CN114293029A - Method for selectively extracting lithium from waste lithium ion batteries - Google Patents
Method for selectively extracting lithium from waste lithium ion batteries Download PDFInfo
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- CN114293029A CN114293029A CN202111658312.8A CN202111658312A CN114293029A CN 114293029 A CN114293029 A CN 114293029A CN 202111658312 A CN202111658312 A CN 202111658312A CN 114293029 A CN114293029 A CN 114293029A
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- 238000000034 method Methods 0.000 title claims abstract description 71
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 58
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims abstract description 29
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000002386 leaching Methods 0.000 claims abstract description 22
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims abstract description 18
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 17
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000011541 reaction mixture Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 23
- 239000013543 active substance Substances 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 208000028659 discharge Diseases 0.000 claims description 6
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 5
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000007790 scraping Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 6
- 150000004706 metal oxides Chemical class 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 5
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000010405 anode material Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000009854 hydrometallurgy Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- -1 manganese metals Chemical class 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention belongs to the technical field of waste lithium ion battery recovery, and provides a method for selectively extracting lithium from waste lithium ion batteries, which comprises the following steps: mixing a positive active material of a lithium ion battery and oxalic acid dihydrate according to a molar ratio of 1: 1-8, and heating for a solid-solid reaction to obtain a reaction mixture; treating the reaction mixture by a water leaching method to obtain a lithium oxalate solution; and adding water-soluble carbonate into the lithium oxalate solution to obtain lithium carbonate precipitate. The oxalic acid and the metal oxide on the anode have solid-solid reaction, so that the pollution of environment caused by using strong acid and a reducing agent is avoided, the one-step leaching and the selective lithium extraction are realized by adopting a water leaching mode, the leaching efficiency is high, and the operability of the method is greatly improved. After the transition metal completely reacts with oxalic acid dihydrate, impurities such as a binder, a carbon additive and the like contained in the positive electrode are removed in a filtering mode, and the separation of all components is realized.
Description
Technical Field
The invention belongs to the technical field of waste lithium ion battery recovery, and particularly relates to a method for selectively extracting lithium from waste lithium ion batteries.
Background
In the last two decades, a wide variety of portable electronic devices have entered into the aspects of people's lives, and a large number of rechargeable batteries have been produced and used. Among the rechargeable batteries, lithium ion batteries are widely used due to their excellent properties such as high operating voltage, high energy density, no memory effect, light weight, small volume, low self-discharge rate, long cycle life, wide operating temperature range, etc. In addition, lithium ion batteries do not contain harmful heavy metals, such as lead and cadmium, and are therefore more environmentally friendly, compared to lead acid batteries and nickel cadmium batteries. However, due to the expansion of market demand, such as the rapid development of new energy automobile industry, the production of lithium ion batteries is rapidly increased, and a large amount of waste lithium ion batteries is inevitably generated. The organic electrolyte and metal elements of the waste lithium ion battery have high toxicity, and if the organic electrolyte and the metal elements are not properly treated, leakage is easy to cause, and serious environmental problems such as soil and underground water pollution are caused. Meanwhile, the positive electrode of the waste lithium ion battery contains a large amount of valuable metals, so that the waste lithium ion battery is properly treated from the viewpoint of environmental protection and economy, and the sustainable development of the lithium ion battery is very necessary.
At present, the processes adopted for recovering valuable metals in the anode of the waste lithium ion battery are mainly hydrometallurgy and pyrometallurgy. Compared with pyrometallurgy, the hydrometallurgy process has the advantages of low energy consumption, small secondary pollution and the like, so that the hydrometallurgy process is widely researched and applied. Although the effect of hydrometallurgy is remarkable, strong acid and reducing agent are used in the process, a large amount of waste water is generated, the human health is affected, the problem of environmental pollution is caused, the whole process is complicated, and the operability of the process is reduced.
Disclosure of Invention
The invention is carried out to solve the problems, and aims to provide a method for selectively extracting lithium from waste lithium ion batteries, which does not need to add a reducing agent additionally, is simple and efficient, has operability and avoids the problem of secondary pollution.
The invention provides a method for selectively extracting lithium from waste lithium ion batteries, which is characterized by comprising the following steps: step S1, mixing the anode active substance of the lithium ion battery and oxalic acid dihydrate according to the molar ratio of 1: 1-8, and heating for solid-solid reaction to obtain a reaction mixture; step S2, processing the reaction mixture by a water leaching method to obtain a lithium oxalate solution; in step S3, a water-soluble carbonate is added to the lithium oxalate solution to obtain a lithium carbonate precipitate.
The method for selectively extracting lithium from the waste lithium ion battery provided by the invention can also have the following characteristics: wherein, in the step S1, the reaction temperature of the solid-solid reaction is 100-180 ℃, and the reaction time is 1-4 h.
The method for selectively extracting lithium from the waste lithium ion battery provided by the invention can also have the following characteristics: the specific operation of step S1 is: mixing the positive active substance and oxalic acid dihydrate, placing the mixture into a round-bottom flask, placing the round-bottom flask into an oil bath, heating to 100-180 ℃ at the heating rate of 5 ℃/min, and reacting for 1-4 h to ensure that the positive active substance and the oxalic acid dihydrate fully react.
The method for selectively extracting lithium from the waste lithium ion battery provided by the invention can also have the following characteristics: the specific operation of step S2 is: adding water into the reaction mixture according to the dosage ratio of 1g to 15-50 ml of the reaction mixture to the water, stirring and reacting for 1-2 h at the temperature of 25-40 ℃, and filtering to obtain the oxalic acid solution.
The method for selectively extracting lithium from the waste lithium ion battery provided by the invention can also have the following characteristics: wherein, the stirring mode is magnetic stirring, and the filtering mode is suction filtration.
The method for selectively extracting lithium from the waste lithium ion battery provided by the invention can also have the following characteristics: in step S3, a 2M sodium carbonate solution or potassium carbonate solution is added to the lithium oxalate solution until no precipitate is formed, and then the lithium carbonate precipitate is obtained by filtration.
The method for selectively extracting lithium from the waste lithium ion battery provided by the invention can also have the following characteristics: wherein the lithium carbonate precipitate is dried in a vacuum drying oven at 60 ℃.
The method for selectively extracting lithium from the waste lithium ion battery provided by the invention can also have the following characteristics: wherein the lithium ion battery is any one of a lithium cobalt oxide battery, a lithium iron phosphate battery, a lithium manganate battery, a ternary nickel cobalt lithium manganate battery or a nickel cobalt lithium aluminate battery.
The method for selectively extracting lithium from the waste lithium ion battery provided by the invention also has the following characteristics that: step S0, a preprocessing step, wherein the preprocessing step specifically includes: placing the lithium ion battery in a salt solution for discharge treatment, then drying at room temperature, disassembling after drying, placing the obtained positive plate in absolute ethyl alcohol for soaking, then washing with a large amount of deionized water, airing at room temperature to obtain a dried positive plate with electrolyte removed, and finally scraping the positive active substance on the positive plate.
Action and Effect of the invention
According to the method for selectively extracting lithium from the waste lithium ion battery, provided by the invention, the anode plate active substance and the oxalic acid dihydrate are heated for solid-solid reaction according to the molar ratio of 1: 1-8, and the metal oxide in the anode plate active substance reacts with the oxalic acid dihydrate, so that the pretreatment process is greatly simplified. The obtained substance can be used for recovering lithium metal by adopting a one-step water leaching method, the rest oxalate metal salts are separated due to the property of difficult water solubility, and then the selective lithium extraction is realized by a precipitation method, so that the operability of the process is greatly improved.
The oxalic acid dihydrate reacts with the metal oxide on the anode without adding a reducing agent, and then the lithium metal is recovered by adopting a one-step water leaching method, so that compared with the traditional process, the recovery process is greatly simplified, the complex pretreatment process is avoided, the recovery process is simplified, the problem of secondary pollution cannot be caused in the whole process, the price of the reagent is low, and the win-win situation of economic benefit and environmental benefit can be realized. In addition, after the transition metal completely reacts with oxalic acid dihydrate, impurities such as a binder and a carbon additive contained in the positive electrode can be removed by filtration, so that separation of the components is realized.
The method realizes the solid-solid reaction of oxalic acid and the anode material, avoids the pollution to the environment caused by using strong acid and a reducing agent, realizes one-step leaching and selective lithium extraction by adopting a water leaching mode, has high leaching efficiency and greatly improves the operability of the method. Therefore, the method is a method for selectively extracting lithium from the waste lithium ion battery with strong operability, environmental friendliness, high efficiency and economy, realizes selective recovery of lithium metal contained in the positive electrode of the waste lithium ion battery, avoids the problems of high recovery cost, high energy consumption, serious secondary pollution, long and complicated treatment process and the like in the traditional treatment process, provides a brand new method for recovering valuable metals in the positive electrode of the waste lithium ion battery, and realizes sustainable development of the lithium ion battery.
Drawings
Fig. 1 is an XRD comparison pattern of lithium carbonate obtained in example 1 of the present invention with commercial lithium carbonate; and
FIG. 2 is a graph showing the results of leaching efficiencies of lithium, nickel, cobalt and manganese in examples 1 and 2 of the present invention.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the method for selectively extracting lithium from the waste lithium ion battery is specifically described below with reference to the embodiment and the accompanying drawings.
Unless otherwise specified, each raw material used in the following examples is a commercially available product, and each apparatus used is a commercially available conventional apparatus.
The invention provides a method for selectively extracting lithium from waste lithium ion batteries, which specifically comprises the following steps:
step S0: pretreatment: the waste lithium ion battery is subjected to discharge treatment, namely the waste lithium ion battery is placed in salt solution of 5 wt% sulfate (such as manganese sulfate) or chloride (such as sodium chloride) and the like, residual electric quantity in the battery cell is consumed based on the electrochemical electrolysis principle, and then the battery cell is dried at room temperature. And after the drying is finished, disassembling, soaking the obtained positive plate in absolute ethyl alcohol, then washing with a large amount of deionized water, airing at room temperature to obtain the dried positive plate with the electrolyte removed, and then scraping the positive active substance (positive material) on the positive plate.
Wherein the lithium ion battery is a lithium cobalt oxide battery, a lithium iron phosphate battery, a lithium manganate battery, a ternary nickel cobalt lithium manganate battery or a nickel cobalt lithium aluminate battery. In the embodiment of the invention, the recycled ternary lithium nickel cobalt manganese oxide battery and the recycled lithium cobalt oxide battery of the apple X mobile phone are taken as examples for experiments, and in practical application, other lithium ion batteries can achieve the same experimental effect.
Step S1: mixing the positive active material and oxalic acid dihydrate according to the molar ratio of 1: 1-8, and heating for solid-solid reaction to obtain a reaction mixture.
The specific operation is as follows: according to the molar ratio of the active substance of the positive plate to the oxalic acid dihydrate of 1: 1-8, mixing the positive plate material with the oxalic acid dihydrate and placing the mixture in a round-bottom flask. In the examples of the present invention, oil bath heating was selected. The round bottom flask is put in an oil bath, the temperature is raised to 100-180 ℃ at the temperature raising rate of 5 ℃/min, and the reaction is carried out for 1-4 h, so that the anode material and the oxalic acid dihydrate are fully reacted, and lithium oxalate which is easy to dissolve in water, oxalic acid metal salt which is difficult to dissolve and other impurities are obtained. In the example of the present invention, the temperature was raised to 115 ℃ at a temperature raising rate of 5 ℃/min, and reacted for 2 hours.
Step S2: and (3) treating the reaction mixture by a water leaching method to obtain a lithium oxalate solution.
The specific operation is as follows: naturally cooling the round-bottom flask to room temperature, transferring the material into the beaker according to the use ratio of the solid matter obtained in the step S1, namely the use amount of the reaction mixture to the deionized water or the secondary distilled water, of 1g: 15-50 ml, placing the material on a magnetic stirrer for reaction at the temperature of 25-40 ℃ for 1-2 h, and performing suction filtration or funnel filtration in a filtration mode to obtain a filtrate, namely a lithium oxalate solution.
Step S3: and adding water-soluble carbonate into the lithium oxalate solution to obtain lithium carbonate precipitate.
The specific operation is as follows: to the lithium oxalate solution was added a 2M solution of sodium or potassium carbonate until no precipitate was formed. And then, drying the filter membrane in a vacuum drying oven at 60 ℃ in a suction filtration mode to obtain a dried lithium carbonate precipitate.
< example 1>
In this embodiment, the recovered ternary nickel cobalt lithium manganate battery is taken as an example to selectively extract lithium.
Step S0: the recovered ternary nickel cobalt lithium manganate battery is placed in 5 wt% sodium chloride solution for 48 hours for discharge treatment, dried at room temperature, and then the anode material on the anode plate is scraped off.
Step S1: according to the molar ratio of the active substance of the positive plate to the oxalic acid dihydrate of 1:2, the positive plate material and the oxalic acid dihydrate are mixed and placed in a round-bottom flask to be heated in oil bath. Heating the oil bath temperature to 115 ℃ at the heating rate of 5 ℃/min, and reacting for 1h to ensure that the anode material and oxalic acid dihydrate are fully reacted to obtain lithium oxalate which is easy to dissolve in water, metal oxalate which is difficult to dissolve and other impurities.
Step S2: naturally cooling the round-bottom flask to room temperature, transferring the material into a beaker, placing the beaker on a magnetic stirrer for reaction at the reaction temperature of 25 ℃ for 1h according to the dosage ratio of 1g to 40ml of oxalate metal salt to deionized water or secondary distilled water, and filtering by adopting suction filtration or funnel filtration.
Step S3: to the resulting lithium oxalate solution was added a 2M sodium carbonate solution until no precipitate was formed. And then, putting the filter membrane in a vacuum drying oven to be dried at 60 ℃ in a suction filtration mode to obtain a lithium carbonate precipitate.
Fig. 1 is an XRD comparison pattern of lithium carbonate obtained in example 1 of the present invention with commercial lithium carbonate.
As shown in fig. 1, by X-ray diffraction detection (XRD), it can be analyzed that the lithium carbonate precipitate (regenerated lithium carbonate) finally obtained by the method of this embodiment is clean and complete without impurity, which indicates that the lithium on the positive electrode of the recycled ternary lithium nickel cobalt manganese oxide battery can be effectively recycled.
< example 2>
Compared with the embodiment 1, the molar ratio of the active material of the positive plate and the oxalic acid dihydrate in the step S1 is 1:4, the positive electrode material is reacted with the oxalic acid dihydrate, and the rest steps are the same.
The metal concentration was measured by Atomic Absorption Spectrophotometer (AAS). The concentration of the metal in the solid before the reaction is C1The concentration of the metal in the solution after water immersion is C2Leaching rate ═ C2×V2)/(C1×V1) Wherein V is1Represents the volume after the positive electrode is digested and the volume is determined, V2Representing the volume after water immersion and volume fixing.
FIG. 2 is a graph showing the results of leaching efficiencies of lithium, nickel, cobalt and manganese in examples 1 and 2 of the present invention.
As shown in fig. 2, in example 1, after 1 hour of reaction at a molar ratio of 1:2, the leaching efficiencies of lithium, nickel, cobalt and manganese metals were 92.58%, 2.47%, 5.36% and 3.17%, respectively. In example 2, the leaching efficiencies of lithium, nickel, cobalt and manganese metals after 1-hour reaction at a molar ratio of 1:4 are 93.49%, 4.91%, 6.08% and 3.54%, respectively. The leaching efficiency of the lithium is equivalent to that of an acid leaching agent commonly used in the traditional hydrometallurgy process, and the leaching amount of other valuable metals is extremely low. The results of examples 1 and 2 show that the method has remarkable lithium selective extraction effect and has potential for commercial application.
< example 3>
In this embodiment, the recovered lithium cobalt oxide battery of the apple X mobile phone is taken as an example to selectively extract lithium.
Step S0: and placing the recovered ternary nickel cobalt lithium manganate battery in a 5 wt% manganese sulfate solution for 48h for discharge treatment, drying at room temperature, and scraping the positive electrode material on the positive plate.
Step S1: according to the molar ratio of the active substance of the positive plate to the oxalic acid dihydrate of 1:6, the positive plate material and the oxalic acid dihydrate are mixed and placed in a round-bottom flask to be heated in oil bath. Heating the oil bath temperature to 120 ℃ at the heating rate of 4 ℃/min, and reacting for 1h to ensure that the anode material and oxalic acid dihydrate are fully reacted to obtain lithium oxalate which is easy to dissolve in water, oxalic acid metal salt which is difficult to dissolve and other impurities.
Step S2: naturally cooling the round-bottom flask to room temperature, transferring the material into a beaker, placing the beaker on a magnetic stirrer for reaction at the reaction temperature of 30 ℃ for 1h according to the dosage ratio of 1g to 50ml of oxalate metal salt to deionized water or secondary distilled water, and filtering by adopting suction filtration or funnel filtration.
Step S3: to the resulting lithium oxalate solution was added a 2M sodium carbonate solution until no precipitate was formed. And then, putting the filter membrane in a vacuum drying oven to be dried at 60 ℃ in a suction filtration mode to obtain a lithium carbonate precipitate.
Effects and effects of the embodiments
According to the method for selectively extracting lithium from the waste lithium ion battery provided by the embodiment of the invention, the anode plate active substance and the oxalic acid dihydrate are heated for a solid-solid reaction according to the molar ratio of 1: 1-8, and the metal oxide in the anode plate active substance reacts with the oxalic acid dihydrate, so that the pretreatment process is greatly simplified. The obtained substance can be used for recovering lithium metal by adopting a one-step water leaching method, the rest oxalate metal salts are separated due to the property of difficult water solubility, and then the selective lithium extraction is realized by a precipitation method, so that the operability of the process is greatly improved.
The oxalic acid dihydrate reacts with the metal oxide on the anode without adding a reducing agent, and then the lithium metal is recovered by adopting a one-step water leaching method, so that compared with the traditional process, the recovery process is greatly simplified, the complex pretreatment process is avoided, the recovery process is simplified, the problem of secondary pollution cannot be caused in the whole process, the price of the reagent is low, and the win-win situation of economic benefit and environmental benefit can be realized. In addition, after the transition metal completely reacts with oxalic acid dihydrate, impurities such as a binder and a carbon additive contained in the positive electrode can be removed by filtration, so that separation of the components is realized.
In addition, the reaction temperature in the solid-solid reaction is 100-180 ℃, the reaction time is 1-4 h, and the metal oxide in the active material of the positive plate and oxalic acid dihydrate are ensured to fully react.
In addition, the reaction mixture after solid-solid reaction and water are stirred for reaction for 1 to 2 hours at the temperature of between 25 and 40 ℃ according to the dosage ratio of 1g to 15 to 50ml, so that lithium oxalate which is easy to dissolve in water is dissolved in water, insoluble oxalate metal salt and other impurities still exist in a solid form, and the pure oxalic acid solution can be filtered, and the selective recovery of lithium ions can be conveniently realized through precipitation.
According to the method provided by the embodiment of the invention, the selective recovery of lithium metal contained in the anode of the waste lithium ion battery is realized, so that the embodiment of the invention provides a method for selectively extracting lithium from the waste lithium ion battery, which has strong operability, is environment-friendly, efficient and economical, the problems of high recovery cost, high energy consumption, serious secondary pollution, complex and long treatment process and the like in the traditional treatment process are solved, a brand new method is provided for recovering valuable metal in the anode of the waste lithium ion battery, and the sustainable development of the lithium ion battery is realized.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A method for selectively extracting lithium from waste lithium ion batteries is characterized by comprising the following steps:
step S1, mixing the anode active substance of the lithium ion battery and oxalic acid dihydrate according to the molar ratio of 1: 1-8, and heating for solid-solid reaction to obtain a reaction mixture;
step S2, processing the reaction mixture by a water leaching method to obtain a lithium oxalate solution;
step S3, adding a water-soluble carbonate to the lithium oxalate solution to obtain a lithium carbonate precipitate.
2. The method for selectively extracting lithium from waste lithium ion batteries according to claim 1, characterized in that:
in the step S1, the reaction temperature of the solid-solid reaction is 100-180 ℃, and the reaction time is 1-4 h.
3. The method for selectively extracting lithium from waste lithium ion batteries according to claim 1, characterized in that:
the specific operation of step S1 is: and mixing the positive active substance and the oxalic acid dihydrate, placing the mixture into a round-bottom flask, placing the round-bottom flask into an oil bath, heating to 100-180 ℃ at the heating rate of 5 ℃/min, and reacting for 1-4 h to ensure that the positive active substance and the oxalic acid dihydrate are fully reacted.
4. The method for selectively extracting lithium from waste lithium ion batteries according to claim 1, characterized in that:
the specific operation of step S2 is: adding water into the reaction mixture according to the dosage ratio of 1g: 15-50 ml of the reaction mixture to the water, stirring and reacting for 1-2 h at the temperature of 25-40 ℃, and filtering to obtain the oxalic acid solution.
5. The method for selectively extracting lithium from waste lithium ion batteries according to claim 4, wherein the method comprises the following steps:
wherein, the stirring mode is magnetic stirring, and the filtering mode is suction filtration.
6. The method for selectively extracting lithium from waste lithium ion batteries according to claim 1, characterized in that:
in step S3, a 2M sodium carbonate solution or potassium carbonate solution is added to the lithium oxalate solution until no precipitate is formed, and then the lithium carbonate precipitate is obtained by filtration.
7. The method for selectively extracting lithium from waste lithium ion batteries according to claim 6, wherein the method comprises the following steps:
wherein the lithium carbonate precipitate is dried in a vacuum drying oven at 60 ℃.
8. The method for selectively extracting lithium from waste lithium ion batteries according to claim 1, characterized in that:
the lithium ion battery is any one of a lithium cobalt oxide battery, a lithium iron phosphate battery, a lithium manganate battery, a ternary lithium nickel cobalt manganate battery or a lithium nickel cobalt aluminate battery.
9. The method for selectively extracting lithium from waste lithium ion batteries according to claim 1, further comprising:
step S0, a preprocessing step,
the pretreatment step comprises the following specific operations: and placing the lithium ion battery in a salt solution for discharge treatment, then drying at room temperature, disassembling after drying, placing the obtained positive plate in absolute ethyl alcohol for soaking, then washing with a large amount of deionized water, airing at room temperature to obtain the dried positive plate with the electrolyte removed, and finally scraping the positive active substance on the positive plate.
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