead of triethanolamine.
Comparative example 6
The preparation method of the positive electrode material precursor of this comparative example is substantially the same as comparative example 2, except that:
In step 1), citric acid is used instead of triethanolamine.
Comparative example 7
The preparation method of the positive electrode material precursor of this comparative example is substantially the same as comparative example 2, except that:
in step 1), the manganese sulfate solution is replaced with a lithium metaaluminate solution.
Comparative example 8
The preparation method of the positive electrode material precursor of this comparative example is substantially the same as comparative example 2, except that:
in step 1), EDTA was not included.
Performance testing
The content of Li + in the lithium-containing waste liquid in the examples and the comparative examples, the content of lithium hydroxide extracted in the examples and the comparative examples, respectively, were tested, and the recovery rate of Li + was calculated from the content of Li + in the lithium-containing waste liquid and the content of lithium hydroxide extracted, and the results are shown in table 1;
the purity of the extracted lithium hydroxide was measured, 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 positive electrode material precursor production waste liquid according to the embodiment of the invention has high yield of Li + and high purity of the recovered lithium hydroxide.
In this specification, each embodiment is described in a related manner, and identical and similar parts of each embodiment are all referred to each other, and each embodiment mainly describes differences from other embodiments. The foregoing is merely illustrative of the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.
Claims (6)
1. A lithium cycle system, comprising: a precursor preparation unit, a transition metal removal unit and an adsorption unit;
The outlet of the precursor preparation unit and/or the outlet of the lithium-containing waste liquid storage unit are/is communicated with the inlet of the transition metal removal unit, a first solution obtained by removing transition metal elements is communicated with the inlet of the adsorption unit through the first outlet of the transition metal removal unit, and after the first solution is adsorbed, the first solution is communicated with the inlet of the precursor preparation unit and/or the inlet of the transition metal removal unit through the outlet of the adsorption unit;
The removing agent of the transition metal removing unit is lithium hydroxide;
The lithium-containing waste liquid is a production waste liquid of a positive electrode material precursor, and at least comprises Li +, transition metal ions, anions and complexing groups;
the device also comprises a crystallization drying unit and a lithium hydroxide dissolving 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 dissolving 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 device also comprises an ammonia distillation unit;
the first outlet of the transition metal removing unit is communicated with the inlet of the adsorption unit through the ammonia distillation unit;
the first outlet of the transition metal removing unit is communicated with the inlet of the ammonia distillation unit, and the first outlet of the ammonia distillation unit is communicated with the inlet of the adsorption unit;
The second outlet of the ammonia distillation unit is communicated with the inlet of the precursor preparation unit;
The second outlet of the transition metal removing unit is communicated with the inlet of the precursor preparing unit, and the transition metal removed by the transition metal removing unit is output through the second outlet of the transition metal removing unit and enters the precursor preparing unit through the inlet of the precursor preparing unit;
The adsorption unit comprises a styrene resin and/or an acrylic resin.
2. A method for preparing a precursor of a positive electrode material, characterized by using the system of claim 1, comprising the steps of:
Carrying out coprecipitation reaction on precursor preparation raw materials of a mixed salt system comprising lithium hydroxide and at least nickel salt and cobalt salt 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, enters the transition metal removal unit through an inlet of the transition metal removal unit to be subjected to transition metal removal treatment, so as to obtain the first solution, and the removal agent of the transition metal removal unit is lithium hydroxide;
The first solution is output through a first outlet of the transition metal removing unit, enters the adsorption unit through an inlet of the adsorption unit, and undergoes an exchange reaction with styrene resin and/or acrylic resin to remove acid radical ions in the solution, so as to obtain a lithium hydroxide solution;
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 number of the groups of groups,
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 precursor preparation raw material also comprises a complexing agent.
3. The method according to claim 2, wherein the complexing agent in the first solution is removed by an exchange reaction with the styrene-based resin and/or the acrylic resin.
4. A method of preparing according to claim 2 or 3, wherein the precursor preparation raw material further comprises a lithium precipitant;
the lithium precipitant is at least one selected from sodium carbonate, sodium bicarbonate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate and phosphoric acid.
5. A production method according to claim 2 or 3, characterized in that in the transition metal removal unit, the pH is 11-12.
6. The process according to claim 4, wherein the pH in the transition metal removing unit is 11 to 12.
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