CN112850808A - Method for recycling scrapped ternary lithium battery powder - Google Patents
Method for recycling scrapped ternary lithium battery powder Download PDFInfo
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- CN112850808A CN112850808A CN202110098035.3A CN202110098035A CN112850808A CN 112850808 A CN112850808 A CN 112850808A CN 202110098035 A CN202110098035 A CN 202110098035A CN 112850808 A CN112850808 A CN 112850808A
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- lithium
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- 239000000843 powder Substances 0.000 title claims abstract description 77
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000004064 recycling Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003513 alkali Substances 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- 238000000227 grinding Methods 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 230000032683 aging Effects 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 18
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000011084 recovery Methods 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 14
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 239000011343 solid material Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims 2
- 238000002791 soaking Methods 0.000 claims 1
- 238000009423 ventilation Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 229910052755 nonmetal Inorganic materials 0.000 abstract 1
- 150000002843 nonmetals Chemical class 0.000 abstract 1
- 238000001223 reverse osmosis Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 235000021110 pickles Nutrition 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- DNUHLCAXBJFONM-UHFFFAOYSA-N [O-2].[Mn+2].[Li+].[Co+2].[Ni+2].[Li+].[O-2].[O-2].[O-2] Chemical compound [O-2].[Mn+2].[Li+].[Co+2].[Ni+2].[Li+].[O-2].[O-2].[O-2] DNUHLCAXBJFONM-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 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
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
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Classifications
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- C01G53/006—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for recycling scrapped ternary lithium battery powder, which takes black battery powder obtained by shelling and coring, electrolyte removal, crushing and sorting of a nickel-cobalt-manganese ternary lithium battery as a raw material, and adopts the methods of alkali washing and aluminum removal, coordination and copper removal, material mixing and ball making, roasting, crushing and grinding, acid leaching, aging, RO film concentration and the like to effectively remove impurities such as copper powder, aluminum powder, graphite powder and the like in the ternary lithium battery powder, thereby finally obtaining a nickel-cobalt-manganese ternary precursor raw material and a lithium-rich solution. The process solves the problem of influence of impurity metals/nonmetals such as copper, aluminum, graphite and the like in the ternary lithium battery powder on the purity of a final product, determines an efficient short-flow green pollution-free industrial recovery method of the discarded ternary lithium battery powder with good separation effect, and has strong social value and considerable economic benefit.
Description
Technical Field
The invention belongs to the technical field of recycling of lithium ion batteries, and particularly relates to a method for recycling scrapped ternary lithium battery powder.
Background
With the increasing prominence of energy and environmental problems, the lithium ion battery attracts much attention as a novel high-energy green battery, and the lithium ion battery has a series of advantages of high specific energy, high specific power, long service life and the like and becomes the most promising power battery. The anode material of the lithium ion battery determines the electrochemical performance, safety performance, price cost and the like of the lithium ion battery. Lithium batteries using lithium nickel cobalt manganese oxide as a positive electrode material are commonly called ternary lithium batteries, and compared with lithium iron phosphate batteries, the lithium nickel cobalt manganese oxide lithium battery has the greatest characteristic of high energy density. Meanwhile, the scrapped ternary lithium battery has higher recovery value, and in addition to valuable substances such as copper, aluminum, plastics and the like obtained through physical disassembly, the scrapped ternary lithium battery has higher value in ternary lithium battery powder.
The ternary lithium battery powder is a black powder obtained by shelling, coring, electrolyte removal, crushing and sorting of a nickel-cobalt-manganese ternary lithium battery, and mainly comprises nickel-cobalt-manganese positive electrode powder and graphite negative electrode powder.
The invention patent of publication number CN201810928779.1 discloses a method for recovering anode powder of waste ternary lithium batteries, which comprises the following steps: the method comprises the steps of primary high-temperature roasting → lithium leaching → nickel leaching → secondary high-temperature roasting → cobalt leaching, and the sulfate solution of lithium, nickel and cobalt with better applicability is obtained by separation in a step-by-step high-temperature treatment and leaching mode, so that classified recovery and harmless utilization of the anode powder of the waste ternary lithium battery are realized. The invention patent of publication number CN201811093703.8 discloses a method and a system for comprehensively recovering valuable metals from waste ternary lithium batteries, which comprises the following steps: disassembling a positive plate from a waste ternary lithium battery; removing the binder in the positive plate, and leaching valuable metal elements in the positive plate by acid dissolution to obtain an acidified leaching solution; carrying out ultrafiltration treatment on the acidified leaching solution by using an ultrafiltration membrane; separating lithium ions from other cations different from the lithium ions in the acidified leachate by using a nanofiltration membrane technology to obtain a lithium-containing solution and a solution containing other cations, concentrating and enriching the lithium-containing solution and the solution respectively by using a reverse osmosis technology, precipitating and separating the lithium ions in the lithium-containing solution by using a lithium precipitator, and precipitating and separating nickel ions, cobalt ions and manganese ions in the solution containing other cations by using an alkaline substance to realize the recovery of valuable metals. Neither of the two patents effectively removes aluminum, copper, graphite and the like, so that the stability of the whole process and the purity of subsequent products have great uncertainty.
The invention with the publication number of CN201910822814.6 discloses a method for recycling all components of a soft package of a waste ternary lithium battery, which comprises the steps of discharging, crushing, screening by a shallow groove separator, acid leaching, step-by-step precipitation, a hydrothermal method and the like in sequence, and is used for respectively recycling all components of a diaphragm, graphite, nickel, cobalt, manganese, copper and aluminum in the waste ternary lithium battery to realize the optimization of economic benefit.
Disclosure of Invention
The invention aims to provide a method for recycling scrapped ternary lithium battery powder, which aims to solve the problem that impurities such as copper powder, aluminum powder and graphite powder in the scrapped ternary lithium battery powder in the prior art influence the product purity and provide an efficient, short-flow, good separation effect, green and pollution-free industrialized recycling method of the scrapped ternary lithium battery powder.
The purpose of the invention is realized by the following technical scheme:
a method for recycling scrapped ternary lithium battery powder comprises the following steps:
s1 alkaline washing to remove aluminum: putting the battery powder and water into a reaction kettle according to the mass ratio of 1: 2-1: 4, adding alkali, reacting at the temperature of 60-80 ℃ for 1-2 hours, and filtering to obtain aluminum-removed battery powder; the battery powder is black battery powder obtained by shelling, coring, electrolyte removing, crushing and sorting of a nickel-cobalt-manganese ternary lithium battery; preferably, the alkali is potassium hydroxide, and the addition amount of the potassium hydroxide is 1.1-1.3 times of the theoretical mass of the reaction with the aluminum;
s2 coordination copper removal: adding water into the aluminum-removed battery powder according to the solid-liquid mass ratio of 1: 3-1: 5, stirring and slurrying for 0.5-1 h, adding ammonia water with the ammonia content being 2-6% of the mass of the aluminum-removed battery powder, adding ammonium salt with the mass being 5-15% of the mass of the aluminum-removed battery powder, blowing air by using an air pump, stirring and reacting for 6-10 h at normal temperature, and filtering to obtain the copper-removed battery powder; preferably, the ammonium salt is at least one of ammonium carbonate, ammonium bicarbonate, ammonium sulfate and ammonium chloride.
S3 mixing: adding the copper-removed battery powder and potassium permanganate into a mixer, and carrying out oscillation mixing, wherein the adding amount of the potassium permanganate accounts for 3-5% of the mass of the battery powder, the rotation speed of the mixer is 30-60 r/min, the revolution speed is 1-3 r/min, and the mixing time is 0.5-1 h; and (3) feeding the mixed material into a hydraulic ball making machine for ball making, wherein the ball making pressure is 0.2-0.4 MPa, and the material balls with the radius R of 10-30 mm are obtained.
S4 roasting: roasting and oxidizing the material balls to remove graphite, and crushing and grinding to obtain a grinding material; wherein: the roasting temperature is as follows: the temperature is 400-600 ℃, and the time is 1-3 h; introducing air or oxygen in the roasting process, wherein the flow rate is controlled to be 10-30L/min; the granularity of the grinding material is as follows: less than or equal to 125 mu m.
Acid leaching of S5: placing the grinding material and pure water into a reaction vessel according to the mass ratio of 1: 3-1: 4 at normal temperature, stirring and slurrying for 0.5-1 h, adding concentrated sulfuric acid, controlling the pH value to be 2-2.5, heating to 60-90 ℃, reacting for 2-4 h, and filtering to obtain an acid leaching solution containing lithium, nickel, cobalt and manganese;
s6 aging: adding alkali into the acid leaching solution, then aging, filtering and separating to obtain a nickel-cobalt-manganese ternary precursor solid material and a lithium-containing solution; preferably, the alkali is potassium hydroxide, and the addition amount of the alkali is 1.05-1.2 times of the theoretical amount of the alkali required for generating the nickel-cobalt-manganese ternary precursor solid material; the temperature of the aging is 5-10 ℃, and the aging is carried out for 2-4 hours under the stirring condition.
Further preferably, the method further comprises a RO membrane (reverse osmosis membrane) concentration step after the aging step, and comprises the following steps: conveying the lithium-containing solution to an RO membrane system by using a high-pressure pump for concentration to obtain a concentrated lithium-rich solution; wherein the feeding pressure of the high-pressure pump is 0.3-0.6 MPa.
Compared with the prior art, the invention has the beneficial effects that:
by specifically adopting the modes of alkaline cleaning aluminum, coordination copper removal and the like for the impurity types and the physical properties of the ternary lithium battery powder, the influence of aluminum powder and copper powder on the purity of subsequent products is firstly solved; potassium permanganate is introduced as an oxide, and the mixture is mixed, pelletized and then roasted, so that the nickel cobalt lithium manganate can be fully oxidized, and the use amount of sulfuric acid in the acid leaching process is greatly reduced; adding potassium hydroxide, and adopting a low-temperature aging mode to fully precipitate nickel, cobalt and manganese elements; and finally, concentrating the lithium-containing solution by using an RO (reverse osmosis) membrane, and providing a pure raw material for preparing battery-grade lithium carbonate.
The method is a new process route for recycling the scrapped ternary lithium battery powder, and has high impurity removal efficiency and high product purity, and extremely high social value and considerable economic benefit.
Description of the drawings:
FIG. 1 is a process flow diagram of a method for recovering scrapped ternary lithium battery powder provided by the invention.
Detailed Description
The present invention will be described in further detail with reference to examples and tables for more clearly illustrating the objects, advantages, technical solutions and process routes of the present invention, and the exemplary embodiments and descriptions thereof are only used for explaining the method of the present invention and are not to be construed as limiting the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all 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.
The reagents used in the following examples are all commercially available products.
Example 1:
raw materials: screening 1 obtained by mechanically and automatically disassembling, crushing and sorting scrapped ternary lithium batteries#Ternary lithium battery powder with quantitative elementsThe analysis was as follows:
s1 alkaline washing to remove aluminum: the battery powder and water are put into a reaction kettle according to the mass ratio of 1:4, potassium hydroxide is added according to the 1.3 times of the theoretical mass of the reaction of potassium hydroxide and aluminum, the reaction temperature is 60 ℃, the reaction time is 2 hours, the aluminum-removed battery powder is obtained by filtration, and the aluminum removal rate is 99.57%.
S2 coordination copper removal: adding bottom water into the aluminum-removed battery powder according to the solid-liquid mass ratio of 1:3, stirring and slurrying for 1h, adding ammonia water according to the ammonia content of 2% of the aluminum-removed battery powder, adding ammonium carbonate according to 10% of the aluminum-removed battery powder, adding ammonium bicarbonate according to 5% of the aluminum-removed battery powder, blowing air by using an air pump, stirring and reacting for 10h at normal temperature, and filtering to obtain the copper-removed battery powder, wherein the copper removal rate is 99.64%. .
S3 mixing: adding the battery powder and the potassium permanganate subjected to impurity removal into a mixer, and performing oscillation mixing, wherein the addition amount of the potassium permanganate accounts for 5% of the mass of the battery powder, the rotation speed of the mixer is 60r/min, the revolution speed is 1r/min, and the mixing time is 0.5 h; and (3) feeding the mixed material into a hydraulic ball making machine for ball making, wherein the ball making pressure is 0.4MPa, and the material ball with the radius R of 10mm is obtained.
S4 roasting: removing graphite from the material balls by roasting and oxidizing, wherein the roasting temperature is as follows: roasting at 600 ℃ for 1h, controlling the flow of introduced oxygen at 10L/min and ensuring that the graphite removal rate is 99.98 percent. The roasted material has partial sintering phenomenon, and the grinding material is obtained by crushing and grinding the material and passing through a 125-micron screen.
Acid leaching of S5: under the condition of normal temperature, putting the grinding material and pure water into a reaction vessel according to the mass ratio of 1:3, stirring and slurrying for 0.5h, adding concentrated sulfuric acid, controlling the pH value to be 2, heating to 90 ℃, reacting for 2h, and filtering to obtain the pickle liquor of lithium, nickel, cobalt and manganese.
S6 low-temperature aging: adding potassium hydroxide into the pickle liquor according to 1.2 times of the theoretical amount of alkali required for generating the solid material of the nickel-cobalt-manganese ternary precursor, controlling the aging temperature at 5 ℃, stirring for 2h, and filtering to obtain the nickel-cobalt-manganese ternary precursor and a lithium-containing solution;
s7RO membrane concentration: and (3) controlling the feeding pressure of the lithium-containing solution at 0.3Mpa by using a high-pressure pump, and concentrating the lithium-containing solution in an RO membrane system to obtain a concentrated lithium-rich solution.
Example 2:
raw materials: after the scrapped ternary lithium battery is mechanically and automatically disassembled, crushed and sorted, 2 obtained by screening#The ternary lithium battery powder has the following quantitative element analysis:
s1 alkaline washing to remove aluminum: the battery powder and water are placed into a reaction kettle according to the mass ratio of 1:2, potassium hydroxide is added according to the 1.1 time of the theoretical mass of the reaction of potassium hydroxide and aluminum, the reaction temperature is 80 ℃, the reaction time is 1h, the aluminum-removed battery powder is obtained by filtering, and the aluminum removal rate is 99.88%.
S2 coordination copper removal: adding bottom water into the aluminum-removed battery powder according to the solid-liquid mass ratio of 1:5, stirring and slurrying for 0.5h, adding ammonia water according to the ammonia content of 6% of the aluminum-removed battery powder, adding ammonium carbonate according to 5% of the aluminum-removed battery powder, adding ammonium sulfate according to 10% of the aluminum-removed battery powder, blowing air by using an air pump, stirring and reacting for 6h at normal temperature, and filtering to obtain the copper-removed battery powder, wherein the copper removal rate is 99.52%.
S3 mixing: adding the battery powder and the potassium permanganate subjected to impurity removal into a mixer, and performing oscillation mixing, wherein the adding amount of the potassium permanganate accounts for 3% of the mass of the battery powder, the rotation speed of the mixer is 30r/min, the revolution speed is 3r/min, and the mixing time is 1 h; and (3) feeding the mixed material into a hydraulic ball making machine to make balls, wherein the ball making pressure is 0.2MPa, and the material balls with the radius R of 30mm are obtained.
S4 roasting: and (3) roasting the material balls at 400 ℃ for 3h to remove graphite, controlling the flow of introduced air at 30L/min, and ensuring that the removal rate of graphite is 100%. The roasted material has partial sintering phenomenon, and the material is crushed, ground and sieved by a 75-micron sieve to obtain the grinding material.
Acid leaching of S5: under the condition of normal temperature, putting the grinding material and pure water into a reaction vessel according to the mass ratio of 1:4, stirring and slurrying for 1h, adding concentrated sulfuric acid, controlling the pH value to be 2.5, heating the temperature to be 60 ℃, reacting for 4h, and filtering to obtain the pickle liquor of lithium, nickel, cobalt and manganese.
S6 low-temperature aging: and adding potassium hydroxide into the pickle liquor according to 1.05 times of the theoretical amount of alkali required for generating the nickel-cobalt-manganese ternary precursor solid material, controlling the aging temperature at 10 ℃, stirring for 4 hours, and filtering to obtain the nickel-cobalt-manganese ternary precursor raw material and a lithium-containing solution.
S7RO membrane concentration: and (3) controlling the feeding pressure of the lithium-containing solution at 0.6Mpa by using a high-pressure pump, and concentrating the lithium-containing solution in an RO membrane system to obtain a concentrated lithium-rich solution.
Example 3:
raw materials: screening the scrapped ternary lithium battery after mechanical automatic disassembly and crushing separation to obtain 3#The ternary lithium battery powder has the following quantitative element analysis:
s1 alkaline washing to remove aluminum: the battery powder and water are placed into a reaction kettle according to the mass ratio of 1:4, potassium hydroxide is added according to the 1.2 times of the theoretical mass of the reaction of the potassium hydroxide and the aluminum, the reaction temperature is 70 ℃, the reaction time is 2 hours, the aluminum-removed battery powder is obtained by filtering, and the aluminum removal rate is 99.68%.
S2 coordination copper removal: adding bottom water into the aluminum-removed battery powder according to the solid-liquid mass ratio of 1:4, stirring and slurrying for 1h, adding ammonia water according to the ammonia content of 4% of the aluminum-removed battery powder, adding ammonium carbonate according to 10% of the aluminum-removed battery powder, adding ammonium chloride according to 10% of the aluminum-removed battery powder, blowing air by using an air pump, stirring and reacting for 10h at normal temperature, and filtering to obtain the copper-removed battery powder, wherein the copper removal rate is 99.86%
S3 mixing: adding the battery powder and the potassium permanganate subjected to impurity removal into a mixer, and performing oscillation mixing, wherein the adding amount of the potassium permanganate accounts for 5% of the mass of the battery powder, the rotation speed of the mixer is 60r/min, the revolution speed is 3r/min, and the mixing time is 1 h; and (3) feeding the mixed material into a hydraulic ball making machine to make balls, wherein the ball making pressure is 0.4MPa, and the material balls with the radius R of 15mm are obtained.
S4 roasting: and (3) roasting the material balls at 500 ℃ for 3h, wherein the graphite is removed by roasting and oxidizing the material balls, the flow of introduced oxygen is controlled at 20L/min, and the graphite removal rate is 99.89%. And (3) partial sintering of the roasted material occurs, and the grinding material passes through a 125-micron screen after crushing and grinding to obtain the grinding material.
Acid leaching of S5: under the condition of normal temperature, putting the grinding material and pure water into a reaction vessel according to the mass ratio of 1:4, stirring and slurrying for 0.5h, adding concentrated sulfuric acid, controlling the pH value to be 2, heating the temperature to be 90 ℃, reacting for 4h, and filtering to obtain the pickle liquor of lithium, nickel, cobalt and manganese.
S6 low-temperature aging: and adding potassium hydroxide into the pickle liquor according to 1.1 times of the theoretical amount of alkali required for generating the nickel-cobalt-manganese ternary precursor solid material, controlling the aging temperature at 5 ℃, stirring for 4 hours, and filtering to obtain the nickel-cobalt-manganese ternary precursor raw material and a lithium-containing solution.
S7RO membrane concentration: and (3) controlling the feeding pressure of the lithium-containing solution at 0.6Mpa by using a high-pressure pump, and concentrating the lithium-containing solution in an RO membrane system to obtain a concentrated lithium-rich solution.
Claims (10)
1. A method for recycling scrapped ternary lithium battery powder is characterized by comprising the following steps: the method comprises the following steps:
s1 alkaline washing to remove aluminum: mixing the battery powder with alkali liquor, soaking the battery powder by using the alkali liquor to dissolve out impurity aluminum in the battery powder, and filtering to obtain aluminum-removed battery powder;
s2 coordination copper removal: adding the aluminum-removed battery powder into water, stirring and slurrying, adding ammonia water and ammonium salt, continuously stirring to dissolve out copper, and filtering to obtain copper-removed battery powder;
s3 mixing: mixing the copper-removed battery powder with potassium permanganate to obtain a mixture;
s4 roasting: roasting and oxidizing the mixture to remove graphite, and crushing and grinding the mixture to obtain a grinding material;
acid leaching of S5: mixing the grinding material with acid liquor, and performing acid liquor impregnation and filtration to obtain acid leaching liquor containing lithium, nickel, cobalt and manganese;
s6 aging: and adding alkali into the acid leaching solution, then aging, filtering and separating to obtain a nickel-cobalt-manganese ternary precursor solid material and a lithium-containing solution.
2. The recycling method according to claim 1, characterized in that: in the step of S1 removing aluminum by alkali washing, the battery powder is black battery powder obtained by shelling, coring, removing electrolyte, crushing and sorting of a nickel-cobalt-manganese ternary lithium battery.
3. The recovery method according to claim 1 or 2, characterized in that: in the step of S1 aluminum removal by alkali washing, the method for mixing the battery powder and the alkali liquor comprises the following steps: putting the battery powder and water into a reaction kettle according to the mass ratio of 1: 2-1: 4, adding alkali, and reacting at the temperature of 60-80 ℃ for 1-2 hours; wherein the alkali is potassium hydroxide, and the addition amount of the alkali is 1.1-1.3 times of the theoretical mass of the reaction with aluminum.
4. The recycling method according to claim 1, characterized in that: in the step of S2 removing aluminum by alkali, the ammonia content in the ammonia water is 2-6% of the mass of the aluminum-removed battery powder, and the mass of ammonium salt is 5-15% of the mass of the aluminum-removed battery powder; and blowing air by using an air pump during the stirring process, wherein the ventilation volume is 20-40L/min.
5. The recycling method according to claim 4, characterized in that: the ammonium salt is at least one of ammonium carbonate, ammonium bicarbonate, ammonium sulfate and ammonium chloride.
6. The recycling method according to claim 1, characterized in that: in the S3 material mixing step, the adding amount of potassium permanganate is 3-5% of the mass of the copper-removed battery powder; the method comprises the following steps of preparing the mixture into spherical material balls, and performing the following steps: and (3) feeding the mixture into a hydraulic ball making machine for ball making, wherein the ball making pressure is 0.2-0.4 MPa, and the material balls with the radius R of 10-30 mm are obtained.
7. The recycling method according to claim 1, characterized in that: in the S4 roasting step, the roasting temperature is as follows: the temperature is 400-600 ℃, and the time is 1-3 h; introducing air or oxygen in the roasting process, wherein the flow rate is controlled to be 10-30L/min; the granularity of the grinding material is less than or equal to 125 mu m.
8. The recycling method according to claim 1, characterized in that: in the step of acid leaching of S5, the method for mixing the grinding material and the acid liquor comprises the following steps: putting the grinding material and water into a reaction vessel according to the mass ratio of 1: 3-1: 4, stirring and slurrying for 0.5-1 h, adding concentrated sulfuric acid, and controlling the pH value to be 2-2.5; the temperature of the acid liquor impregnation is 60-90 ℃, and the time is 2-4 h.
9. The recycling method according to claim 1, characterized in that: in the aging step of S6, the alkali is potassium hydroxide, and the addition amount of the alkali is 1.05-1.2 times of the theoretical amount of the alkali needed for generating the nickel-cobalt-manganese ternary precursor solid material; the temperature of the aging is 5-10 ℃, and the aging is carried out for 2-4 hours under the stirring condition.
10. The recycling method according to claim 1, characterized in that: the method also comprises a RO membrane concentration step after the S6 aging step, and comprises the following steps: conveying the lithium-containing solution to an RO membrane system by using a high-pressure pump for concentration to obtain a concentrated lithium-rich solution; wherein the feeding pressure of the high-pressure pump is 0.3-0.6 MPa.
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