CN113621802A - Method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole piece - Google Patents
Method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole piece Download PDFInfo
- Publication number
- CN113621802A CN113621802A CN202010375997.4A CN202010375997A CN113621802A CN 113621802 A CN113621802 A CN 113621802A CN 202010375997 A CN202010375997 A CN 202010375997A CN 113621802 A CN113621802 A CN 113621802A
- Authority
- CN
- China
- Prior art keywords
- waste
- cobalt
- manganese
- lithium
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000010941 cobalt Substances 0.000 title claims abstract description 41
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 41
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 41
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 41
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 36
- 239000011572 manganese Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims description 18
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000003480 eluent Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000011888 foil Substances 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 238000012360 testing method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000012634 fragment Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 4
- 239000010926 waste battery Substances 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000010828 elution Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 239000012445 acidic reagent Substances 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 39
- 238000000605 extraction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 7
- 238000010248 power generation Methods 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 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 4
- 239000003292 glue Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for recovering nickel, cobalt, manganese and lithium from waste ternary battery pole pieces, which comprises the steps of eluting ternary waste from a battery pole piece by using an eluent to separate the ternary waste from an aluminum foil, then separating the dissolved waste from an organic solvent, repeatedly using the eluent, adding an acid reagent into filtered ternary powder, crushing and dissolving out the ternary powder, and filtering (rubber) carbon to obtain a nickel, cobalt, manganese and lithium mixed solution and the like. The invention mainly adopts wet elution and dissolution processes, has low energy consumption, environmental protection, high dissolution rate of valuable components, good economic benefit and wide application prospect.
Description
Technical Field
The invention relates to the technical field of waste battery recovery, in particular to a method for recovering nickel, cobalt, manganese and lithium from waste ternary battery pole pieces.
Technical Field
The automobile is an important transportation tool in modern society, and provides comfortable and convenient travel service for people. However, the traditional fuel oil produces a large amount of harmful waste gas in the using process, which generates huge environmental pressure and further increases the dependence on the traditional non-renewable petroleum resources. Nowadays, with increasingly severe forms of energy and environment, new energy automobiles have the remarkable characteristics of cleanness and energy conservation, and become a new industry which is paid more attention in all countries in the world. China is a large population country and a country with large resource consumption, and the environment is overwhelmed after decades of wild development. Today of industrialization and urbanization, the new energy automobile industry is very consistent with the basic ideas of sustainable development and resource-intensive and environment-friendly equipment in China. Therefore, the government of China increases the investment and the supporting strength of the electric automobile at present. Under such a large policy environment, the domestic new energy automobile industry is developed vigorously. The lithium ion ternary cathode material is widely applied to the fields of new energy automobiles, energy storage batteries and the like due to high energy density. However, in the use process of the battery, the battery is inevitably scrapped and retired, the battery has potential safety hazards, and simultaneously contains a large amount of valuable components, particularly the anode material contains a large amount of rare elements such as nickel, cobalt and lithium, and has important recycling value and significance.
At present, a lot of methods for recycling ternary battery waste materials are provided, and patents CN201711338941.6 and CN108439438A both refer to a method for recycling ternary positive electrode materials, the ternary positive electrode materials are treated by falling off and dissolving out of a pole piece, and a roasting (burning) -acid dissolving process is adopted to recycle nickel, cobalt, manganese, lithium and the like in waste batteries, although the process is simple, the process relates to high-temperature sol (400-700 ℃), a large amount of energy consumption is needed, in addition, the investment cost of high-temperature equipment is high, and the operating environment is poor.
This patent chooses for use, act as the eluant with organic solvent and elute, wash the anodal waste material from the aluminium foil fast, reach the separation of powder and aluminium foil, a large amount of energy consumptions that high temperature melten gel brought have been avoided simultaneously, and when acidification dissolves the powder, adopt the ball-milling mode of dissolving, will be exposed by the ternary anodal material of colloid and carbon-layer parcel through the ball-milling, reached not high temperature sintering and also not destroy the purpose of ternary anodal material waste material, this method furthest's reduction traditional high temperature technology, reduce the energy consumption, green.
Disclosure of Invention
The invention discloses a method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole pieces. The method mainly provides a method for eluting the waste material from the pole piece, which is green, cyclic, efficient, simple and low in energy consumption. The technical problem to be solved by the invention is realized by adopting the following technical scheme:
a method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole pieces comprises the following steps:
1) disassembling the waste battery, and crushing the disassembled positive plate into fragments with the size of 1cm multiplied by 1 cm-10 cm multiplied by 10 cm;
2) preparing an eluent from a solvent and an additive according to a ratio, weighing the waste ternary positive fragments and the eluent, wherein the weighing solid-liquid ratio is 1: (1.0-5.0);
3) placing the weighed waste ternary positive plate and an eluant into a washing and dehydrating machine, stirring and soaking for 1-5 hours to ensure that the powder is eluted from the foil;
4) filtering the eluted powder and the foil to obtain a foil and an eluant turbid liquid containing the powder; further filtering the turbid solution to obtain powder slurry with high solid content and an eluant, and recovering the eluant for recycling;
5) placing the filtered powder in a heat preservation device, preserving heat for 1-5 hours at the temperature of 60-100 ℃, evaporating to remove the eluent carried in the powder, condensing and recycling the eluent, and testing the collected powder to obtain the contents of valuable components such as lithium, nickel, cobalt, manganese and the like;
6) mixing the evaporated powder waste with an acid solution according to the element content tested in the powder in 5), wherein the mixing ratio is n waste: n (H)+) Dissolving the powder (1) (2.0-2.8) in a ball mill;
7) taking out the dissolved turbid liquid from the ball mill, and filtering the turbid liquid by using a filtering device to obtain primary filter residue and primary filter liquid;
8) and washing and filtering the primary filter residue twice by using deionized water to obtain secondary filter liquor, tertiary filter liquor and tertiary filter residue, adding acid into the tertiary filter liquor to serve as next leaching liquor, mixing the secondary filter liquor and the primary filter liquor to obtain nickel, cobalt, manganese and lithium, and calculating the leaching rate.
Preferably, the eluent in the step 1) mainly comprises N-methyl pyrrolidone (NMP) solution.
Preferably, the additive component in the eluent in the step 1) comprises at least one of Dimethylformamide (DMF) and N-methyl-methanol amide (NMF), and the addition amount thereof is m eluent: m is 1 (0.1 to 0.5).
Preferably, the acid in 6) comprises at least one of hydrochloric acid, sulfuric acid and nitric acid, and the acid concentration is C (H)+)＝2～4mol/L。
Compared with the prior art, the invention has the beneficial effects that:
1. the invention selects N-methyl pyrrolidone as eluent, because the N-methyl pyrrolidone can dissolve the common colloid PVDF in the battery to a certain extent; meanwhile, additives of Dimethylformamide (DMF) and N-methyl-methanol amide (NMF) are introduced, PVDF colloid can be rapidly and effectively separated by the additives, and the problem that powder is bonded on a pole piece is solved; and because the N-methyl pyrrolidone is harmless to human bodies, green, environment-friendly and volatile, the N-methyl pyrrolidone carried in the powder can be completely volatilized only by keeping the temperature of 60-100 ℃ for 1-5 hours, and the method is efficient and energy-saving.
2. When the waste is dissolved by acid, ball milling equipment is selected, and the waste is continuously impacted and crushed by the balls in the ball mill, so that the colloid-coated ternary waste can be broken and ground to be exposed, and the waste can be conveniently dissolved by the acid; on the other hand, the stirring strengthening effect can be achieved, so that the problem that the particles are not sintered and are wrapped by colloid is solved.
3. According to the method, an organic solvent is used as an eluent for elution, the anode waste is quickly washed from the aluminum foil, the separation of powder and the aluminum foil is achieved, meanwhile, a large amount of energy consumption caused by high-temperature glue melting is avoided, when the powder is dissolved by adding acid, a ball milling dissolving mode is adopted, the ternary anode material wrapped by the glue and the carbon layer is exposed through ball milling, and the purpose that the ternary anode material waste is damaged without high-temperature sintering is achieved.
Drawings
Embodiments of the invention are described below with reference to the accompanying drawings, in which:
FIG. 1 is a process flow diagram.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1(523 type)
The method comprises the steps of disassembling a scrapped automobile power battery, cutting a waste positive plate in the disassembled battery, weighing 1500g of small pieces with the size of 1cm multiplied by 10cm, preparing a stripping agent solution from 1000g of a solvent N-methyl pyrrolidone (NMP) solution and 500g of Dimethylformamide (DMF), placing the pieces in an eluant, stirring for 30min, observing that powder completely falls off from an aluminum foil, and separating the aluminum foil from a waste turbid liquid eluted. Filtering the separated waste turbid liquid to obtain clear filtrate for recycling, placing the obtained waste in an oven, keeping the temperature at 60 ℃ for 5 hours to ensure that powder is dried and removed, and measuring the components of the waste, wherein the mass contents are respectively as follows: 6.65% of lithium, 28.28% of nickel, 12.21% of cobalt, 17.08% of manganese and the balance of oxygen, carbon and other components. 207.55g (2mol) of the powder was weighed, 220g (2.2mol) of concentrated sulfuric acid having a purity of 98% was weighed, 2200g of water was added to prepare C (H) from sulfuric acid+) Adding weighed powder into dilute sulfuric acid to perform ball milling reaction for 30min, filtering to obtain 2215.8g of primary filtrate and primary filter residue, removing 500g of water to wash the primary filter residue to obtain 508.1g of secondary filtrate and secondary filter residue, and washing the secondary filter residue with 500g of deionized water to obtain 501.2g of tertiary filtrate and tertiary filter residue. The obtained primary filtrate and secondary filtrate mixed liquor is used for extracting lithium, nickel, cobalt and manganese, the obtained tertiary filtrate is used as a solvent for acid preparation when the obtained tertiary filtrate is used for dissolving waste materials subsequently, and the obtained filter residue can be used for thermal power generation and incineration power generation. Mixing the primary filtrate with the secondary filtrateThe mass contents of the elements are respectively as follows: 0.75% of lithium, 3.19% of nickel, 1.28% of cobalt and 1.79% of manganese; and testing the three filtrates to respectively obtain the following elements in mass content: 0.08 percent of lithium, 0.28 percent of nickel, 0.10 percent of cobalt and 0.17 percent of manganese. The primary and secondary mixed solutions had a lithium extraction rate of 95.20%, a nickel extraction rate of 95.10%, a cobalt extraction rate of 95.30%, a manganese extraction rate of 94.80%, a tertiary filtrate lithium extraction rate of 2.37%, a nickel extraction rate of 2.02%, a cobalt extraction rate of 1.84%, and a manganese extraction rate of 2.12%. The total dissolution rates calculated according to the first, second and third filtrates are respectively as follows: the dissolution rate of lithium was 97.57%, that of nickel was 97.12%, that of cobalt was 97.13%, and that of manganese was 96.9%.
Example 2(622 type)
The method comprises the steps of disassembling a scrapped automobile power battery, cutting a waste positive plate in the disassembled battery, weighing 1500g of small fragments with the size of 10cm multiplied by 10cm, preparing a desolventizing agent solution from 6750g of a solvent N-methyl pyrrolidone (NMP) solution and 750g of Dimethylformamide (DMF), placing the fragments in an eluant, stirring for 30min, observing that powder completely falls off from an aluminum foil, and separating the aluminum foil from waste turbid liquid eluted. Filtering the separated waste turbid liquid to obtain clear filtrate for recycling, placing the obtained waste in an oven, keeping the temperature at 100 ℃ for 1h to ensure that powder is dried and removed, and measuring the components of the waste, wherein the mass contents are respectively as follows: 6.48 percent of lithium, 33.07 percent of nickel, 11.07 percent of cobalt, 10.32 percent of manganese and the balance of oxygen, carbon and other components. 212.9g (2mol) of the powder was weighed, 584g (5.6mol) of concentrated hydrochloric acid having a purity of 35% was weighed, and 1020g of water was added to prepare C (H) from sulfuric acid+) Adding the weighed powder into dilute sulfuric acid to perform ball milling reaction for 60min and then filtering to obtain 1585.2g of primary filtrate and primary filter residue, removing 500g of water to wash the primary filter residue to obtain 525.3g of secondary filtrate and secondary filter residue, and washing the secondary filter residue with 500g of deionized water to obtain 507.6g of tertiary filtrate and tertiary filter residue. The obtained primary filtrate and secondary filtrate mixed liquor is used for extracting lithium, nickel, cobalt and manganese, the obtained tertiary filtrate is used as a solvent for acid preparation when the obtained tertiary filtrate is used for dissolving waste materials subsequently, and the obtained filter residue can be used for thermal power generation and incineration power generation. Filtering the primary filtrate and the secondary filtrateThe liquid mixing test shows that the mass contents of the elements are respectively as follows: 0.62 percent of lithium, 3.14 percent of nickel, 1.04 percent of cobalt and 0.97 percent of manganese; and testing the three filtrates to respectively obtain the following elements in mass content: 0.86% of lithium, 0.44% of nickel, 0.17% of cobalt and 0.15% of manganese. The dissolution rate of lithium was 94.30%, the dissolution rate of nickel was 94.11%, the dissolution rate of cobalt was 93.50%, the dissolution rate of manganese was 93.32%, the dissolution rate of lithium from the third filtrate was 2.89%, the dissolution rate of nickel was 2.92%, the dissolution rate of cobalt was 2.67%, and the dissolution rate of manganese was 3.12%. The total dissolution rates calculated according to the first, second and third filtrates are respectively as follows: the dissolution rate of lithium was 97.19%, the dissolution rate of nickel was 97.03%, the dissolution rate of cobalt was 96.17%, and the dissolution rate of manganese was 96.44%.
Comparative example 1(622)
The scrapped automobile power battery is disassembled, the waste positive plate in the disassembled battery is placed in a sintering furnace, the temperature is kept at 650 ℃ for 4 hours for degumming, then the temperature is reduced for 8 hours, the room temperature is reached, the degummed powder is tested, and the mass content is as follows: 6.84% of lithium, 34.89% of nickel, 11.68% of cobalt and 10.89% of manganese. 201.85g of sintered powder was weighed, 584g (5.6mol) of concentrated hydrochloric acid having a purity of 35% was added to 1020g of water to prepare C (H) from sulfuric acid+) Dissolving the diluted acid liquid in a stirring tank for 60min to obtain 1543.8g of primary filtrate and primary filter residue, removing 500g of water to wash the primary filter residue to obtain 529.8g of secondary filtrate and secondary filter residue, and washing the secondary filter residue with 500g of deionized water to obtain 502.3g of tertiary filtrate and tertiary filter residue. The obtained primary filtrate and secondary filtrate mixed liquor is used for extracting lithium, nickel, cobalt and manganese, the obtained tertiary filtrate is used as a solvent for acid preparation when the obtained tertiary filtrate is used for dissolving waste materials subsequently, and the obtained filter residue can be used for thermal power generation and incineration power generation. And mixing the primary filtrate and the secondary filtrate to test the mass contents of elements in the filtrate as follows: 0.61% of lithium, 3.10% of nickel, 1.03% of cobalt and 0.96% of manganese; and testing the three filtrates to respectively obtain the following elements in mass content: 0.07% of lithium, 0.35% of nickel, 0.11% of cobalt and 0.11% of manganese. The dissolution rate of lithium was 92.28%, the dissolution rate of nickel was 92.02%, the dissolution rate of cobalt was 91.41%, the dissolution rate of manganese was 91.41%, the dissolution rate of lithium from the third filtrate was 2.61%, the dissolution rate of nickel was 2.52%, the dissolution rate of cobalt was 2.39%, and the dissolution rate of manganese was 3.53%. Press oneThe total dissolution rates calculated by the second filtrate and the third filtrate are respectively as follows: the dissolution rate of lithium was 94.89%, the dissolution rate of nickel was 94.54%, the dissolution rate of cobalt was 93.80%, and the dissolution rate of manganese was 93.81%.
Compared with the comparative example 1, the dissolution rates of lithium, nickel, cobalt and manganese in the examples 1-2 are 1-2% higher than that in the comparative example 1, because when the anode in the comparative example 1 is subjected to high temperature, glue in the anode material is subjected to pyrolysis and carbonization, so that carbon in the waste is increased, the adsorption of slag is enhanced due to the increased carbon, and the filtrate is difficult to filter, so that the dissolution rates of lithium, nickel, cobalt and manganese in the comparative example 1 are lower than those in the examples 1-2.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. The invention discloses a method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole pieces.
A method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole pieces comprises the following steps:
1) disassembling the waste battery, and crushing the disassembled positive plate into fragments with the size of 1cm multiplied by 1 cm-10 cm multiplied by 10 cm;
2) preparing an eluent from a solvent and an additive according to a ratio, weighing the waste ternary positive fragments and the eluent, wherein the weighing solid-liquid ratio is 1: (1.0-5.0);
3) placing the weighed waste ternary positive plate and an eluant into a washing and dehydrating machine, stirring and soaking for 1-5 hours to ensure that the powder is eluted from the foil;
4) filtering the eluted powder and the foil to obtain a foil and an eluent turbid liquid containing the powder; further filtering the turbid solution to obtain powder slurry with high solid content and an eluant, and recovering the eluant for recycling;
5) and (3) placing the filtered powder in a heat preservation device, preserving the heat for 1-5 h at the temperature of 60-100 ℃, evaporating to remove the eluent carried in the powder, condensing and recycling the eluent, and testing the collected powder. Obtaining the contents of valuable components such as lithium, nickel, cobalt, manganese and the like in the solution;
6) mixing the evaporated powder waste with an acid solution according to the element content tested in the powder in 5), wherein the mixing ratio is n waste: n (H)+) Dissolving the powder (1) (2.0-2.8) in a ball mill;
7) taking out the dissolved turbid liquid from the ball mill, and filtering the turbid liquid by using a filtering device to obtain primary filter residue and primary filter liquid;
8) and washing and filtering the primary filter residue twice by using deionized water to obtain secondary filter liquor, tertiary filter liquor and tertiary filter residue, adding acid into the tertiary filter liquor to serve as next leaching liquor, mixing the secondary filter liquor and the primary filter liquor to obtain nickel, cobalt, manganese and lithium, and calculating the leaching rate.
2. The method for recycling nickel, cobalt, manganese and lithium from the waste ternary battery pole piece according to claim 1, characterized in that: the eluent in the step 1) mainly comprises N-methyl pyrrolidone (NMP) solution.
3. The method for recycling nickel, cobalt, manganese and lithium from the waste ternary battery pole piece according to claim 1, characterized in that: the additive component in the eluent in the step 1) comprises at least one of Dimethylformamide (DMF) and N-methyl-methanol amide (NMF), and the addition amount of the additive component is m eluent: m is 1 (0.1 to 0.5).
4. The method for recycling nickel, cobalt, manganese and lithium from the waste ternary battery pole piece according to claim 1, characterized in that: the acid in the 6) comprises at least one of hydrochloric acid, sulfuric acid and nitric acid, and the acid concentration is C (H)+)＝2～4mol/L。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010375997.4A CN113621802A (en) | 2020-05-07 | 2020-05-07 | Method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole piece |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010375997.4A CN113621802A (en) | 2020-05-07 | 2020-05-07 | Method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole piece |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113621802A true CN113621802A (en) | 2021-11-09 |
Family
ID=78376742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010375997.4A Withdrawn CN113621802A (en) | 2020-05-07 | 2020-05-07 | Method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole piece |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113621802A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676827A (en) * | 2012-06-01 | 2012-09-19 | 奇瑞汽车股份有限公司 | Method for recovering valuable metal from nickel cobalt lithium manganate batteries and positive pole materials |
| CN102903985A (en) * | 2012-10-22 | 2013-01-30 | 四川天齐锂业股份有限公司 | Method for recycling lithium carbonate from lithium iron phosphate waste material |
| CN106848471A (en) * | 2017-04-18 | 2017-06-13 | 中科过程（北京）科技有限公司 | A kind of nitration mixture of waste lithium ion cell anode material is leached and recovery method |
| WO2018047147A1 (en) * | 2016-09-12 | 2018-03-15 | Attero Recycling Pvt. Ltd. | Process for recovering pure cobalt and nickel from spent lithium batteries |
| CN107994288A (en) * | 2017-12-14 | 2018-05-04 | 眉山顺应动力电池材料有限公司 | Valuable metal recovery method in waste and old nickle cobalt lithium manganate ternary cell positive material |
-
2020
- 2020-05-07 CN CN202010375997.4A patent/CN113621802A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102676827A (en) * | 2012-06-01 | 2012-09-19 | 奇瑞汽车股份有限公司 | Method for recovering valuable metal from nickel cobalt lithium manganate batteries and positive pole materials |
| CN102903985A (en) * | 2012-10-22 | 2013-01-30 | 四川天齐锂业股份有限公司 | Method for recycling lithium carbonate from lithium iron phosphate waste material |
| WO2018047147A1 (en) * | 2016-09-12 | 2018-03-15 | Attero Recycling Pvt. Ltd. | Process for recovering pure cobalt and nickel from spent lithium batteries |
| CN106848471A (en) * | 2017-04-18 | 2017-06-13 | 中科过程（北京）科技有限公司 | A kind of nitration mixture of waste lithium ion cell anode material is leached and recovery method |
| CN107994288A (en) * | 2017-12-14 | 2018-05-04 | 眉山顺应动力电池材料有限公司 | Valuable metal recovery method in waste and old nickle cobalt lithium manganate ternary cell positive material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101710632B (en) | Method for recovering and restoring anode material graphite of waste lithium ion battery | |
| CN107955879B (en) | A method for recovering valuable elements in waste lithium-ion battery electrode materials | |
| CN101383442B (en) | Method for recovering and preparing lithium cobaltate from waste lithium ionic cell | |
| CN111430831B (en) | Method for recovering waste lithium ion battery negative electrode material | |
| CN106848469A (en) | A kind of method that valuable metal is reclaimed in the material from waste lithium ion cell anode | |
| CN114614133B (en) | Combined treatment method for betel nut residues and waste anode materials | |
| CN107326181A (en) | Waste and old lithium ion battery, which is peeled off, leaches the recovery method that a step is completed | |
| CN103346365A (en) | Method for recycling negative material from waste lithium ion battery | |
| CN101969148A (en) | Pretreatment method for recovering valuable metal from anode material of waste lithium ion battery | |
| EP4151593B1 (en) | Method for graphite purification and lattice reconstruction in power battery | |
| JP2025516972A (en) | A method for producing battery-grade graphite using mixed waste of cathode and anode materials from damaged lithium-ion batteries as raw material | |
| CN116723999B (en) | Repairing and regenerating method of lithium iron phosphate | |
| CN103334012B (en) | Method for preparing metal-doped manganese dioxide powder by using electrolytic manganese anode slag and application | |
| CN109402396A (en) | A kind of waste lithium cell positive electrode pressure leaching method | |
| CN114204151A (en) | Method for repairing and modifying waste lithium ion battery positive electrode active material | |
| CN114231744A (en) | Method for recovering lithium, cobalt, nickel and manganese from waste lithium batteries | |
| CN114784271B (en) | A regenerated lithium iron phosphate positive electrode material, preparation method and application | |
| CN105355997A (en) | Method for separating current collector from active material of lithium battery and application of method | |
| CN113415814A (en) | Method for selectively recovering lithium from waste lithium ion batteries by using ultralow-temperature roasting | |
| CN105489960A (en) | Separation method for current collector and active material of lithium battery and application of separation method | |
| CN113621802A (en) | Method for recycling nickel, cobalt, manganese and lithium from waste ternary battery pole piece | |
| CN115181866B (en) | Combined leaching agent and application thereof in positive electrode leaching | |
| CN109777957B (en) | Solvent composition suitable for leaching and separating waste lithium battery material and leaching and separating method | |
| CN114381601A (en) | A method for step separation of valuable metals in positive electrode materials of waste ternary lithium ion batteries | |
| CN114804049B (en) | Method for recovering high-purity ferric phosphate from lithium iron phosphate waste batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20211109 |