CN118028833A - Lithium resource recovery method - Google Patents
Lithium resource recovery method Download PDFInfo
- Publication number
- CN118028833A CN118028833A CN202410015557.6A CN202410015557A CN118028833A CN 118028833 A CN118028833 A CN 118028833A CN 202410015557 A CN202410015557 A CN 202410015557A CN 118028833 A CN118028833 A CN 118028833A
- Authority
- CN
- China
- Prior art keywords
- lithium
- electrolyte
- anode
- current collector
- leaching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 179
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 238000000034 method Methods 0.000 title claims abstract description 84
- 238000011084 recovery Methods 0.000 title claims abstract description 27
- 239000003792 electrolyte Substances 0.000 claims abstract description 98
- 230000003647 oxidation Effects 0.000 claims abstract description 51
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 51
- 238000002386 leaching Methods 0.000 claims abstract description 46
- 238000011065 in-situ storage Methods 0.000 claims abstract description 20
- 230000005684 electric field Effects 0.000 claims abstract description 17
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 41
- 230000008569 process Effects 0.000 claims description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 27
- 239000010936 titanium Substances 0.000 claims description 27
- 229910052719 titanium Inorganic materials 0.000 claims description 27
- 239000012266 salt solution Substances 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910000831 Steel Inorganic materials 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 239000010959 steel Substances 0.000 claims description 9
- 150000003841 chloride salts Chemical class 0.000 claims description 7
- 150000003842 bromide salts Chemical class 0.000 claims description 5
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 5
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 5
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 5
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 5
- 230000007246 mechanism Effects 0.000 abstract description 22
- 239000013078 crystal Substances 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 150000002739 metals Chemical class 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 9
- 239000013535 sea water Substances 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 4
- 229910015645 LiMn Inorganic materials 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 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 4
- 239000013626 chemical specie Substances 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000006056 electrooxidation reaction Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 229910052642 spodumene Inorganic materials 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000013341 scale-up Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- -1 Mg2+ ions Chemical class 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 229910052629 lepidolite Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910002703 Al K Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910004403 Li(Ni0.6Co0.2Mn0.2)O2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017246 Ni0.8Co0.1Mn0.1 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides a method for recycling lithium resources, which comprises the steps of forming an electrolytic cell by an anode, a cathode and electrolyte solution, leaching lithium elements from the anode through electrode plate oxidation driven by an electric field and electrolyte in-situ oxidation driven by electrocatalytic activity, wherein the anode is prepared by utilizing the lithium resources. The recovery method can utilize various lithium resources to prepare the anode to form the electrolytic cell, and when the electrolytic cell works, the anode is coupled with an electrocatalytic driving electrolyte in-situ oxidation mechanism through an electrode plate oxidation mechanism driven by an electric field, so that a double oxidation mechanism is coupled with various lithium resources, and the high-selectivity leaching of lithium metal from crystal lattices of anode materials is promoted.
Description
Technical Field
The invention belongs to the technical field of lithium resource recycling, and particularly relates to a lithium resource recycling method.
Background
Lithium metal has an irreplaceable role in new materials, new energy sources, information technology, aerospace, national defense and military industry and other emerging industries. In recent years, with the rapid development of the new energy automobile industry, the application requirements of power batteries and energy storage batteries which depend on lithium metal supply are increased in an explosive manner, and meanwhile, the huge lithium metal resource market requirements are brought to the energy storage industry chain.
In the related art, the recycling technology of lithium metal is lagging behind. The acquisition path of lithium metal mainly depends on natural resource exploitation of lithium-rich ores or recovery of lithium metal from retired lithium ion batteries for reuse. Currently, the two methods for obtaining lithium resources are mainly focused on two aspects of pyrometallurgy and hydrometallurgy. The wet metallurgy process uses a large amount of strong acid as a leaching agent, and simultaneously uses hydrogen peroxide reagent with high-risk attribute as a reducing agent, so that all metals in various lithium resources such as a retired battery anode material, lithium ore and the like are leached in a non-selective way, a leaching solution obtained by mixing lithium and other metal elements is obtained, lithium metal cannot be recovered in a selective way, and various metals are separated by the subsequent process through technologies such as extraction, precipitation and the like, so that the process is complicated. The pyrometallurgical process usually processes various lithium resources such as retired battery anode materials, lithium ores and the like at a high temperature exceeding 800 ℃, and is often combined with the hydrometallurgical process after roasting to further leach lithium and other valuable metals in the powder, so that the problems of low selective lithium leaching, low lithium recovery rate, high energy consumption, high pollution and the like exist.
The prior art can not realize high-selectivity leaching and recovery of lithium from various lithium resources such as retired batteries, lithium ores and the like, and the process is often accompanied with the problems of high-risk chemical reagent use, high energy consumption, high pollution and the like. Therefore, a method with high lithium selectivity extraction rate, simple process, low energy consumption and low environmental risk needs to be developed to reduce the cost of lithium resource exploitation and recovery and relieve the contradiction between supply and demand of lithium resources.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention provides a recovery method of lithium resources, which can utilize various lithium resources to prepare anodes (working electrodes) to form an electrolytic cell, and when the electrolytic cell works, the anodes couple with an electrocatalytic driven electrolyte in-situ oxidation mechanism through an electrode plate oxidation mechanism driven by an electric field, so that a double oxidation mechanism is coupled to various lithium resources, and the high-selectivity leaching of lithium metal from crystal lattices of anode materials is promoted. After leaching, the obtained lithium-rich electrolyte can be used for obtaining products such as lithium carbonate and the like by a precipitation method, and the precipitated electrolyte can be recycled and reused for the operation of an electrolytic cell.
The first aspect of the invention provides a method for recovering lithium resources, comprising the steps of forming an electrolytic cell by an anode, a cathode and an electrolyte solution, leaching lithium elements from the anode through electric field driven electrode plate oxidation and electrocatalytically driven electrolyte in-situ oxidation, wherein the anode is prepared by utilizing the lithium resources.
The invention relates to a technical scheme in a lithium resource recovery method, which at least has the following beneficial effects:
the method for recycling lithium resources can utilize various lithium resources to prepare the anode (working electrode) to form the electrolytic cell, and when the electrolytic cell works, the anode couples with an electrocatalytic driving electrolyte in-situ oxidation mechanism through an electrode plate oxidation mechanism driven by an electric field, so that a double oxidation mechanism is coupled with various lithium resources, and the high-selectivity leaching of lithium metal from crystal lattices of anode materials is promoted. After leaching, the obtained lithium-rich electrolyte can be used for obtaining products such as lithium carbonate and the like by a precipitation method, and the precipitated electrolyte can be recycled and reused for the operation of an electrolytic cell.
The method for recovering lithium resources can utilize various lithium resources to prepare anodes (working electrodes), takes a titanium plate as a current collector as a cathode (counter electrode), takes various salt solutions as oxidizing electrolytes, and takes power generation of a photovoltaic solar cell panel and power storage of a storage battery as an energy supply system to form a closed-loop electrooxidation process. When the electrolytic cell works, the anode is coupled with an electrocatalytic driven electrolyte in-situ oxidation to generate an active species mechanism through an electric field driven electrode plate oxidation mechanism, so that a double oxidation mechanism is coupled to various lithium resources, and the high-selectivity leaching of lithium metal from crystal lattices of anode materials is promoted. After leaching, the obtained lithium-rich electrolyte can be used for obtaining products such as lithium carbonate and the like by a precipitation method, and the precipitated electrolyte can be recycled and reused for the operation of an electrolytic cell.
Electrocatalytically driven in situ oxidation of electrolytes produces an active species mechanism, where "active species" refers to chemical species that have oxidizing ability. Examples of the solution of NaCl are chlorine radicals, chlorine gas and other chemical species having oxidizing ability. Other iodine solutions and sulfate solutions may also have iodine radicals, sulfate radicals, and the like. For NaCl solutions, "active species" includes HClO, cl 2, clO.
According to the lithium resource recovery method, the constructed electrolytic cell is not limited by morphology and structure, and various configurations can be used for effectively leaching metal lithium.
According to the recovery method of lithium resources, the lithium extraction time is shorter (the reaction balance is started in the case of retired batteries in 40min, the recovery rate data of 90min is higher), the reaction kinetics is faster, and the production capacity of the assembled battery in unit time is stronger.
The lithium resource recovery method is environment-friendly in the whole process and low in carbon footprint. In the lithium leaching process, no toxic and harmful chemical reagent is used in the whole process, and only electric driven oxidation is used for selectively extracting lithium. In addition, the recycling method can also be used for supplying power by using a photovoltaic power generation system in the whole process, and can be used for making an advanced layout for future green intelligent recycling park construction.
The recovery method of lithium resources can extract lithium with high selectivity. The lithium extraction process does not damage the frame structure of the material, only extracts lithium in the crystal lattice of the material, has mild lithium extraction reaction, does not leach other transition metals such as Ni, co, mn and the like, and has the characteristic of high-selectivity lithium leaching. However, the processes of fire method, wet method and the like generally cannot selectively leach lithium metal, only all metals can be leached, and then various metals are recovered in sequence.
Since lithium leaches out of the crystal lattice of the material, there are ion channels. And nickel, cobalt and manganese are used as a framework of the material, so that intermolecular acting force is stronger. The uniqueness of lithium leaching is mainly the same as that of battery charging and discharging, the double oxidation of the invention takes electrode oxidation as a main part, and chemical oxidant as an auxiliary part, and compared with strong acid leaching, the generated active oxidant is milder, therefore, the invention is mainly aimed at lithium leaching, but not nickel, cobalt and manganese leaching.
According to the lithium resource recovery method, only the current collector is needed to conduct electricity for the cathode counter electrode, and other active materials are not needed to load.
According to some embodiments of the invention, the electrolyte solution is a salt solution capable of forming an active species having an oxidizing ability under anodic oxidation.
According to some embodiments of the invention, the salt solution comprises at least one of a chloride salt solution, a bromide salt solution, an iodide salt solution, and a sulfate salt solution.
According to some embodiments of the invention, the lithium resource comprises at least one of retired lithium ion battery positive electrode powder and lithium ore powder.
According to some embodiments of the invention, the method further comprises the step of applying a slurry comprising the lithium source to a current collector to obtain the anode.
According to some embodiments of the invention, the current collector comprises at least one of a titanium plate current collector, a carbon cloth current collector, a steel plate current collector, and an iron plate current collector.
According to some embodiments of the invention, the method further comprises a step of obtaining a lithium-containing electrolyte after leaching the lithium element, and adding a precipitant to the lithium-containing electrolyte to obtain a lithium-containing precipitate.
According to some embodiments of the invention, the lithium-containing precipitate includes lithium carbonate, lithium phosphate, and lithium oxalate.
According to some embodiments of the invention, the operating voltage of the electrolysis process is less than or equal to 36V.
According to some embodiments of the invention, the working time of the electrolysis process is less than or equal to 120 minutes.
The operating voltage and operating time of the electrolysis process refer to the voltage and time of the electrode plate oxidation driven by the electric field and the in-situ oxidation of the electrolyte driven by the electrocatalytic reaction.
According to some embodiments of the invention, the method comprises the steps of:
s1: coating a slurry containing the lithium resource on a current collector to obtain the anode;
S2: selecting a cathode, oxidizing electrolyte and an energy supply system, and constructing an electrolytic cell with the anode;
S3: the electrolytic cell is subjected to electrode plate oxidation driven by an electric field and electrolyte in-situ electrocatalytic oxidation under the power supply condition so as to drive lithium leaching, so that lithium-containing electrolyte is obtained;
S4: filtering impurities in the lithium-containing electrolyte to obtain a supernatant, and adding a precipitant into the supernatant to obtain lithium-containing precipitate.
According to some embodiments of the present invention, in step S1, the method for preparing a slurry containing the lithium resource includes the steps of: and (3) preprocessing the lithium resource to obtain lithium-containing powder, and mixing the lithium-containing powder with a binder and a solvent to obtain the slurry.
According to some embodiments of the invention, the pretreatment comprises drying, crushing, sieving the lithium source to obtain a lithium metal-containing powder.
According to some embodiments of the invention, the particle size of the lithium metal-containing powder is less than 1mm.
According to some embodiments of the invention, the binder comprises polyvinylidene fluoride (PVDF).
According to some embodiments of the invention, the solvent comprises N-methylpyrrolidone (NMP).
In the slurry, the mass ratio of the powder containing lithium metal, the binder and the solvent is 20:0-2:5-10.
According to some embodiments of the invention, the lithium resource comprises at least one of retired lithium ion battery positive electrode powder and lithium ore powder.
According to some embodiments of the invention, the retired lithium ion battery positive electrode powder comprises at least one of lithium iron phosphate battery (LiFePO 4) powder, lithium cobalt oxide battery (LiCoO 2) powder, lithium manganate battery (LiMn 2O4) powder, nickel cobalt manganese ternary lithium battery (Li (Ni xCoyMnz)O2) powder.
According to some embodiments of the invention, the lithium ore powder comprises at least one of spodumene, lepidolite.
According to some embodiments of the invention, the current collector comprises a mature industry that is available on a large scale.
According to some embodiments of the invention, the current collector comprises at least one of a titanium plate current collector, a carbon cloth current collector, a steel plate current collector, and an iron plate current collector.
The current collector may be any current collector formed of a conductive substance other than those listed above.
According to some embodiments of the invention, the anode current collector comprises at least one of a titanium plate current collector, a carbon cloth current collector, a steel plate current collector, and an iron plate current collector.
According to some embodiments of the invention, the cathode current collector comprises at least one of a titanium plate current collector, a carbon cloth current collector, a steel plate current collector, and an iron plate current collector.
In addition to the above materials, the current collector may be replaced with other corrosion resistant materials having good electrical conductivity.
According to some embodiments of the invention, in step S1, the slurry containing the lithium resource is coated on a current collector, and the anode is obtained after drying.
The drying temperature may be about 20 to 80 ℃.
According to some embodiments of the invention, the oxidizing electrolyte comprises at least one of a chloride salt electrolyte, a bromide salt electrolyte, an iodide salt electrolyte, and a sulfate salt electrolyte.
According to some embodiments of the invention, the chloride salt electrolyte comprises sodium chloride, natural seawater electrolyte.
When the electrolyte is a natural seawater electrolyte, KOH needs to be added to adjust the pH so as to precipitate calcium ions and magnesium ions.
According to some embodiments of the invention, the bromine salt electrolyte comprises a sodium bromide electrolyte.
According to some embodiments of the invention, the iodinated salt electrolyte comprises sodium iodide electrolyte.
According to some embodiments of the invention, the sulfate electrolyte comprises sodium sulfate electrolyte.
According to some embodiments of the invention, the energy supply system comprises a photovoltaic solar panel in combination with a battery.
According to some embodiments of the invention, the photovoltaic solar panel comprises at least one of a silicon-based solar cell, a perovskite solar cell, a thin film solar cell, and an organic solar cell.
According to some embodiments of the invention, the battery comprises at least one of a lithium ion battery and a sodium ion battery.
According to some embodiments of the invention, in step S2, anodes and cathodes may be alternately arranged in an electrolytic cell to form a multi-channel parallel electrolytic system for further use in scale-up.
According to some embodiments of the invention, in step S3, the operating voltage of the electrolysis process is less than or equal to 36V.
The above voltage is only a preferable voltage, and does not mean that the voltage must be limited to the above range.
According to some embodiments of the invention, in step S3, the working time of the electrolysis process is less than or equal to 120min.
The above-described time is only a preferable time, and does not mean that the time is necessarily limited to the above-described range.
And (3) under the condition of stable voltage power supply, the electrolytic cell performs an electro-oxidation mechanism to drive lithium leaching reaction, and after the reaction is completed, the electrolyte rich in lithium ions is obtained.
According to some embodiments of the invention, in step S3, the anode undergoes electrolytic in situ electrocatalytic oxidation simultaneously with the oxidation of the electric field driven anode electrode plate.
According to some embodiments of the invention, in step S3, the time of in situ electrocatalytic oxidation of the electrolyte is less than or equal to 120min.
The above-described time is only a preferable time, and does not mean that the time is necessarily limited to the above-described range.
According to some embodiments of the invention, in step S4, when the lithium-containing electrolyte uses seawater as the electrolyte, the pH of the electrolyte needs to be adjusted in order to remove Ca 2+、Mg2+ ions in the seawater.
According to some embodiments of the invention, in step S4, the precipitant comprises potassium carbonate, sodium carbonate, potassium phosphate, sodium phosphate, carbon dioxide, oxalic acid.
According to some embodiments of the invention, in step S4, the precipitating agent comprises an agent capable of forming a precipitate with lithium ions.
According to some embodiments of the invention, the lithium-containing precipitate includes lithium carbonate, lithium phosphate, and lithium oxalate.
According to some embodiments of the invention, in step S4, a step of drying the lithium-containing precipitate is further included.
According to some embodiments of the invention, the lithium-containing precipitate is dried, and the temperature may be around 100 ℃ and the time may be around 1 h.
Drawings
FIG. 1 is an XRD spectrum of Li 2CO3 product recovered during a multi-channel scale-up process.
Fig. 2 is an XRD spectrum of the recovered Li 3PO4 product.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these embodiments.
The first aspect of the invention provides a method for recovering lithium resources, comprising the steps of forming an electrolytic cell by an anode, a cathode and an electrolyte solution, leaching lithium elements from the anode through electrode plate oxidation driven by an electric field and electrolyte in-situ oxidation driven by electrocatalytic activity, wherein the anode is prepared by utilizing the lithium resources.
It can be appreciated that the method for recovering lithium resources of the present invention can utilize various lithium resources to prepare anodes (working electrodes) to form an electrolytic cell, and when the electrolytic cell works, the anodes couple with an electrocatalytic driven electrolyte in-situ oxidation mechanism through an electrode plate oxidation mechanism driven by an electric field, thereby coupling a double oxidation mechanism to various lithium resources and promoting the high-selectivity leaching of lithium metal from crystal lattices of anode materials. After leaching, the obtained lithium-rich electrolyte can be used for obtaining products such as lithium carbonate and the like by a precipitation method, and the precipitated electrolyte can be recycled and reused for the operation of an electrolytic cell.
The method for recovering lithium resources can utilize various lithium resources to prepare anodes (working electrodes), takes a titanium plate as a current collector as a cathode (counter electrode), takes various salt solutions as oxidizing electrolytes, and takes power generation of a photovoltaic solar cell panel and power storage of a storage battery as an energy supply system to form a closed-loop electrooxidation process. When the electrolytic cell works, the anode is coupled with an electrocatalytic driven electrolyte in-situ oxidation to generate an active species mechanism through an electric field driven electrode plate oxidation mechanism, so that a double oxidation mechanism is coupled to various lithium resources, and the high-selectivity leaching of lithium metal from crystal lattices of anode materials is promoted. After leaching, the obtained lithium-rich electrolyte can be used for obtaining products such as lithium carbonate and the like by a precipitation method, and the precipitated electrolyte can be recycled and reused for the operation of an electrolytic cell.
It should be noted that the electrocatalytically driven in situ oxidation of the electrolyte produces an active species mechanism, wherein "active species" refers to chemical species having oxidizing ability. Examples of the solution of NaCl are chlorine radicals, chlorine gas and other chemical species having oxidizing ability. Other iodine solutions and sulfate solutions may also have iodine radicals, sulfate radicals, and the like. For NaCl solutions, "active species" includes HClO, cl 2, clO.
According to the lithium resource recovery method, the constructed electrolytic cell is not limited by morphology and structure, and various configurations can be used for effectively leaching metal lithium.
According to the recovery method of lithium resources, the lithium extraction time is shorter (the reaction balance is started in the case of retired batteries in 40min, the recovery rate data of 90min is higher), the reaction kinetics is faster, and the production capacity of the assembled battery in unit time is stronger.
The lithium resource recovery method is environment-friendly in the whole process and low in carbon footprint. In the lithium leaching process, no toxic and harmful chemical reagent is used in the whole process, and only electric driven oxidation is used for selectively extracting lithium. In addition, the recycling method can also be used for supplying power by using a photovoltaic power generation system in the whole process, and can be used for making an advanced layout for future green intelligent recycling park construction.
The recovery method of lithium resources can extract lithium with high selectivity. The lithium extraction process does not damage the frame structure of the material, only extracts lithium in the crystal lattice of the material, has mild lithium extraction reaction, does not leach other transition metals such as Ni, co, mn and the like, and has the characteristic of high-selectivity lithium leaching. However, the processes of fire method, wet method and the like generally cannot selectively leach lithium metal, only all metals can be leached, and then various metals are recovered in sequence.
It should also be noted that since lithium leaches out of the crystal lattice of the material, there are ion channels. And nickel, cobalt and manganese are used as a framework of the material, so that intermolecular acting force is stronger. The uniqueness of lithium leaching is mainly the same as that of battery charging and discharging, the double oxidation of the invention takes electrode oxidation as a main part, and chemical oxidant as an auxiliary part, and compared with strong acid leaching, the generated active oxidant is milder, therefore, the invention is mainly aimed at lithium leaching, but not nickel, cobalt and manganese leaching.
According to the lithium resource recovery method, only the current collector is needed to conduct electricity for the cathode counter electrode, and other active materials are not needed to load.
In some embodiments of the invention, the electrolyte solution is a salt solution capable of forming an active species having oxidizing ability under anodic oxidation.
In some embodiments of the invention, the salt solution comprises at least one of a chloride salt solution, a bromide salt solution, an iodide salt solution, and a sulfate salt solution.
In some embodiments of the invention, the lithium resource comprises at least one of retired lithium ion battery positive electrode powder and lithium ore powder.
In some embodiments of the invention, the method further comprises the step of applying a slurry comprising lithium resources to the current collector to obtain an anode.
In some embodiments of the present invention, the current collector includes at least one of a titanium plate current collector, a carbon cloth current collector, a steel plate current collector, and an iron plate current collector.
In some embodiments of the present invention, the method further comprises a step of obtaining a lithium-containing electrolyte after leaching of the lithium element, and adding a precipitant to the lithium-containing electrolyte to obtain a lithium-containing precipitate.
In some embodiments of the invention, the lithium-containing precipitate includes lithium carbonate, lithium phosphate, and lithium oxalate.
In some embodiments of the invention, the operating voltage of the electrolysis process is less than or equal to 36V.
In some embodiments of the invention, the working time of the electrolysis process is less than or equal to 120 minutes.
In some embodiments of the present invention, the method specifically comprises the following steps:
s1: coating slurry containing lithium resources on a current collector to obtain an anode;
S2: selecting a cathode, oxidizing electrolyte and an energy supply system, and constructing an electrolytic cell with the anode;
S3: electrode plate oxidation driven by an electric field and electrolyte in-situ electrocatalytic oxidation are carried out on the electrolytic cell under the power supply condition so as to drive lithium leaching, so that lithium-containing electrolyte is obtained;
S4: filtering impurities in the lithium-containing electrolyte to obtain supernatant, and adding a precipitant into the supernatant to obtain lithium-containing precipitate.
In some embodiments of the present invention, in step S1, a method for preparing a slurry containing lithium resources includes the steps of: and (3) preprocessing the lithium resource to obtain lithium-containing powder, and mixing the lithium-containing powder with a binder and a solvent to obtain slurry.
In some embodiments of the invention, the pretreatment includes drying, crushing, and sieving the lithium source to obtain a powder containing lithium metal.
In some embodiments of the invention, the particle size of the lithium metal-containing powder is less than 1mm.
In some embodiments of the invention, the binder comprises polyvinylidene fluoride (PVDF).
In some embodiments of the invention, the solvent comprises N-methylpyrrolidone (NMP).
In the slurry, the mass ratio of the powder containing lithium metal, the binder and the solvent is 20:0-2:5-10.
In some embodiments of the invention, the lithium resource comprises at least one of retired lithium ion battery positive electrode powder and lithium ore powder.
In some embodiments of the invention, the retired lithium ion battery positive electrode powder comprises at least one of lithium iron phosphate battery (LiFePO 4) powder, lithium cobalt oxide battery (LiCoO 2) powder, lithium manganate battery (LiMn 2O4) powder, nickel cobalt manganese ternary lithium battery (Li (Ni xCoyMnz)O2) powder.
In some embodiments of the invention, the lithium ore powder comprises at least one of spodumene, lepidolite.
In some embodiments of the invention, the current collector comprises a mature industry that is available on a large scale.
In some embodiments of the present invention, the current collector includes at least one of a titanium plate current collector, a carbon cloth current collector, a steel plate current collector, and an iron plate current collector.
The current collector may be any current collector formed of a conductive substance other than those listed above.
In some embodiments of the present invention, the anode current collector includes at least one of a titanium plate current collector, a carbon cloth current collector, a steel plate current collector, and an iron plate current collector.
In some embodiments of the present invention, the cathode current collector includes at least one of a titanium plate current collector, a carbon cloth current collector, a steel plate current collector, and an iron plate current collector.
In addition to the above materials, the current collector may be replaced with other corrosion resistant materials having good electrical conductivity.
In some embodiments of the present invention, in step S1, a slurry containing lithium resources is coated on a current collector, and dried to obtain an anode.
The drying temperature may be about 20 to 80 ℃.
In some embodiments of the invention, the oxidizing electrolyte comprises at least one of a chloride salt electrolyte, a bromide salt electrolyte, an iodide salt electrolyte, and a sulfate salt electrolyte.
In some embodiments of the invention, the chloride salt electrolyte comprises sodium chloride, natural seawater electrolyte.
When the electrolyte is a natural seawater electrolyte, KOH needs to be added to adjust the pH so as to precipitate calcium ions and magnesium ions.
In some embodiments of the invention, the bromine salt electrolyte comprises a sodium bromide electrolyte.
In some embodiments of the invention, the iodinated salt electrolyte comprises a sodium iodide electrolyte.
In some embodiments of the invention, the sulfate electrolyte comprises sodium sulfate electrolyte.
In some embodiments of the invention, the energy supply system comprises a photovoltaic solar panel in combination with a battery.
In some embodiments of the invention, the photovoltaic solar panel comprises at least one of a silicon-based solar cell, a perovskite solar cell, a thin film solar cell, and an organic solar cell.
In some embodiments of the invention, the battery includes at least one of a lithium ion battery and a sodium ion battery.
In some embodiments of the present invention, in step S2, anodes and cathodes may be alternately arranged in an electrolytic cell to form a multi-channel parallel electrolytic system for further use in scale-up.
In some embodiments of the invention, in step S3, the voltage of the oxidation of the electrode plate driven by the electric field is less than or equal to 36V.
The above voltage is only a preferable voltage, and does not mean that the voltage must be limited to the above range.
In some embodiments of the present invention, in step S3, the time of oxidizing the electrode plate driven by the electric field is less than or equal to 120min.
The above-described time is only a preferable time, and does not mean that the time is necessarily limited to the above-described range.
And (3) under the condition of stable voltage power supply, the electrolytic cell performs an electro-oxidation mechanism to drive lithium leaching reaction, and after the reaction is completed, the electrolyte rich in lithium ions is obtained.
In some embodiments of the invention, in step S3, the anode undergoes electrolytic in situ electrocatalytic oxidation simultaneously with the oxidation of the electric field driven anode electrode plate.
In some embodiments of the invention, in step S3, the voltage of the in situ electrocatalytic oxidation of the electrolyte is less than or equal to 36V.
In some embodiments of the invention, in step S3, the time of in situ electrocatalytic oxidation of the electrolyte is less than or equal to 120 minutes.
The above-described time is only a preferable time, and does not mean that the time is necessarily limited to the above-described range.
In some embodiments of the present invention, in step S4, when the lithium-containing electrolyte uses seawater as the electrolyte, the pH of the electrolyte needs to be adjusted in order to remove Ca 2+、Mg2+ ions in the seawater.
In some embodiments of the invention, in step S4, the precipitant comprises potassium carbonate, sodium carbonate, potassium phosphate, sodium phosphate, carbon dioxide, oxalic acid.
In some embodiments of the invention, in step S4, the precipitation agent comprises an agent capable of forming a precipitate with lithium ions.
In some embodiments of the invention, the lithium-containing precipitate includes lithium carbonate, lithium phosphate, and lithium oxalate.
In some embodiments of the invention, in step S4, a step of drying the lithium-containing precipitate is further included.
In some embodiments of the invention, the lithium-containing precipitate is dried, and the temperature may be around 100 ℃ and the time may be around 1 hour.
The technical solution of the present invention will be better understood by combining the following specific embodiments.
All reagents in the examples were obtained from commercial sources.
The lithium source in the examples is various ex-service lithium battery positive electrode material powders, or mineral powders, which have been pretreated.
Example 1
Preparing an anode by using the anode powder of a retired lithium iron phosphate (LiFePO 4) battery, wherein the size of the anode is 5cm multiplied by 0.5mm, and connecting the anode with a power supply anode; using a titanium plate as a cathode, wherein the size of the titanium plate is 5cm multiplied by 0.5mm, and connecting the titanium plate with a power supply cathode; meanwhile, 8 pairs of electrode plates are connected in parallel, the distance between an anode and a cathode plate is controlled to be 2cm, 340mL of NaCl with the concentration of 0.5mol/L is used as electrolyte, and an electrolytic cell is formed. And reacting for 90 minutes at a stable voltage of 2.5V to obtain the lithium-rich electrolyte. K 2CO3 is added into the electrolyte to obtain Li 2CO3 sediment, and the Li 2CO3 product is obtained after filtration and drying. The Li 2CO3 product was characterized by X-ray powder diffraction and the results are shown in FIG. 1.
Table 1 leaching rates of metals in LiFePO 4 during multi-pass scale processing
TABLE 2 purity of Li 2CO3 recovered during multichannel Scale treatment
| Element(s) | Li | Fe | Al | K | Others |
| Content (%) | 99.602 | 0.127 | 0.048 | 0.020 | 0.203 |
The purity of the industrial grade lithium carbonate is more than or equal to 99.5 percent. In this example, the recovery rate was 99.6%, which is already satisfactory for industrial grade supply, and therefore the precipitation process was not further optimized. The precipitation process can be optimized according to actual needs to obtain the lithium carbonate with higher purity.
Example 2
Preparing an anode by using the anode powder of a retired lithium iron phosphate (LiFePO 4) battery, wherein the size of the anode is 5cm multiplied by 0.5mm, and connecting the anode with a power supply anode; using a titanium plate as a cathode, wherein the size of the titanium plate is 5cm multiplied by 0.5mm, and connecting the titanium plate with a power supply cathode; the distance between the anode and the cathode plate is controlled to be 2cm, and 180mL of Na 2SO4 with the concentration of 0.5mol/L is taken as electrolyte to form an electrolytic cell. And reacting for 90 minutes at a stable voltage of 3.0V to obtain the lithium-rich electrolyte. Na 3PO4 is added into the electrolyte to obtain Li 3PO4 sediment, and the Li 3PO4 product is obtained after filtration and drying. The Li 3PO4 product was characterized by X-ray powder diffraction and the results are shown in FIG. 2.
Table 3 leaching rate of metals in LiFePO 4
Example 3
Preparing anode with size of 5cm×5cm×0.5mm by using retired lithium cobalt oxide (LiCoO 2) battery anode powder, and connecting to power supply anode; using a titanium plate as a cathode, wherein the size of the titanium plate is 5cm multiplied by 0.5mm, and connecting the titanium plate with a power supply cathode; the distance between the anode and the cathode plate is controlled to be 2cm, 180mL of seawater is used as electrolyte, and the electrolytic cell is formed. And reacting for 90 minutes at a stable voltage of 2.5V to obtain the lithium-rich electrolyte. Subsequently, the pH of the electrolyte was adjusted to 13 with 1mol/L KOH, and calcium and magnesium impurities were precipitated to obtain a supernatant. Adding K 2CO3 into the supernatant to obtain Li 2CO3 precipitate, and filtering and drying to obtain Li 2CO3 product.
Table 4 leaching rates of metals from LiCoO 2
Example 4
Preparing an anode by using the anode powder of a retired lithium manganate (LiMn 2O4) battery, wherein the size of the anode is 5cm multiplied by 0.5mm, and connecting the anode with a power supply anode; using a titanium plate as a cathode, wherein the size of the titanium plate is 5cm multiplied by 0.5mm, and connecting the titanium plate with a power supply cathode; the distance between the anode and the cathode plate is controlled to be 2cm, 180mL of NaCl with the concentration of 0.5mol/L is used as electrolyte, and the electrolytic cell is formed. And reacting for 90 minutes at a stable voltage of 2.5V to obtain the lithium-rich electrolyte. K 2CO3 is added into the electrolyte to obtain Li 2CO3 sediment, and the Li 2CO3 product is obtained after filtration and drying.
Table 5 leaching rate of metals from LiMn 2O4
Example 5
Preparing anode by using retired nickel cobalt manganese ternary lithium battery (Li (Ni 0.6Co0.2Mn0.2)O2) battery anode powder, the size is 5cm multiplied by 0.5mm, connecting with power supply anode, using titanium plate as cathode, the size is 5cm multiplied by 0.5mm, connecting with power supply cathode, controlling the distance between anode and cathode plate to be 2cm, using 180mL NaCl with concentration of 0.5mol/L as electrolyte, forming electrolytic cell, reacting for 90 min under stable 2.5V voltage to obtain lithium-rich electrolyte, adding K 2CO3 into the electrolyte to obtain Li 2CO3 precipitate, filtering and drying to obtain Li 2CO3 product.
TABLE 6Li (leaching rate of metals from Ni 0.8Co0.1Mn0.1)O2)
Example 6
Preparing an anode by using spodumene powder, wherein the size of the anode is 5cm multiplied by 0.5mm, and connecting the anode with a power supply anode; using a titanium plate as a cathode, wherein the size of the titanium plate is 5cm multiplied by 0.5mm, and connecting the titanium plate with a power supply cathode; the distance between the anode and the cathode plate is controlled to be 2cm, 180mL of NaCl with the concentration of 0.5mol/L is used as electrolyte, and the electrolytic cell is formed. And reacting for 90 minutes at a stable voltage of 2.5V to obtain the lithium-rich electrolyte. K 2CO3 is added into the electrolyte to obtain Li 2CO3 sediment, and the Li 2CO3 product is obtained after filtration and drying.
TABLE 7 leaching of metals from spodumene
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. The method for recycling the lithium resource is characterized by comprising the steps of forming an electrolytic cell by an anode, a cathode and an electrolyte solution, leaching lithium element from the anode through electrode plate oxidation driven by an electric field and electrolyte in-situ oxidation driven by electrocatalytic activity, wherein the anode is prepared by utilizing the lithium resource.
2. The recovery method according to claim 1, wherein the electrolyte solution is a salt solution capable of forming an active species having an oxidizing ability under anodic oxidation.
3. The recovery method of claim 2, wherein the salt solution comprises at least one of a chloride salt solution, a bromide salt solution, an iodide salt solution, and a sulfate salt solution.
4. The recycling method according to claim 1, wherein the lithium resource comprises at least one of retired lithium ion battery positive electrode powder and lithium ore powder.
5. The method of claim 1, further comprising the step of applying a slurry containing the lithium resource to a current collector to obtain the anode.
6. The recycling method according to claim 5, wherein the current collector comprises at least one of a titanium plate current collector, a carbon cloth current collector, a steel plate current collector, and an iron plate current collector.
7. The method according to claim 1, further comprising a step of obtaining a lithium-containing electrolyte after leaching of the lithium element, and adding a precipitant to the lithium-containing electrolyte to obtain a lithium-containing precipitate.
8. The recovery method of claim 7, wherein the lithium-containing precipitate comprises lithium carbonate, lithium phosphate, and lithium oxalate.
9. The recovery method according to any one of claims 1 to 8, wherein the operating voltage of the electrolysis process is 36V or less.
10. The recovery method according to any one of claims 1 to 8, wherein the working time of the electrolysis process is 120min or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410015557.6A CN118028833A (en) | 2024-01-04 | 2024-01-04 | Lithium resource recovery method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410015557.6A CN118028833A (en) | 2024-01-04 | 2024-01-04 | Lithium resource recovery method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118028833A true CN118028833A (en) | 2024-05-14 |
Family
ID=91003171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410015557.6A Pending CN118028833A (en) | 2024-01-04 | 2024-01-04 | Lithium resource recovery method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118028833A (en) |
-
2024
- 2024-01-04 CN CN202410015557.6A patent/CN118028833A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mishra et al. | A review on recycling of lithium-ion batteries to recover critical metals | |
| CN111118294A (en) | Method for recycling valuable metals from waste lithium ion battery materials step by step | |
| WO2017215282A1 (en) | Method for recycling lithium in anode material of lithium battery by means of electrochemical process | |
| CN111270072B (en) | Recycling method of waste lithium iron phosphate battery positive electrode material | |
| CN106785174B (en) | Method for leaching and recovering metal from lithium ion battery anode waste based on electrochemical method | |
| CN111477985B (en) | Method for recycling waste lithium ion batteries | |
| Li et al. | Electrochemical methods contribute to the recycling and regeneration path of lithium-ion batteries | |
| WO2017215283A1 (en) | Method for recycling lithium in lithium iron phosphate by means of electrochemical process | |
| CN113802002A (en) | Method for recovering valuable metals in lithium battery by wet process | |
| CN113322376B (en) | Method for recovering valuable metals from waste lithium ion battery active materials | |
| Rácz et al. | Electrolytic recovery of Mn3O4 and Zn from sulphuric acid leach liquors of spent zinc–carbon–MnO2 battery powder | |
| CN112531159B (en) | Recycling method and application of waste lithium ion battery | |
| Rautela et al. | A review on technologies for recovery of metals from waste lithium-ion batteries | |
| CN111477986B (en) | Method for preparing ternary lithium ion battery precursor by electrolyzing sodium sulfate waste liquid | |
| Yasa et al. | Recycling valuable materials from the cathodes of spent lithium-ion batteries: A comprehensive review | |
| CN112645362A (en) | Method for preparing lithium carbonate by electrochemically extracting lithium from chloride type lithium-containing brine | |
| Zhao et al. | Recovery of lithium iron phosphate batteries through electrochemical oxidation in Na2CO3 solutions | |
| CN115149140B (en) | Method for recovering iron and lithium from waste lithium iron phosphate batteries | |
| Qin et al. | Electrochemical selective lithium extraction and regeneration of spent lithium iron phosphate | |
| CN115472948A (en) | Method for regenerating sodium-electricity positive electrode material by using waste lithium manganate | |
| CN118028833A (en) | Lithium resource recovery method | |
| CN114875240A (en) | Method for treating copper-cobalt alloy of waste lithium battery and application | |
| CN113904015A (en) | Regeneration method of waste lithium battery positive electrode material | |
| Zhou et al. | The Recycling Technologies for Spent Lithium Ion Battery | |
| CN110247129B (en) | Method for recycling positive active substances of waste lithium ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |