CN115896461B - Method for recycling waste lithium batteries by extracting lithium from ammonia - Google Patents
Method for recycling waste lithium batteries by extracting lithium from ammonia Download PDFInfo
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- CN115896461B CN115896461B CN202211655110.2A CN202211655110A CN115896461B CN 115896461 B CN115896461 B CN 115896461B CN 202211655110 A CN202211655110 A CN 202211655110A CN 115896461 B CN115896461 B CN 115896461B
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002699 waste material Substances 0.000 title claims abstract description 35
- 238000004064 recycling Methods 0.000 title claims abstract description 11
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 56
- 238000002386 leaching Methods 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 26
- 239000002002 slurry Substances 0.000 claims abstract description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 22
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011888 foil Substances 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- XTOOSYPCCZOKMC-UHFFFAOYSA-L [OH-].[OH-].[Co].[Ni++] Chemical compound [OH-].[OH-].[Co].[Ni++] XTOOSYPCCZOKMC-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010439 graphite Substances 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 10
- 239000002893 slag Substances 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000008020 evaporation Effects 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 37
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 21
- 229910001416 lithium ion Inorganic materials 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- 238000007654 immersion Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 235000015173 baked goods and baking mixes Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 12
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 238000000197 pyrolysis Methods 0.000 abstract description 7
- 238000003795 desorption Methods 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 16
- 230000008569 process Effects 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000004317 sodium nitrate Substances 0.000 description 8
- 235000010344 sodium nitrate Nutrition 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- -1 hydrogen ions Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000021110 pickles Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007133 aluminothermic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical class [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002604 ultrasonography 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 waste lithium batteries by ammonia leaching lithium, which comprises the steps of crushing waste lithium batteries, drying to remove electrolyte, mixing with sodium nitrite, heating, removing positive electrode powder, adding ammonia water to quickly dissolve sodium salt, screening to obtain copper aluminum foil and slurry, soaking the slurry, adding calcium nitrate to obtain graphite slag and ammonia leaching solution, performing ammonia distillation treatment to obtain cobalt nickel hydroxide and lithium-containing solution, introducing carbon dioxide to precipitate lithium, and evaporating and concentrating the sodium salt solution to obtain sodium nitrite. The invention adopts the combined treatment of fused salt pyrolysis desorption, ammonia leaching lithium, ammonia evaporation and precipitation, and high-value copper aluminum foil, lithium carbonate and crude cobalt nickel hydroxide are recovered and obtained, and regenerated sodium nitrite is continuously used as fused salt.
Description
Technical Field
The invention belongs to the technical field of battery recovery, and particularly relates to a method for recovering waste lithium batteries by extracting lithium from ammonia.
Background
With the rapid updating of electronic products and the rapid development of power automobiles, more and more waste lithium ion batteries are generated. The waste lithium ion battery contains a large amount of toxic and harmful substances, which can cause serious harm to the environment and human health, and in addition, the waste lithium ion battery contains abundant valuable metals and can be used as important secondary resources, so that the recovery of the waste lithium ion battery has become a hot spot of global concern.
The leaching of the battery powder refers to that valuable metals in the obtained positive electrode active material powder are converted into water-soluble ionic states from oxide states by a hydrometallurgy method to obtain enriched metal ions (Li + ，Ni 2+ ，Co 2+ And Mn of 2+ Etc.). The leaching process is a key step for recovering valuable metal elements in the waste lithium ion batteries through whole hydrometallurgy. Comprehensive related literature reports that the leaching of the positive electrode powder can be classified into inorganic acid leaching, organic acid leaching, ammonia leaching and bioleaching according to the difference of the leaching agent and the leaching method. In addition, the leaching process of valuable metal elements can be significantly enhanced by adopting auxiliary measures such as mechanochemical methods, ultrasound and electric fields.
The principle of mineral acids, organic acids and bioleaching is based on the reaction between hydrogen ions and the positive active powder in an acidic medium. The concentration of residual acid in the leachate obtained after acid leaching treatment is often high, and the pH of the complete precipitation of nickel, cobalt and manganese hydroxides is above 10 for example, so that a large amount of alkali is required to neutralize the residual acid in the leachate, which causes additional expense. Unlike the leaching methods described above, ammonia leaching is based on the interaction between ammonia ions and metal ions in a strongly alkaline environment. The ammonia leaching process avoids the problem of high concentration of residual acid in the leaching solution obtained in the acid leaching process, and can realize efficient leaching of Co and Ni without leaching of Mn and Al basically by adjusting the composition of the leaching agent. However, there are few studies on the treatment of leachate following the ammonia leaching process.
In addition, in the recycling process of the battery powder, a pyrolysis pretreatment process is often adopted to remove the binder, so that the black powder is fallen off, the binder is decomposed at a higher temperature, otherwise, the black powder is lost due to incomplete stripping, but the higher pyrolysis temperature has a higher safety risk, such as severe local combustion reaction, the instant temperature rise caused by aluminothermic reaction, copper and aluminum are oxidized by pyrolysis, part of oxidized copper and aluminum can enter the battery powder, the cost of subsequent purification is increased, and the copper and aluminum oxidation condition can be improved by anaerobic pyrolysis through inert gas, but the current equipment is difficult to achieve complete sealing, and the copper and aluminum are still partially oxidized.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a method for recovering waste lithium batteries by extracting lithium with ammonia, which is characterized in that positive and negative electrode powder is separated by low-temperature molten salt co-heating to obtain complete copper aluminum foil, and further ammonia leaching is carried out to recover transition metal elements.
According to one aspect of the invention, a method for recovering waste lithium batteries by extracting lithium from ammonia is provided, which comprises the following steps:
s1: discharging, disassembling and crushing the waste lithium ion batteries, and heating and drying the obtained crushed materials to obtain a dried material;
s2: mixing the drying material with sodium nitrite, heating to 280-320 ℃ for reaction, adding ammonia water after the reaction is finished, and sieving the obtained mixture to obtain copper-aluminum foil and slurry;
s3: adding calcium nitrate into the slurry, heating for reaction, and performing solid-liquid separation after the reaction is finished to obtain graphite slag and ammonia immersion liquid;
s4: heating the ammonia leaching solution to distill ammonia, and carrying out solid-liquid separation to obtain crude cobalt nickel hydroxide and lithium-containing solution;
s5: introducing carbon dioxide into the lithium-containing solution to perform lithium precipitation reaction, performing solid-liquid separation to obtain lithium carbonate and sodium salt solution, adding nitrous acid into the sodium salt solution to adjust pH, and performing evaporation concentration to obtain sodium nitrite crystals.
In some embodiments of the invention, in step S1, the crushed material has a particle size of 5cm or less.
In some embodiments of the present invention, in step S1, the waste lithium ion battery is at least one of a ternary lithium ion battery, a lithium cobaltate battery or a lithium nickelate battery.
In some embodiments of the present invention, in step S1, the temperature of the heating and drying is 180-200 ℃. Further, the heating and drying time is 1-2h. The purpose of the heat drying is to remove the electrolyte.
In some embodiments of the present invention, in step S2, the mass ratio of the drying material to sodium nitrite is 1: (1.5-2.0).
In some embodiments of the invention, in step S2, the reaction time is 1-2 hours.
In some embodiments of the invention, in step S2, the screened mesh size is 2-3mm.
In some embodiments of the invention, in step S2, the solid-to-liquid ratio of the reacted material to the aqueous ammonia is 1g: (5-10) mL, wherein the concentration of the ammonia water is 4-10mol/L.
In some embodiments of the present invention, in step S3, the calcium nitrate is added in an amount of 2% -5% of the mass of the baked goods.
In some embodiments of the present invention, in step S3, the heating reaction is performed at a temperature of 40 to 60 ℃ for a time of 8 to 12 hours.
In some embodiments of the invention, in step S4, the temperature of the heated ammonia distillation is 70-90 ℃.
In some embodiments of the invention, in step S4, the heating evaporates ammonia until the ammonia concentration in the ammonia immersion liquid is below 10mg/L.
In some embodiments of the invention, in step S5, the pH is 8-9.
According to a preferred embodiment of the invention, there is at least the following advantageous effect:
1. according to the invention, aiming at the problems that the waste lithium ion battery is extremely easy to have potential safety hazard at a higher pyrolysis temperature, copper and aluminum are oxidized in a large area and the acid leaching process has large residual acid quantity, the combined treatment of fused salt pyrolysis desorption, ammonia leaching lithium and ammonia evaporation precipitation is adopted, high-value copper aluminum foil, lithium carbonate and crude cobalt nickel hydroxide (MHP) are recovered, and sodium nitrite is regenerated to be continuously used as fused salt.
2. Firstly, crushing a waste lithium battery, drying to remove electrolyte, mixing the crushed waste lithium battery with sodium nitrite, heating the mixture, wherein the sodium nitrite has high reducibility and high oxidability in a molten state, and the binder on the positive plate is melted and oxidized and decomposed by the sodium nitrite when the sodium nitrite is melted, so that positive electrode powder is dropped off, the sodium nitrite also has a certain reducibility and can further react with the positive electrode powder, the subsequent leaching process is facilitated, the ammonia leaching efficiency is improved, and the main reaction formula is as follows;
NaNO 2 +2LiCoO 2 →NaNO 3 +2CoO+Li 2 O
the sodium salt can be quickly dissolved by ammonia water, and the mixture is screened to obtain the complete copper-aluminum foil;
further soaking to dissolve nickel and cobalt, adding calcium nitrate, precipitating fluoride ions and phosphate ions, avoiding combination with lithium ions to generate precipitate, and reducing lithium yield, wherein the main reaction formula is as follows;
6NH 3 ·H 2 O+CoO→[Co(NH 3 ) 6 ] 2+ +2OH - +5H 2 O
finally, ammonia distillation treatment is carried out, and nickel cobalt gradually forms precipitation along with the reduction of ammonia concentration, so as to obtain crude cobalt nickel hydroxide; meanwhile, sodium nitrate has stronger oxidizing property and is reduced by ammonia water, so that only Li, na and NO are present in the solution 2 - And (3) introducing carbon dioxide into ammonia water, precipitating and separating out lithium carbonate, adding nitrous acid to adjust pH, evaporating and concentrating to obtain recovered sodium nitrite, and reusing the recovered sodium nitrite as molten salt for desorption.
3. Compared with other molten salt desorption modes, the sodium nitrite is favorable for further reduction of the anode material, the leaching efficiency is improved, meanwhile, as the sodium nitrate has oxidability and is difficult to react with the anode material, the generated sodium nitrate is consumed in the subsequent reaction with ammonia water, and the ammonia water is used as a leaching agent and a reducing agent, so that the problem of recycling a large amount of sodium nitrate remained in the obtained sodium nitrite is avoided, and the recycled sodium nitrite can be directly used for molten salt desorption.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
fig. 1 is a process flow diagram of example 1 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The method for recycling the waste lithium battery by extracting lithium from ammonia refers to a method shown in fig. 1, and comprises the following specific steps:
step 1, after the waste ternary lithium ion battery is discharged and disassembled, crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, heating the crushed material to 180 ℃, drying for 2 hours, and removing electrolyte to obtain a dried material;
step 3, mixing the drying material and sodium nitrite according to a mass ratio of 1:1.5, heating to 310 ℃, and preserving heat for 1h;
step 4, adding the mixture into 10mol/L ammonia water according to a solid-to-liquid ratio of 1g to 5mL, and sieving through a sieve with a pore diameter of 0.25mm to obtain copper aluminum foil and slurry;
step 5, adding calcium nitrate accounting for 2% of the mass of the drying material into the slurry, and heating the slurry to 40 ℃ for 12 hours;
step 6, performing filter pressing on the slurry to obtain graphite slag and ammonia immersion liquid;
step 7, placing the ammonia immersion liquid in an evaporator, heating to 70 ℃, condensing the generated gas by a condenser to obtain ammonia water, and discharging the generated non-condensable gas until the ammonia concentration in the ammonia immersion liquid is lower than 10mg/L;
step 8, solid-liquid separation is carried out to obtain crude cobalt nickel hydroxide and lithium-containing solution;
step 9, introducing carbon dioxide into the lithium-containing solution until no precipitation is generated, and carrying out solid-liquid separation to obtain lithium carbonate and sodium salt solution;
and step 10, adding nitrous acid into the sodium salt solution to adjust the pH to 8-9, evaporating and concentrating, and recovering to obtain sodium nitrite crystals.
Example 2
The method for recycling the waste lithium battery by extracting lithium from ammonia comprises the following specific processes:
step 1, after discharging and disassembling a waste lithium cobaltate battery, crushing the waste lithium cobaltate battery into a crushed material with granularity below 5 cm;
step 2, heating the crushed material to 190 ℃, drying for 1.5 hours, and removing electrolyte to obtain a dried material;
step 3, mixing the drying material and sodium nitrite according to a mass ratio of 1:1.8, heating to 300 ℃, and preserving heat for 1.5 hours;
step 4, adding the mixture into 7mol/L ammonia water according to a solid-to-liquid ratio of 1g to 8mL, and sieving the mixture through a sieve with the aperture of 0.25mm to obtain copper aluminum foil and slurry;
step 5, adding calcium nitrate accounting for 4% of the mass of the drying material into the slurry, and heating the slurry to 50 ℃ for 10 hours;
step 6, performing filter pressing on the slurry to obtain graphite slag and ammonia immersion liquid;
step 7, placing the ammonia immersion liquid in an evaporator, heating to 80 ℃, condensing the generated gas by a condenser to obtain ammonia water, and discharging the generated non-condensable gas until the ammonia concentration in the ammonia immersion liquid is lower than 10mg/L;
step 8, solid-liquid separation is carried out to obtain crude cobalt nickel hydroxide and lithium-containing solution;
step 9, introducing carbon dioxide into the lithium-containing solution until no precipitation is generated, and carrying out solid-liquid separation to obtain lithium carbonate and sodium salt solution;
and step 10, adding nitrous acid into the sodium salt solution to adjust the pH to 8-9, evaporating and concentrating, and recovering to obtain sodium nitrite crystals.
Example 3
The method for recycling the waste lithium battery by extracting lithium from ammonia comprises the following specific processes:
step 1, after the waste ternary lithium ion battery is discharged and disassembled, crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, heating the crushed material to 200 ℃, drying for 1h, and removing electrolyte to obtain a dried material;
step 3, mixing the drying material and sodium nitrite according to a mass ratio of 1:2.0, heating to 290 ℃, and preserving heat for 1h;
step 4, adding the mixture into ammonia water with the concentration of 4mol/L according to the solid-to-liquid ratio of 1g to 10mL, and sieving the mixture through a sieve with the aperture of 0.25mm to obtain copper aluminum foil and slurry;
step 5, adding calcium nitrate accounting for 5% of the mass of the drying material into the slurry, and heating the slurry to 60 ℃ for 8 hours;
step 6, performing filter pressing on the slurry to obtain graphite slag and ammonia immersion liquid;
step 7, placing the ammonia immersion liquid in an evaporator, heating to 90 ℃, condensing the generated gas by a condenser to obtain ammonia water, and discharging the generated non-condensable gas until the ammonia concentration in the ammonia immersion liquid is lower than 10mg/L;
step 8, solid-liquid separation is carried out to obtain crude cobalt nickel hydroxide and lithium-containing solution;
step 9, introducing carbon dioxide into the lithium-containing solution until no precipitation is generated, and carrying out solid-liquid separation to obtain lithium carbonate and sodium salt solution;
and step 10, adding nitrous acid into the sodium salt solution to adjust the pH to 8-9, evaporating and concentrating, and recovering to obtain sodium nitrite crystals.
Comparative example 1
The method for recycling waste lithium batteries by leaching lithium with ammonia is different from the method in the embodiment 1 in that the molten salt in the step 3 is sodium nitrate, and the molten salt is centrifugally separated when the molten salt is hot, and the specific process is as follows:
step 1, after the waste ternary lithium ion battery is discharged and disassembled, crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, heating the crushed material to 180 ℃, drying for 2 hours, and removing electrolyte to obtain a dried material;
step 3, mixing the baking material and sodium nitrate according to the mass ratio of 1:1.5, heating to 310 ℃, preserving heat for 1h, and centrifuging to separate molten salt at the temperature to obtain a solid material (so as to avoid consumption of a large amount of ammonia water by sodium nitrate);
step 4, adding the solid material into 10mol/L ammonia water according to a solid-to-liquid ratio of 1g to 5mL, and sieving through a sieve with a pore diameter of 0.25mm to obtain copper aluminum foil and slurry;
step 5, adding calcium nitrate accounting for 2% of the mass of the drying material into the slurry, and heating the slurry to 40 ℃ for 12 hours;
step 6, performing filter pressing on the slurry to obtain graphite slag and ammonia immersion liquid;
step 7, placing the ammonia immersion liquid in an evaporator, heating to 70 ℃, condensing the generated gas by a condenser to obtain ammonia water, and discharging the generated non-condensable gas until the ammonia concentration in the ammonia immersion liquid is lower than 10mg/L;
step 8, solid-liquid separation is carried out to obtain crude cobalt nickel hydroxide and lithium-containing solution;
step 9, introducing carbon dioxide into the lithium-containing solution until no sediment is generated, and carrying out solid-liquid separation to obtain lithium carbonate and wastewater;
and step 10, adding nitrous acid into the wastewater to adjust the pH to 8-9, and evaporating and concentrating to obtain sodium salt crystals.
Comparative example 2
The method for recycling waste lithium batteries by leaching lithium with ammonia is different from the method in the embodiment 3 in that the step 4 replaces ammonia water with hydrochloric acid, and the specific process is as follows:
step 1, after the waste ternary lithium ion battery is discharged and disassembled, crushing the waste ternary lithium ion battery into a crushed material with the granularity of less than 5 cm;
step 2, heating the crushed material to 200 ℃, drying for 1h, and removing electrolyte to obtain a dried material;
step 3, mixing the drying material and sodium nitrite according to a mass ratio of 1:2.0, heating to 290 ℃, and preserving heat for 1h;
step 4, adding the mixture into hydrochloric acid with the concentration of 4mol/L according to the solid-to-liquid ratio of 1g to 10mL, and sieving the mixture through a sieve with the aperture of 0.25mm to obtain copper aluminum foil and slurry;
step 5, adding calcium nitrate accounting for 5% of the mass of the drying material into the slurry, and heating the slurry to 60 ℃ for 8 hours;
step 6, performing filter pressing on the slurry to obtain graphite slag and pickle liquor;
step 7, adding sodium hydroxide into the pickle liquor to adjust the pH to 10.5-11.0;
step 8, solid-liquid separation is carried out to obtain crude cobalt nickel hydroxide and lithium-containing solution;
step 9, introducing carbon dioxide into the lithium-containing solution until no precipitation is generated, and carrying out solid-liquid separation to obtain lithium carbonate and sodium salt solution;
and step 10, evaporating and concentrating the sodium salt solution, and recovering to obtain sodium salt crystals.
The graphite slag, copper aluminum foil and sodium salt crystals of the examples and comparative examples were examined, and the results are shown in table 1.
TABLE 1
As can be seen from table 1, the graphite slag of comparative example 1 has high nickel and cobalt content, which indicates that the ammonia leaching rate is low, a large amount of nickel and cobalt remains, and sodium nitrate cannot play a role in promoting leaching; in comparative example 2, acid leaching is adopted, a large amount of sodium salt is introduced, and nitrite ions are easy to decompose under strong acid, so that the content of sodium nitrite in the recovered sodium salt crystals is low.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The method for recycling the waste lithium battery by extracting lithium from ammonia is characterized by comprising the following steps of:
s1: discharging, disassembling and crushing the waste lithium ion batteries, and heating and drying the obtained crushed materials to obtain a dried material;
s2: mixing the drying material with sodium nitrite, heating to 280-320 ℃ for reaction, adding ammonia water after the reaction is finished, and sieving the obtained mixture to obtain copper-aluminum foil and slurry;
s3: adding calcium nitrate into the slurry, heating for reaction, and performing solid-liquid separation after the reaction is finished to obtain graphite slag and ammonia immersion liquid;
s4: heating the ammonia leaching solution to distill ammonia, and carrying out solid-liquid separation to obtain crude cobalt nickel hydroxide and lithium-containing solution;
s5: introducing carbon dioxide into the lithium-containing solution to perform lithium precipitation reaction, performing solid-liquid separation to obtain lithium carbonate and sodium salt solution, adding nitrous acid into the sodium salt solution to adjust pH, and performing evaporation concentration to obtain sodium nitrite crystals.
2. The method according to claim 1, wherein in step S1, the particle size of the crushed material is less than or equal to 5cm.
3. The method of claim 1, wherein in step S1, the waste lithium ion battery is a ternary lithium ion battery.
4. The method according to claim 1, wherein in step S1, the temperature of the heat-drying is 180-200 ℃.
5. The method according to claim 1, wherein in step S2, the mass ratio of the drying material to sodium nitrite is 1: (1.5-2.0).
6. The method according to claim 1, wherein in step S2, the solid-to-liquid ratio of the reacted material to the aqueous ammonia is 1g: (5-10) mL, wherein the concentration of the ammonia water is 4-10mol/L.
7. The method according to claim 1, wherein in the step S3, the calcium nitrate is added in an amount of 2% -5% of the mass of the baked goods.
8. The method according to claim 1, wherein in step S3, the heating reaction is performed at a temperature of 40 to 60 ℃ for a time of 8 to 12 hours.
9. The method according to claim 1, wherein in step S4, the temperature of the heated ammonia is 70-90 ℃.
10. The method according to claim 1, wherein in step S5, the pH is 8-9.
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| CN107017443A (en) * | 2017-03-28 | 2017-08-04 | 北京科技大学 | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery |
| JP2018040035A (en) * | 2016-09-07 | 2018-03-15 | Ｊｘ金属株式会社 | Process for treating lithium-ion battery scrap |
| CN109193057A (en) * | 2018-09-07 | 2019-01-11 | 昆明理工大学 | A method of positive electrode material precursor is prepared using waste and old ternary lithium battery |
| CN111690812A (en) * | 2020-06-15 | 2020-09-22 | 南方科技大学 | Recovery method of waste ternary lithium battery |
| CN115058605A (en) * | 2022-06-29 | 2022-09-16 | 广东邦普循环科技有限公司 | Method for recovering waste lithium battery material |
| CN115161483A (en) * | 2022-07-05 | 2022-10-11 | 广西师范大学 | Method for fully recycling waste lithium ion batteries and realizing metal separation |
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| JP2018040035A (en) * | 2016-09-07 | 2018-03-15 | Ｊｘ金属株式会社 | Process for treating lithium-ion battery scrap |
| CN107017443A (en) * | 2017-03-28 | 2017-08-04 | 北京科技大学 | A kind of method of the comprehensively recovering valuable metal from waste and old lithium ion battery |
| CN109193057A (en) * | 2018-09-07 | 2019-01-11 | 昆明理工大学 | A method of positive electrode material precursor is prepared using waste and old ternary lithium battery |
| CN111690812A (en) * | 2020-06-15 | 2020-09-22 | 南方科技大学 | Recovery method of waste ternary lithium battery |
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