CN115784324B - Method for recycling and preparing ternary positive electrode material precursor by using waste ternary lithium battery - Google Patents
Method for recycling and preparing ternary positive electrode material precursor by using waste ternary lithium battery Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 49
- 239000002699 waste material Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002243 precursor Substances 0.000 title claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 238000002386 leaching Methods 0.000 claims abstract description 73
- 239000002253 acid Substances 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 150000007524 organic acids Chemical class 0.000 claims abstract description 23
- 239000010405 anode material Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 18
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 72
- 235000006408 oxalic acid Nutrition 0.000 claims description 24
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 30
- 239000011572 manganese Substances 0.000 abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 abstract description 15
- 239000010941 cobalt Substances 0.000 abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052759 nickel Inorganic materials 0.000 abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052748 manganese Inorganic materials 0.000 abstract description 11
- 238000001914 filtration Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 16
- 238000011084 recovery Methods 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000011888 foil Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 102100024452 DNA-directed RNA polymerase III subunit RPC1 Human genes 0.000 description 1
- 101000689002 Homo sapiens DNA-directed RNA polymerase III subunit RPC1 Proteins 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004540 process dynamic Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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 discloses a method for preparing a ternary positive electrode material precursor by recycling waste ternary lithium batteries, which comprises the following steps: A. pretreating a waste ternary lithium battery to obtain waste anode material powder; B. mixing acidic inorganic matters and organic acid to prepare a mixed acid solution, adding waste anode material powder into the mixed acid solution, leaching under high-temperature pressurizing conditions, and filtering after the reaction is finished to obtain a reaction filtrate; C. adding an alkali solution into the reaction filtrate, and recovering by adopting a precipitation method to obtain the nickel-cobalt-manganese ternary anode material precursor. According to the invention, through a mixed acid leaching system mainly taking organic acid as a main component, and simultaneously with the cooperation of high-temperature pressure leaching conditions, not only is nickel, cobalt, manganese and lithium elements selectively leached, but also the problem of low leaching efficiency of the organic acid is overcome, the use amount of the organic acid and the impurity content in the recovered product are reduced, the leaching process is environment-friendly, and industrial application is facilitated.
Description
Technical Field
The invention relates to the technical field of waste lithium ion battery recovery, in particular to a method for preparing a ternary positive electrode material precursor by recycling waste ternary lithium batteries.
Background
The industry of electric automobiles in China has been rapidly developing over the last 10 years. Meanwhile, the electric vehicles that were first introduced into the market have been currently introduced into the battery retirement stage, and the number of retired batteries has been drastically increased in the next few years. According to market research prediction, the scrapped amount of the lithium battery for the vehicle in 2020 reaches 32GWh, and the scrapped battery is converted into about 50 ten thousand tons in mass; by 2030, the scrapped amount of the lithium battery for the vehicle can reach 300GWh, and the scrapped amount of the lithium battery is about 300 ten thousand tons. Lithium batteries are mainly divided into lithium iron phosphate batteries and ternary lithium batteries according to different positive electrode materials, and the ternary lithium batteries become the main stream of new energy automobile batteries due to the advantages of high energy density, long service life and the like. The ternary lithium battery contains cobalt, nickel and other metal elements, if the ternary lithium battery is not recycled, the ternary lithium battery not only causes great waste of resources, but also causes ecological environment pollution, thereby limiting the sustainable development of new energy automobile industry. At present, the raw materials of metals such as nickel, cobalt, lithium and the like for preparing the ternary positive electrode material are high in price and large in demand. Therefore, the method extracts metals such as nickel, cobalt, lithium and the like from the ternary waste lithium battery, not only can solve the problem of raw material supply, but also can create great benefits for society. With the great development of new energy automobile industry in China, in recent years, the lithium battery industry has shown explosive growth. According to GGII research data, the output of the power battery in 2017 China is 44.5GWh, which accounts for more than 50% of the total world, and China becomes the largest lithium battery production and consumption market in the world, so that the method has very important significance for recycling the waste lithium batteries.
The wet metallurgy recovery method is generally adopted for recovering the ternary cathode material from the waste lithium battery in China: and (3) disassembling and crushing the waste lithium batteries, separating out anode powder with low impurity content, and leaching manganese, nickel, cobalt and lithium in the anode powder to recover nickel, cobalt and manganese. In the wet recovery process, although the inorganic acid leaching efficiency is high and the cost is low, the leaching process can generate toxic gas, the acid is too strong to corrode equipment, the defect is obvious, the organic acid is mild in acidity and has little effect on equipment corrosion, the leaching process does not generate toxic gas, the hot spot direction of the current research is (can refer to the research progress of the existing literature of the hydrometallurgical recovery technology of waste lithium ion batteries, li Linlin, cao Linjuan and the like, the energy storage science and technology, 2020.09 (06)), but the leaching efficiency of the organic acid is low, the industrial requirement is difficult to meet, so a mixed acid leaching system of inorganic acid-organic acid is proposed, the problem of the low leaching of the organic acid can only be improved to a limited extent, the leaching efficiency of the organic acid can not be improved remarkably, meanwhile, under the mixed acid system, the elements such as aluminum, calcium, magnesium and the like in the anode material are leached more, the impurity elements have influence on the recovery of nickel cobalt manganese, and the impurity content of the final precursor product is higher, so that the electrochemical performance of the ternary anode material is influenced.
Disclosure of Invention
The invention aims at: aiming at the problems, the invention provides a method for preparing the ternary positive electrode material precursor by recycling the waste ternary lithium battery, and the method has the advantages that by designing a mixed acid leaching system mainly comprising organic acid and simultaneously cooperating with high-temperature pressure leaching conditions, the problem of low leaching efficiency of the organic acid is solved, the impurity content of the leached ternary positive electrode material precursor is effectively reduced, and the defects in the prior art are overcome.
The technical scheme adopted by the invention is as follows: a method for preparing ternary positive electrode material precursors by recycling waste ternary lithium batteries comprises the following steps:
A. pretreating a waste ternary lithium battery to obtain waste anode material powder;
B. mixing acidic inorganic matters and organic acid to prepare a mixed acid solution, adding waste anode material powder into the mixed acid solution, leaching under high-temperature pressurizing conditions, and filtering after the reaction is finished to obtain a reaction filtrate;
C. adding an alkali solution into the reaction filtrate, and recovering by adopting a precipitation method to obtain the nickel-cobalt-manganese ternary anode material precursor.
In the invention, the reaction is carried out by adopting a high-temperature pressure leaching mode, compared with the conventional leaching, the high temperature is favorable for activating a leaching system, so that the chemical reaction degree is increased, but the organic acid is easily decomposed and sublimated at the high temperature, and the oxalic acid used in the invention is taken as an example, the theoretical thermal decomposition temperature of the oxalic acid is 157 ℃, and in industrial application, the thermal decomposition phenomenon exists when the temperature reaches 100 ℃, and the leaching is easily carried out under 100 ℃ along with the escape of water vapor, so that the leaching efficiency is difficult to be effectively improved. In order to remarkably improve the leaching efficiency of oxalic acid and avoid the decomposition and high Wen Yichu of oxalic acid, the invention also cooperates with a pressurizing process to apply certain pressure to a leaching system when adopting high-temperature leaching at 120-180 ℃, and the invention can prevent the decomposition and high Wen Yichu of oxalic acid and aggravate the reaction degree, so that the refractory material is easy to leach, the consumption of oxalic acid is not increased, the consumption of oxalic acid is reduced, and higher metal recovery rate can be obtained under the same acidic condition. Experiments prove that in a short time (within 0.5-2 h), the recovery rate of lithium is more than 98%, the leaching rate of noble metals of nickel, cobalt and manganese reaches more than 95%, and the leaching efficiency is obviously improved. Furthermore, the invention adopts a high-temperature pressurizing means, so that the consumption of oxalic acid is reduced, the residual acid amount is reduced, the reduction of the residual amount is not only beneficial to the subsequent treatment of the leaching solution, but also reduces the content of impurity metals such as calcium, magnesium and the like in the leaching solution, so that the impurity content in the recovered ternary positive electrode material precursor is effectively controlled, and the quality of the recovered product is improved.
Therefore, the invention greatly improves the process dynamics condition by a high-temperature pressure leaching mode, not only improves the leaching efficiency, but also reduces the use amount of organic acid, has higher metal recovery rate, improves the quality of recovered products, is more environment-friendly, and is beneficial to industrial application.
In step B, the high-temperature pressure leaching is carried out at 120 to 180℃and, for example, 120℃130℃140℃150℃160℃180℃and the pressure is 0.5 to 1.0MPa, for example, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 1.0MPa and the like.
Further, in the step B, the high-temperature pressure leaching time is 0.5-2 hours (for example, 0.5 hours, 1.0 hours, 1.5 hours, 2 hours, etc.), and the stirring speed is 300-800r/min, for example, 300r/min, 350r/min, 400r/min, 500r/min, 600r/min, 800r/min, etc.
Preferably, in the mixed acid solution, the acidic inorganic substance is ammonium sulfate, and the organic acid is oxalic acid.
Further, the molar ratio of oxalic acid to ammonium sulfate is 6-8:2-4, for example, 6:2, 6:3, 7:2, 7:3, 8:3, 8:4, etc., preferably 8:3.
Further, the mixed acid solution also contains d-glucose. The introduction of d-glucose helps to further increase the leaching efficiency, while also helping to more stably leach the entire leaching system.
Further, the molar ratio of oxalic acid, ammonium sulfate and d-glucose is 6-8:2-4:1.
Further, in the step B, the solid-to-liquid ratio of the mixed acid solution to the waste positive electrode material powder is 10-50g/L, and for example, 10g/L, 20g/L, 25g/L, 30g/L, 40g/L, 50g/L and the like can be adopted.
Further, in the mixed acid solution, the concentration of oxalic acid is 1 to 2mol/L, and for example, 1mol/L, 1.25mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, and the like can be used.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows: the invention designs a mixed acid leaching system mainly based on organic acid, and simultaneously cooperates with high-temperature pressure leaching conditions, so that not only can nickel, cobalt, manganese and lithium elements be selectively leached, the total selectivity is more than 98%, but also the problem of low leaching efficiency of the organic acid is overcome, the leaching period is shortened, the use amount of the organic acid and the impurity content in a recovered product are reduced, the recovery cost is reduced, the quality of the recovered product is improved, the leaching process is environment-friendly, and the industrial application is facilitated.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
A method for preparing ternary positive electrode material precursors by recycling waste ternary lithium batteries comprises the following steps:
A. placing the waste ternary lithium battery in saline water until discharging is completed, disassembling the battery to obtain an aluminum foil containing an anode active component, and carrying out ultrasonic stripping on the anode active component on the aluminum foil to obtain waste anode material powder;
B. mixing oxalic acid, ammonium sulfate and d-glucose according to a molar ratio of 8:3:1 to prepare a 1L solution, wherein the concentration of the oxalic acid is 1.25mol/L, adding 10g of waste anode material powder into the mixed acid solution, introducing compressed air to maintain the pressure of 0.8MPa, heating the solution to 180 ℃ by using steam, keeping the temperature for 1h, simultaneously stirring by using a motor at the speed of 500r/min, filtering and washing to obtain clear filtrate, and measuring leaching rates of valuable metals lithium, nickel, cobalt and manganese in the reaction filtrate by using ICP to obtain a solution with the leaching rates of E respectively Li ＝99.1％、E Ni ＝95.5％、E Co ＝95.3％、E Mn ＝97.7％；
C. Slowly adding 1mol/L ammonia water solution into the reaction filtrate to perform precipitation recovery on metal nickel cobalt manganese, filtering, performing solid-liquid separation, drying the precipitate, recycling the filtrate, calcining the dried precipitate at 700 ℃ for 6 hours to obtain a nickel cobalt manganese ternary positive electrode material precursor, and detecting that the content of calcium and magnesium in the nickel cobalt manganese ternary positive electrode material precursor is 0.018 percent, and the content of calcium and magnesium is reduced by 0.1-0.3 percent compared with the content of calcium and magnesium in the traditional organic acid process.
Example 2
A method for preparing ternary positive electrode material precursors by recycling waste ternary lithium batteries comprises the following steps:
A. placing the waste ternary lithium battery in saline water until discharging is completed, disassembling the battery to obtain an aluminum foil containing an anode active component, and carrying out ultrasonic stripping on the anode active component on the aluminum foil to obtain waste anode material powder;
B. mixing oxalic acid, ammonium sulfate and d-glucose according to a molar ratio of 6:3:1 to prepare a 1L solution, wherein the concentration of the oxalic acid is 1.75mol/L, adding 30g of waste anode material powder into the mixed acid solution, introducing compressed air to maintain the pressure of 1.0MPa, heating the solution to 150 ℃ by using steam, keeping the temperature for 0.5h, simultaneously stirring by using a motor at the speed of 700r/min, filtering and washing to obtain clear filtrate, and measuring the leaching rates of valuable metals lithium, nickel, cobalt and manganese in the reaction filtrate by using ICP to obtain a leaching rate E respectively Li ＝99.3％、E Ni ＝96.3％、E Co ＝97.1％、E Mn ＝95.9％；
C. Slowly adding 1mol/L ammonia water solution into the reaction filtrate to perform precipitation recovery on metal nickel cobalt manganese, filtering, performing solid-liquid separation, drying the precipitate, recycling the filtrate, calcining the dried precipitate at 800 ℃ for 5 hours to obtain a nickel cobalt manganese ternary positive electrode material precursor, and detecting that the content of calcium and magnesium in the nickel cobalt manganese ternary positive electrode material precursor is 0.012 percent, wherein the content of calcium and magnesium is reduced by 0.1-0.3 percent compared with the traditional organic acid leaching process.
Example 3
A method for preparing ternary positive electrode material precursors by recycling waste ternary lithium batteries comprises the following steps:
A. placing the waste ternary lithium battery in saline water until discharging is completed, disassembling the battery to obtain an aluminum foil containing an anode active component, and carrying out ultrasonic stripping on the anode active component on the aluminum foil to obtain waste anode material powder;
B. mixing oxalic acid, ammonium sulfate and d-glucose according to a molar ratio of 8:4:1 to prepare a 1L solution, wherein the concentration of the oxalic acid is 2mol/L, adding 50g of waste anode material powder into a mixed acid solution, introducing compressed air to maintain the pressure of 0.6MPa, heating the solution to 140 ℃ by using steam, keeping the temperature for 1.5 hours, simultaneously stirring by using a motor at the speed of 800r/min, filtering and washing to obtain clear filtrate, and measuring leaching rates of valuable metals lithium, nickel, cobalt and manganese in the reaction filtrate by using ICP to obtain a solution with the leaching rates of E respectively Li ＝98.4％、E Ni ＝95.7％、E Co ＝98.2％、E Mn ＝97.9％；
C. Slowly adding 1mol/L ammonia water solution into the reaction filtrate to perform precipitation recovery on metal nickel cobalt manganese, filtering, performing solid-liquid separation, drying the precipitate, recycling the filtrate, calcining the dried precipitate at 750 ℃ for 6 hours to obtain a nickel cobalt manganese ternary positive electrode material precursor, and detecting that the content of calcium and magnesium in the nickel cobalt manganese ternary positive electrode material precursor is 0.011%, wherein the content of calcium and magnesium is reduced by 0.1-0.3% compared with the traditional organic acid leaching process.
Example 4
A method for preparing ternary positive electrode material precursors by recycling waste ternary lithium batteries comprises the following steps:
A. placing the waste ternary lithium battery in saline water until discharging is completed, disassembling the battery to obtain an aluminum foil containing an anode active component, and carrying out ultrasonic stripping on the anode active component on the aluminum foil to obtain waste anode material powder;
B. mixing oxalic acid, ammonium sulfate and d-glucose according to a molar ratio of 7:3:1 to prepare a 1L solution, wherein the concentration of the oxalic acid is 1.5mol/L, adding 30g of waste anode material powder into the mixed acid solution, introducing compressed air to maintain the pressure of 0.7MPa, heating the solution to 160 ℃ by using steam, keeping the temperature for 1h, simultaneously stirring by using a motor at the speed of 600r/min, filtering and washing to obtain clear filtrate, and measuring the leaching rates of valuable metals lithium, nickel, cobalt and manganese in the reaction filtrate by using ICP to obtain a leaching rate E respectively Li ＝99.4％、E Ni ＝96.2％、E Co ＝98.5％、E Mn ＝97.4％；
C. Slowly adding 1mol/L ammonia water solution into the reaction filtrate to perform precipitation recovery on metal nickel cobalt manganese, filtering, performing solid-liquid separation, drying the precipitate, recycling the filtrate, calcining the dried precipitate at 650 ℃ for 8 hours to obtain a nickel cobalt manganese ternary positive electrode material precursor, and detecting that the content of calcium and magnesium in the nickel cobalt manganese ternary positive electrode material precursor is 0.015%, wherein the content of calcium and magnesium is reduced by 0.1-0.3% compared with the traditional organic acid leaching process.
Comparative example 1
Comparative example 1 and example1 are identical, except that the leaching process is carried out for 1h at 80 ℃ under normal pressure. The leaching rate of valuable metals lithium, nickel, cobalt and manganese in the reaction filtrate is measured by ICP to be E respectively Li ＝87.4％、E Ni ＝83.3％、E Co ＝77.6％、E Mn =81.6%. Therefore, leaching is carried out under the conditions of normal temperature and normal pressure, the leaching efficiency is low, and the industrial requirement is difficult to meet.
Comparative example 2
Comparative example 2 is the same as example 1 except that the leaching process is carried out at normal pressure. In the leaching process, acid gas escapes, which has obvious influence on the surrounding environment, and meanwhile, the leaching rates of valuable metals lithium, nickel, cobalt and manganese in the reaction filtrate are respectively E by ICP Li ＝85.5％、E Ni ＝76.9％、E Co ＝82.5％、E Mn =81.3%. The leaching rate can be obtained by comparing the leaching rate, and only the leaching temperature is improved, although the leaching efficiency is not obviously changed, the leaching rate is still lower and obviously inferior to that of the embodiment 1, and the leaching process has acid gas generation, so that the pollution to the surrounding environment is caused, and the leaching method is difficult to be applied to industrialization.
Comparative example 3
Comparative example 3 is identical to comparative example 1 except that the leaching process is carried out for 1h at 80℃and a pressure of 0.8 MPa. The leaching rate of valuable metals lithium, nickel, cobalt and manganese in the reaction filtrate is measured by ICP to be E respectively Li ＝86.3％、E Ni ＝74.1％、E Co ＝83.1％、E Mn =78.3%. The leaching efficiency of the mixed acid solution can be improved obviously by comparing the leaching rate in a conventional leaching system in a pressurizing mode.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (4)
1. The method for preparing the ternary cathode material precursor by recycling the waste ternary lithium battery is characterized by comprising the following steps of:
A. pretreating a waste ternary lithium battery to obtain waste anode material powder;
B. mixing acidic inorganic matters and organic acid to prepare a mixed acid solution, wherein the acidic inorganic matters are ammonium sulfate, the organic acid is oxalic acid, d-glucose is further contained in the mixed acid solution, the molar ratio of the oxalic acid to the ammonium sulfate to the d-glucose is 6-8:2-4:1, waste anode material powder is added into the mixed acid solution, leaching is carried out under high-temperature pressurizing conditions, the high-temperature pressurizing leaching temperature is 120-180 ℃, the pressure is applied by introducing compressed air, the pressure is 0.5-1.0MPa, the high-temperature pressurizing leaching time is 0.5-2h, the stirring speed is 300-800r/min, and the reaction filtrate is obtained after the reaction is finished;
C. adding an alkali solution into the reaction filtrate, and recovering by adopting a precipitation method to obtain the nickel-cobalt-manganese ternary anode material precursor.
2. The method for preparing a ternary positive electrode material precursor by recycling waste ternary lithium batteries according to claim 1, wherein the molar ratio of oxalic acid to ammonium sulfate is 8:3.
3. The method for preparing ternary positive electrode material precursors by recycling waste ternary lithium batteries according to claim 2, wherein in the step B, the solid-to-liquid ratio of the mixed acid solution to the waste positive electrode material powder is 10-50g/L.
4. The method for preparing a ternary positive electrode material precursor by recycling waste ternary lithium batteries according to claim 3, wherein the concentration of oxalic acid in the mixed acid solution is 1-2mol/L.
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