CN115784324A - Method for recycling and preparing ternary cathode material precursor by using waste ternary lithium battery - Google Patents
Method for recycling and preparing ternary cathode 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 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 50
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002243 precursor Substances 0.000 title claims abstract description 34
- 239000010406 cathode material Substances 0.000 title claims abstract description 33
- 238000004064 recycling Methods 0.000 title claims abstract description 24
- 238000002386 leaching Methods 0.000 claims abstract description 66
- 150000007524 organic acids Chemical class 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 239000007774 positive electrode material Substances 0.000 claims abstract description 3
- 238000001556 precipitation Methods 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 63
- 235000006408 oxalic acid Nutrition 0.000 claims description 21
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 11
- 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
- 239000000463 material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 48
- 229910017052 cobalt Inorganic materials 0.000 abstract description 24
- 239000010941 cobalt Substances 0.000 abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052759 nickel Inorganic materials 0.000 abstract description 24
- 239000011572 manganese Substances 0.000 abstract description 22
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052748 manganese Inorganic materials 0.000 abstract description 15
- 239000012535 impurity Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 5
- 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 5
- 150000002739 metals Chemical class 0.000 description 5
- 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
- 238000011160 research Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 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
- 238000009854 hydrometallurgy Methods 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
- 230000003213 activating effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 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
- 238000004519 manufacturing process 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
- 238000004904 shortening Methods 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 recycling and preparing a ternary cathode material precursor by utilizing waste ternary lithium batteries, which comprises the following steps of: A. pretreating the waste ternary lithium battery to obtain waste anode material powder; B. mixing an acidic inorganic substance and an organic acid to prepare a mixed acid solution, adding the waste anode material powder into the mixed acid solution, leaching under the condition of high temperature and pressurization, and filtering after the reaction is finished to obtain a reaction filtrate; C. and adding an alkali solution into the reaction filtrate, and recovering by adopting a precipitation method to obtain the precursor of the nickel-cobalt-manganese ternary positive electrode material. According to the invention, through a mixed acid leaching system mainly comprising organic acid and cooperating with a high-temperature pressure leaching condition, the nickel, cobalt, manganese and lithium elements can be selectively leached, the problem of low leaching efficiency of the organic acid is solved, the usage amount of the organic acid and the impurity content in a recovered product are reduced, the leaching process is environment-friendly, and the industrial application is favorably realized.
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 cathode material precursor by recovering waste ternary lithium batteries.
Background
In recent 10 years, the electric automobile industry in China has been rapidly developed. Meanwhile, electric vehicles, which have entered the market earliest, have now entered the battery decommissioning stage, and the number of decommissioned batteries has also increased dramatically in the next few years. According to the market research and prediction, the scrappage of the lithium battery for the automobile reaches 32GWh in 2020, and the scrappage of the battery is converted into the quality of about 50 ten thousand tons; by 2030 years, the scrappage of the lithium battery for the vehicle can reach 300GWH, and the scrappage of the lithium battery is about 300 ten thousand tons. Lithium batteries are mainly classified into lithium iron phosphate batteries and ternary lithium batteries according to different anode materials, and the ternary lithium batteries become the mainstream of new energy automobile batteries due to the advantages of high energy density, long service life and the like. The ternary lithium battery contains metal elements such as cobalt and nickel, and if the ternary lithium battery is not recycled, not only is the resource greatly wasted, but also the ecological environment is polluted, so that the sustainable development of the new energy automobile industry is limited. At present, the price of the metal raw materials such as nickel, cobalt, lithium and the like for preparing the ternary cathode material is high and the demand is large. Therefore, metals such as nickel, cobalt, lithium and the like are extracted from the ternary waste lithium battery, so that the problem of raw material supply can be solved, and huge benefits can be created for the society. With the vigorous development of new energy automobile industry in China, in recent years, the lithium battery industry has explosive growth. According to GGII research data, the output of a Chinese power battery in 2017 is 44.5GWH, which accounts for more than 50% of the total amount of the whole 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 waste lithium batteries.
The method for recovering the ternary cathode material from the waste lithium battery at home generally adopts a hydrometallurgy recovery method: the waste lithium batteries are disassembled and crushed, the anode powder with lower impurity content is sorted out, and manganese, nickel, cobalt and lithium in the anode powder are leached together to recover nickel, cobalt and manganese. In the wet recovery process, although the inorganic acid has the characteristics of high leaching efficiency and low cost, the leaching process generates toxic gas, the acidity is too strong, the corrosion to equipment is large, the defects are obvious, the organic acid has mild property and small corrosion effect to equipment, and the leaching process does not generate toxic gas, which is a hot direction in the current research (refer to the existing literature, "research progress of organic acid hydrometallurgy recovery technology of waste lithium ion batteries," li lin, cao lin juan and the like, science and technology of energy storage, 2020.09 (06)), but the organic acid leaching efficiency is low and is difficult to meet the industrial requirements, so that an inorganic acid-organic acid mixed acid leaching system is proposed, the system only can improve the problem of low organic acid leaching, but can not improve the leaching efficiency of the organic acid remarkably, and meanwhile, under the mixed acid system, more elements such as aluminum, calcium, magnesium and the like in the anode material are leached, and the impurity elements affect the recovery of nickel, cobalt and the impurity content of the final precursor product is high, thereby affecting the electrochemical performance of the ternary anode material.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the invention provides a method for recycling and preparing a ternary cathode material precursor by utilizing waste ternary lithium batteries, and the method is characterized in that by designing a mixed acid leaching system mainly comprising organic acid and cooperating with high-temperature pressure leaching conditions, the problem of low organic acid leaching efficiency is solved, the impurity content of the ternary cathode material precursor obtained by leaching 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 recycling and preparing a ternary cathode material precursor by utilizing a waste ternary lithium battery comprises the following steps:
A. pretreating a waste ternary lithium battery to obtain waste anode material powder;
B. mixing an acidic inorganic substance and an organic acid to prepare a mixed acid solution, adding waste anode material powder into the mixed acid solution, leaching under a high-temperature and pressurized condition, and filtering after the reaction is finished to obtain a reaction filtrate;
C. and adding an alkali solution into the reaction filtrate, and recovering by adopting a precipitation method to obtain a nickel-cobalt-manganese ternary positive electrode 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 beneficial to activating a leaching system and intensifying the chemical reaction degree, but the high temperature is easy to decompose and sublimate organic acid, the oxalic acid used in the invention is taken as an example, the theoretical thermal decomposition temperature of the oxalic acid is 157 ℃, in industrial application, the thermal decomposition phenomenon exists when the temperature reaches 100 ℃, in addition, the leaching is easy to escape along with water vapor and is carried out below 100 ℃, and the leaching efficiency is difficult to effectively improve. In order to obviously improve the leaching efficiency of the oxalic acid and simultaneously avoid the decomposition and high-temperature escape of the oxalic acid, the invention also cooperates with a pressurizing process to carry out the leaching at the high temperature of 120-180 ℃, applies certain pressure to a leaching system, and accelerates the reaction degree while avoiding the decomposition and high-temperature escape of the oxalic acid, so that the difficult-to-leach materials become easy to leach, thereby not only not increasing the consumption of the oxalic acid, but also reducing the dosage of the oxalic acid, and obtaining higher metal recovery rate under the same acidic condition. Experiments prove that the lithium recovery rate is more than 98 percent in a short time (within 0.5-2 h), the leaching rate of the nickel, cobalt and manganese noble metals reaches more than 95 percent, and the leaching efficiency is improved obviously. Furthermore, after the high-temperature pressurizing means is adopted, the consumption of oxalic acid is reduced, so that the residual acid amount is reduced, the reduction of the residual acid amount is beneficial to the subsequent treatment of the leaching solution, the content of impurity metals such as calcium, magnesium and the like in the leaching solution is reduced, the impurity content in the recovered ternary cathode material precursor is effectively controlled, and the quality of the recovered product is improved.
Therefore, the invention greatly improves the process dynamic condition by a high-temperature pressure leaching mode, not only improves the leaching efficiency, but also reduces the usage 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.
Further, in the step B, the temperature of the high-temperature pressure leaching is 120 to 180 ℃, for example, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 180 ℃ or the like, and the pressure is 0.5 to 1.0MPa, for example, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 1.0MPa or the like.
Further, in the step B, the high-temperature pressure leaching time is 0.5-2h (for example, 0.5h, 1.0h, 1.5h, 2h and the like can be realized), and the stirring speed is 300-800r/min, for example, 300r/min, 350r/min, 400r/min, 500r/min, 600r/min, 800r/min and the like can be realized.
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 to 8, and may be, for example, 6.
Further, the mixed acid solution also contains d-glucose. The introduction of d-glucose helps to further improve the leaching efficiency, and also helps to make the whole leaching system more stable in leaching.
Further, the molar ratio of oxalic acid, ammonium sulfate and d-glucose is 6-8.
Further, in the step B, the solid-to-liquid ratio of the mixed acid solution to the waste cathode material powder is 10-50g/L, for example, 10g/L, 20g/L, 25g/L, 30g/L, 40g/L, 50g/L, etc.
Further, the concentration of oxalic acid in the mixed acid solution is 1 to 2mol/L, for example, 1mol/L, 1.25mol/L, 1.5mol/L, 1.8mol/L, 2mol/L, etc.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that: the invention designs a mixed acid leaching system mainly comprising organic acid, and simultaneously cooperates with high-temperature pressure leaching conditions, thereby not only realizing selective leaching of nickel, cobalt, manganese and lithium elements with total selectivity more than 98%, but also overcoming the problem of low leaching efficiency of the organic acid, shortening the leaching period, reducing the usage amount of the organic acid and the impurity content in the recovered product, reducing the recovery cost, improving the quality of the recovered product, ensuring that the leaching process is environment-friendly, and being beneficial to realizing industrial application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A method for recycling and preparing a ternary cathode material precursor by utilizing a waste ternary lithium battery 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 a positive active component, and ultrasonically stripping the positive active component on the aluminum foil to obtain waste positive material powder;
B. mixing oxalic acid, ammonium sulfate and d-glucose according to a molar ratio of 8 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 precipitate and recover metal nickel, cobalt and manganese, filtering, carrying out solid-liquid separation, drying the precipitate, recycling the filtrate, calcining the dried precipitate at 700 ℃ for 6h to obtain a nickel, cobalt and manganese ternary cathode material precursor, wherein the content of calcium and magnesium in the nickel, cobalt and manganese ternary cathode material precursor is 0.018%, and the content of calcium and magnesium is reduced by 0.1-0.3% compared with that in the traditional organic acid process.
Example 2
A method for recycling and preparing a ternary cathode material precursor by using a waste ternary lithium battery 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 a positive active component, and ultrasonically stripping the positive active component on the aluminum foil to obtain waste positive material powder;
B. mixing oxalic acid, ammonium sulfate and d-glucose according to a molar ratio of 6 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 precipitate and recover metal nickel, cobalt and manganese, drying the precipitate after filtering and solid-liquid separation, recycling the filtrate, calcining the dried precipitate at 800 ℃ for 5 hours to obtain a nickel, cobalt and manganese ternary cathode material precursor, wherein the content of calcium and magnesium in the nickel, cobalt and manganese ternary cathode material precursor is 0.012 percent, and 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 recycling and preparing a ternary cathode material precursor by utilizing a waste ternary lithium battery 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 a positive active component, and ultrasonically stripping the positive active component on the aluminum foil to obtain waste positive material powder;
B. mixing oxalic acid, ammonium sulfate and d-glucose according to a molar ratio of 8 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 precipitate and recover metal nickel, cobalt and manganese, drying the precipitate after filtering and solid-liquid separation, recycling the filtrate, calcining the dried precipitate at 750 ℃ for 6h to obtain a nickel, cobalt and manganese ternary cathode material precursor, wherein the content of calcium and magnesium in the nickel, cobalt and manganese ternary cathode material precursor is 0.011 percent and is reduced by 0.1-0.3 percent compared with the traditional organic acid leaching process.
Example 4
A method for recycling and preparing a ternary cathode material precursor by utilizing a waste ternary lithium battery 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 a positive active component, and ultrasonically stripping the positive active component on the aluminum foil to obtain waste positive material powder;
B. mixing oxalic acid, ammonium sulfate and d-glucose according to a molar ratio of 7Respectively, the leaching rates of 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 precipitate and recover metal nickel, cobalt and manganese, drying the precipitate after filtering and solid-liquid separation, recycling the filtrate, calcining the dried precipitate at 650 ℃ for 8h to obtain a nickel, cobalt and manganese ternary cathode material precursor, wherein the content of calcium and magnesium in the nickel, cobalt and manganese ternary cathode material precursor is 0.015 percent and is reduced by 0.1-0.3 percent compared with the traditional organic acid leaching process.
Comparative example 1
Comparative example 1 is the same as example 1 except that the leaching process was carried out at 80 c under atmospheric pressure for 1 hour. The leaching rates of valuable metals lithium, nickel, cobalt and manganese in the reaction filtrate are respectively measured as E by ICP Li ＝87.4％、E Ni ＝83.3％、E Co ＝77.6％、E Mn =81.6%. Therefore, the leaching efficiency is low when the leaching is carried out under the conventional temperature and normal pressure conditions, 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 atmospheric pressure. In the leaching process, acidic gas escapes to obviously influence the ambient environment, and ICP is used for measuring the leaching rates of valuable metals lithium, nickel, cobalt and manganese in the reaction filtrate as E respectively 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 rates, the leaching rate is still lower although the leaching efficiency is not obviously changed, which is obviously inferior to that of the embodiment 1, and acid gas is generated in the leaching process, so that the environmental pollution is caused, and the method is difficult to be applied to industrialization.
Comparative example 3
Comparative example 3 is the same as comparative example 1 except that the leaching process was carried out at 80 c under a pressure of 0.8MPa for 1 hour. ICP is used for measuring leaching rate of valuable metals lithium, nickel, cobalt and manganese in reaction filtrateIs other than E Li ＝86.3％、E Ni ＝74.1％、E Co ＝83.1％、E Mn =78.3%. By comparing the leaching rates, the leaching efficiency of the mixed acid solution cannot be obviously improved by the pressurization mode in the conventional leaching system.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
1. A method for recycling and preparing a ternary cathode material precursor by utilizing a 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 an acidic inorganic substance and an organic acid to prepare a mixed acid solution, adding the waste anode material powder into the mixed acid solution, leaching under the condition of high temperature and pressurization, and filtering after the reaction is finished to obtain a reaction filtrate;
C. and adding an alkali solution into the reaction filtrate, and recovering by adopting a precipitation method to obtain the precursor of the nickel-cobalt-manganese ternary positive electrode material.
2. The method for recycling and preparing the precursor of the ternary cathode material by using the waste ternary lithium battery as claimed in claim 1, wherein in the step B, the temperature of the high-temperature pressure leaching is 120-180 ℃, and the pressure is 0.5-1.0MPa.
3. The method for recycling and preparing the precursor of the ternary cathode material by using the waste ternary lithium battery as claimed in claim 2, wherein in the step B, the high-temperature pressure leaching time is 0.5-2h, and the stirring speed is 300-800r/min.
4. The method for recycling and preparing the ternary cathode material precursor by using the waste ternary lithium battery as claimed in any one of claims 1 to 3, wherein in the mixed acid solution, the acidic inorganic substance is ammonium sulfate, and the organic acid is oxalic acid.
5. The method for recycling and preparing the ternary cathode material precursor by using the waste ternary lithium battery as claimed in claim 4, wherein the molar ratio of oxalic acid to ammonium sulfate is 6-8.
6. The method for recycling and preparing the ternary cathode material precursor by using the waste ternary lithium battery as claimed in claim 5, wherein the molar ratio of oxalic acid to ammonium sulfate is 8.
7. The method for recycling and preparing the precursor of the ternary cathode material by using the waste ternary lithium battery as claimed in claim 5, wherein the mixed acid solution further contains d-glucose.
8. The method for recycling and preparing the ternary positive material precursor by using the waste ternary lithium battery as claimed in claim 7, wherein the molar ratio of oxalic acid, ammonium sulfate and d-glucose is 6-8.
9. The method for recycling and preparing the ternary cathode material precursor by using the waste ternary lithium battery as claimed in claim 8, wherein in the step B, the solid-to-liquid ratio of the mixed acid solution to the waste cathode material powder is 10-50g/L.
10. The method for recycling and preparing the precursor of the ternary cathode material by using the waste ternary lithium battery as claimed in claim 9, wherein the concentration of oxalic acid in the mixed acid solution is 1-2mol/L.
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