CN114381604B - Method for recycling lithium ion battery anode waste by composite biomass powder assisted stepwise mechanical activation - Google Patents
Method for recycling lithium ion battery anode waste by composite biomass powder assisted stepwise mechanical activation Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 82
- 238000004137 mechanical activation Methods 0.000 title claims abstract description 76
- 239000000843 powder Substances 0.000 title claims abstract description 70
- 239000002699 waste material Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000002028 Biomass Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000004064 recycling Methods 0.000 title claims abstract description 23
- 238000002386 leaching Methods 0.000 claims abstract description 75
- 239000007774 positive electrode material Substances 0.000 claims abstract description 20
- 150000007524 organic acids Chemical class 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 13
- 244000183278 Nephelium litchi Species 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000006183 anode active material Substances 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 241000283690 Bos taurus Species 0.000 claims description 3
- 235000009754 Vitis X bourquina Nutrition 0.000 claims description 3
- 235000012333 Vitis X labruscana Nutrition 0.000 claims description 3
- 240000006365 Vitis vinifera Species 0.000 claims description 3
- 235000014787 Vitis vinifera Nutrition 0.000 claims description 3
- 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 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 244000099147 Ananas comosus Species 0.000 claims description 2
- 235000007119 Ananas comosus Nutrition 0.000 claims description 2
- 244000294611 Punica granatum Species 0.000 claims description 2
- 235000014360 Punica granatum Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 24
- 239000002184 metal Substances 0.000 abstract description 24
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 239000011812 mixed powder Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 description 17
- 238000001994 activation Methods 0.000 description 11
- 230000004913 activation Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 6
- 235000015742 Nephelium litchi Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical class [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
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- 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
- C22B7/007—Wet processes by acid leaching
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
- C22B3/1608—Leaching with acyclic or carbocyclic agents
- C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
- C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
-
- 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
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- 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
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- 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
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- 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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- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recycling lithium ion battery anode waste by mechanical activation step by step assisted by composite biomass powder. The method comprises the following steps: pretreating lithium ion battery positive electrode waste to obtain a lithium ion battery positive electrode active material; mixing the positive electrode active material with the composite biomass powder for dry mechanical activation; adding organic acid into the mixed powder after dry mechanical activation for wet mechanical activation, and then directly leaching to obtain leaching liquid and filter residues. The invention adopts the mechanical activation method with low energy consumption assisted by the solid waste-composite biomass powder to recycle the lithium ion battery anode waste, and the whole recycling method is green, efficient, low in energy consumption, free of secondary pollution, simple in process flow and high in valuable metal leaching rate, and meets the requirements of industrial application in the lithium ion battery anode waste treatment recycling industry.
Description
Technical Field
The invention relates to the technical field of solid waste recycling, in particular to a method for recycling lithium ion battery anode waste by mechanical activation step by step under the assistance of composite biomass powder.
Background
With the rapid development of electronic products such as mobile phones, computers and new energy automobiles, the demand of lithium ion batteries is increasing dramatically. The service life of the lithium ion battery is generally 3-6 years, and the scrapping amount of the waste lithium ion battery can reach 98.8 ten thousand tons in 2025 years, so that the scrapping amount per year is obviously accelerated. On the one hand, the waste lithium ion battery has a certain flammable and explosive risk, contains toxic and harmful components such as organic electrolyte, organic binder and the like, and must be subjected to harmless treatment; on the other hand, the waste lithium ion battery has high recovery value and potential.
At present, the recovery of lithium ion batteries is mainly focused on the recovery of valuable metals in positive electrode wastes, and common recovery methods are mainly classified into a wet method, a fire method and a microbial method.
(1) Wet recovery
The wet recovery has the advantages of low energy consumption, high recovery rate, high purity of recovered metal, no volatilization loss of lithium and aluminum caused by high temperature, and the like. Is widely applied to the industrial recovery of waste lithium ion batteries. In previous studies, wet recovery mainly used inorganic acid (CN 110512080 a), organic acid (CN 112591806 a) and ammonia (CN 111129488A) as leaches for lithium ion battery positive electrode waste. However, inorganic acid leaching is easier to produce pollutants such as acid gas, and hydrochloric acid in the inorganic acid is easy to volatilize during leaching and has certain corrosiveness to leaching equipment. The organic acid leaching has the characteristic of environmental friendliness, but under the same acid concentration, the organic acid leaching effect is poorer than that of inorganic acid, and the leaching process is slow. And hydrogen peroxide is often required as a reducing agent for either organic or inorganic acid leaching. The ammonia leaching method can selectively leach valuable metals, but has low leaching rate, unstable leaching reagent, easy volatilization of ammonia water and the like, and is inconvenient for industrial application.
(2) Recovery by pyrogenic process
The patent (Zhang Jiafeng and the like, CN 111733328A) discloses a method for leaching metal in a positive electrode material of a waste lithium ion battery, which adopts a sulfur-containing reducing agent and chloride to reduce and bake the waste lithium ion battery in a segmented manner, simplifies the recovery step of the waste lithium ion battery and realizes the efficient utilization of the metal, but the two-stage baking is carried out at a higher reaction temperature, the baking time is longer, and the leaching is carried out by acid after the two-stage baking is finished, so that the energy consumption is high. The invention discloses a pyrogenic recovery process of waste lithium ion battery powder (cycle et al, CN 112111651A), which comprises the steps of uniformly mixing the recovered positive electrode powder, negative electrode powder and hydrogen ion salt, and roasting in two stages. However, the two-stage fire roasting temperature is still higher, the chemical reaction of the whole system is more complex, and the higher reaction temperature can cause the volatilization of low-boiling-point metals such as lithium, aluminum and the like and simultaneously promote the reaction of organic substances in the waste lithium ion battery, release toxic gases and cause secondary pollution.
(3) Microorganism recovery
The patent (Zeng Guisheng and the like, CN 101174717) discloses a method from bacterial culture to valuable metal leaching in lithium ion batteries, and the method provides a new way for recycling treatment of the waste lithium ion batteries. Patent (Li Li, et al, CN 112899485A) discloses a method for leaching metal ions by a microorganism-matched fermentation kettle and a precipitation kettle, wherein a culture solution containing bacterial strains is adopted to leach a lithium ion battery anode material, the method replaces the effect of acid in the traditional wet recovery, is green and safe, but the culture and leaching effects of bacterial strains need strict operation conditions, the bacterial strain culture is complex, the operation threshold is high, the leaching process period is long, and large-scale industrial application is difficult to realize.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for recycling lithium ion battery positive electrode waste by auxiliary stepwise mechanical activation of composite biomass powder. The whole recovery process has low energy consumption, short period and few steps, and all the used reagents can be degraded, so that the green and efficient recovery of the lithium ion battery anode waste is realized.
The technical scheme of the invention is as follows:
a method for recovering lithium ion battery positive electrode waste materials by composite biomass powder auxiliary stepwise mechanical activation comprises the steps of carrying out dry mechanical activation on waste lithium ion battery positive electrode active materials and composite biomass powder, adding organic acid to carry out wet mechanical activation, then leaching with water, and carrying out solid-liquid separation after the reaction is completed. The method comprises the following steps:
(1) And (3) pretreating the waste anode materials of the waste lithium ion batteries to obtain anode active substances A, mixing the anode active substances A with the composite biomass powder, and carrying out dry mechanical activation for 0.5-3 h to obtain a mixed material B. Wherein the composite biomass powder is one or more of pineapple peel powder, grape peel powder, pomegranate seed powder and litchi rind powder, and the addition amount of the composite biomass powder is 5-25% of the mass of the positive electrode active material;
(2) Mixing the mixed material B after the dry mechanical activation in the step (1) with an organic acid for wet mechanical activation of 0.5-4 h to obtain a mixed solution C;
(3) Soaking the mixed solution C in deionized water at 25-50deg.C for 0.5-2 h to obtain water soaked residue D and leachate E;
(4) And (3) feeding the water immersed residues D obtained in the step (3) into a dryer for drying, and returning to the step (1) for dry mechanical activation.
According to the invention, the composite biomass powder is innovatively adopted as a dry mechanical activation co-grinding agent and a wet mechanical activation reducing agent, and is subjected to two-step mechanical activation under the determined experimental conditions and then leached, so that research shows that the composite biomass powder can rapidly realize efficient leaching of valuable metals in lithium ion battery positive electrode waste under the condition of low acid and low temperature compared with the traditional reducing agent, and in addition, compared with the traditional planetary ball milling, the composite biomass powder is a solid waste material, and the waste is truly treated by waste by controlling the discharge voltage of a plasma ball mill in the dry mechanical activation, so that the mixed embedding activation and refinement of the lithium ion battery positive electrode waste and the composite biomass powder can be realized, the activation energy is reduced, the components of the composite biomass powder are not destroyed, the composite biomass powder is decomposed in the wet mechanical activation process, and the effective components serve as the reducing agent to efficiently leach the lithium ion battery positive electrode waste.
The invention discloses a method for recycling lithium ion battery positive electrode waste by using composite biomass powder to assist in stepwise mechanical activation, wherein the lithium ion battery positive electrode waste in the step (1) is one or more of lithium cobaltate, lithium manganate and lithium nickel cobalt manganate.
The invention discloses a method for recycling lithium ion battery anode waste by composite biomass powder auxiliary stepwise mechanical activation, wherein in the step (1), dry mechanical activation equipment is a plasma ball mill.
According to the invention, the composite biomass powder and the lithium ion battery positive electrode waste are innovatively adopted for dry mechanical activation, and researches show that the method is more beneficial to the activation of the lithium ion battery positive electrode waste, and is beneficial to accelerating the leaching time in the subsequent leaching process and improving the leaching rate.
Preferably, the dry mechanical activation time is 1-2 h.
Preferably, the discharge voltage of the dry mechanical activation plasma ball mill is 13 kV-16 kV.
Preferably, the addition amount of the composite biomass material is 10% -20% of the mass of the positive electrode active material.
The invention relates to a method for recycling lithium ion battery anode waste by composite biomass powder auxiliary stepwise mechanical activation, wherein in the step (2), wet mechanical activation equipment is a planetary ball mill.
The invention relates to a method for recycling lithium ion battery anode waste by using composite biomass powder to assist in stepwise mechanical activation, wherein in the step (2), organic acid is citric acid.
The invention innovatively adopts organic acid to cooperate with the composite biomass powder to leach the lithium ion battery anode waste through wet mechanical activation, and researches show that the composite biomass powder is fully decomposed in the wet mechanical activation, and cooperates with the organic acid to reduce and leach the lithium ion battery anode waste.
Preferably, the wet mechanical activation time is 1-2 h.
Preferably, the rotational speed of the planetary ball mill in the wet mechanical activation is 300-550 rpm.
Preferably, the concentration of the aqueous citric acid solution is 0.8 mol/L to 1.5 mol/L.
Preferably, the liquid-to-solid ratio (ml: g) of aqueous citric acid solution to the dry mechanically activated mixture B obtained in step (1) during wet milling is from 1:1 to 50:1, more preferably from 5:1 to 15:1.
The invention innovatively adopts composite biomass powder to assist organic acid to perform wet mechanical activation, and can directly leach the valuable metal in the positive electrode active material of the lithium ion battery after the activation, leaching solution E and water leaching residue D (mixed solid residue of incompletely decomposed biomass powder and the non-leached completely positive electrode active material of the lithium ion battery) containing the valuable metal can be obtained after the leaching, and the water leaching residue D can be subjected to secondary activation leaching again after being dried, so that the high-efficiency rapid leaching of the positive electrode waste material of the lithium ion battery can be realized in the whole process.
Preferably, the leaching time during water leaching is 0.5-1 h.
Preferably, in the water leaching process, the volume ratio of deionized water to the mixed solution C obtained after the wet mechanical activation in the step (2) is 1:1-20:1, more preferably 5:1-10:1.
Preferably, the temperature during water immersion is 25 ℃ (normal temperature).
The invention relates to a method for recycling lithium ion battery anode waste by composite biomass powder auxiliary stepwise mechanical activation, wherein the addition amount of the composite biomass material is 10-20% of the mass of an anode active substance, the discharge voltage of a dry mechanical activation plasma ball mill is 13 kV-16 kV, and the dry mechanical activation time is 1-2 h; wet mechanical activation is carried out by a planetary ball mill, the rotating speed of the planetary ball mill is 300-550 rpm, and the ball milling time is 1-2 h:
when the lithium ion battery positive electrode waste contains metal Li, the Li leaching rate is more than 99%;
when the positive electrode waste of the lithium ion battery contains metal Ni, the leaching rate of Ni is more than 98%;
when the lithium ion battery positive electrode waste contains metal Co, the leaching rate of Co is more than 98%;
when the lithium ion battery anode waste contains metal Mn, the leaching rate of Mn is more than 98 percent.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the scheme, the environment-friendly organic acid is matched with the composite biomass powder, and compared with a traditional system, the method has the advantages that the organic acid is low, the temperature is low, and the leaching rate of valuable metals of lithium ion positive electrode waste is over 98 percent;
(2) The whole process is green and clean, no secondary pollutant is generated, the composite biomass powder is taken from solid waste, the recycling of solid waste is realized, and the purpose of treating waste by waste is truly achieved;
(3) The invention has simple process flow and low energy consumption by a mechanical activation method, and meets the requirements of industrial application in the lithium ion battery anode waste treatment industry.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Fig. 2 is an XRD pattern of the positive electrode active material of the lithium ion battery used in example 1 of the present invention.
Fig. 3 is a graph showing the variation of the metal leaching rate with the addition amount of biomass powder in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.
Referring to fig. 1, fig. 1 is a process flow chart of a method for recovering lithium ion battery positive electrode waste material by auxiliary stepwise mechanical activation of composite biomass powder, and the method comprises the steps of preprocessing lithium ion battery positive electrode waste material to obtain lithium ion battery positive electrode active material, adding composite biomass powder for dry mechanical activation, adding organic acid for wet mechanical activation, soaking in water, and performing dry mechanical activation on filter residues after soaking again to obtain valuable metal leaching in the lithium ion battery positive electrode waste material.
Example 1:
(1) Heat-treating the lithium ion battery positive electrode waste (positive electrode active material is lithium cobaltate) at 500 ℃ for 4 h, and separating aluminum foil to obtain a lithium ion battery positive electrode active material A;
(2) Weighing 5 g lithium ion battery anode active material A, feeding into a plasma ball mill, adding litchi shell powder with the addition amount of 10% of the anode active material, and setting the plasma ball mill to run 1 h under a discharge voltage of 15 kV to obtain a dry-method mechanically activated mixed material B;
(3) The above-mentioned mixture B was taken out, fed into a planetary ball mill, and an aqueous solution of citric acid of 55 ml in a ratio of 1mol/L (ml: g) of 10:1 was added, followed by wet planetary ball milling at 500 rpm for 1 h. Obtaining a mixed solution C after wet mechanical activation;
(4) Taking out the mixed solution C, adding the mixed solution C into 275 ml deionized water according to the volume ratio of the deionized water to the mixed solution C of 5:1, and magnetically stirring for 45 min at 25 ℃ to obtain water leaching residues D and leaching liquid E;
(5) The water immersed residue D was fed into a dryer and baked at 80 ℃ for 24 h, and then returned to the dry mechanical activation step for two-step activation leaching again.
According to detection, in the embodiment, the leaching rate of Li is 99.45%; the leaching rate of Co is 99.22 percent. Fig. 3 is a graph showing the variation trend of the metal leaching rate with the addition amount of the biomass powder in the embodiment 1 of the present invention, and the result shows that the leaching rates of the metals Li and Co are only 77.95% and 72.32% when the addition amount is 2%. The lower addition amount of the litchi rind powder leads to insufficient reduction leaching capability and reduced leaching effect.
Example 2:
(1) Heat-treating the lithium ion battery positive electrode waste (positive electrode active material is lithium manganate) at 500 ℃ for 4 h, and separating aluminum foil to obtain a lithium ion battery positive electrode active material A;
(2) Weighing 5 g lithium ion battery anode active material A, feeding into a plasma ball mill, adding mixed powder of pericarpium Granati and semen Granati, wherein the addition amount of the mixed powder is 20% of that of the anode active material, and setting the plasma ball mill to operate 2 h under a discharge voltage of 15 kV to obtain a mixed material B after a dry mechanical activation method;
(3) The above-mentioned mixture B was taken out, fed into a planetary ball mill, 1.2 mol/L of 60 ml was added at a liquid-solid ratio (ml: g) of 10:1, and then wet planetary ball milling was carried out at 550rpm for 1 h. Obtaining a mixed solution C after wet mechanical activation;
(4) Taking out the mixed solution C, adding the mixed solution C into the deionized water of 600 ml according to the volume ratio of the deionized water to the mixed solution C of 10:1, and magnetically stirring for 60 min at 25 ℃ to obtain water leaching residues D and leaching liquid E;
(5) The water immersed residue D was fed into a dryer and baked at 80 ℃ for 24 h, and then returned to the dry mechanical activation step for two-step activation leaching again.
According to detection, in the embodiment, the leaching rate of Li is 99.82%; the leaching rate of Mn is 98.13%.
Example 3:
(1) Heat-treating the lithium ion battery anode waste (the anode active material is nickel cobalt lithium manganate) at 500 ℃ for 4 h, and separating aluminum foil to obtain an anode active material A of the lithium ion battery;
(2) Weighing 10 g lithium ion battery anode active material A, feeding into a plasma ball mill, adding grape skin powder with the addition amount of 20% of the anode active material, and setting the plasma ball mill to run at a discharge voltage of 14 kV for 1.5 h to obtain a dry mechanical active mixed material B;
(3) The above-mentioned mixture B was taken out, fed into a planetary ball mill, and 60 ml of 1mol/L aqueous solution of citric acid was added at a liquid-solid ratio (ml: g) of 5:1, followed by wet planetary ball milling at 550rpm for 1 h. Obtaining a mixed solution C after wet mechanical activation;
(4) Taking out the mixed solution C, adding the mixed solution C into 300 ml deionized water according to the volume ratio of the deionized water to the mixed solution C of 5:1, and magnetically stirring for 45 min at 50 ℃ to obtain water leaching residues D and leaching liquid E;
(5) The water immersed residue D was fed into a dryer and baked at 80 ℃ for 24 h, and then returned to the dry mechanical activation step for two-step activation leaching again.
According to detection, in the embodiment, the leaching rate of Li is 99.63%; the leaching rate of Ni is 99.56%; the leaching rate of Co is 99.22%; the leaching rate of Mn is 98.22%.
Comparative example 1:
other conditions and steps are consistent with those of the example 1, the wet ball milling time in the example 1 is changed to 20 min, the too low ball milling time is insufficient to activate the positive electrode active material of the lithium ion battery and the litchi shell powder, the reducing components in the litchi shell powder are not completely decomposed, the reducing capability is insufficient, the leaching effect is reduced, and the leaching rates of metal Li and Co are 67.55% and 60.32% respectively.
Comparative example 2:
other conditions and steps are consistent with those of the embodiment 1, the dry mechanical activation of the embodiment 1 is changed to the Co-ball milling of the lychee shell powder, the lychee shell powder which is not subjected to the plasma ball milling is added in the wet mechanical activation, the lychee shell powder is difficult to adsorb active substances of the positive electrode of the lithium ion battery, the activity of the active substances of the positive electrode of the lithium ion battery is reduced, the activation energy of a mixed material in the wet mechanical activation is further increased, the higher activation energy reduces the leaching effect of metal, the reducing component in the lychee shell powder which is not subjected to the dry mechanical activation is difficult to decompose in the wet mechanical activation, the reduction capability of the lychee shell powder is insufficient, the leaching effect is reduced, and the leaching rates of metal Li and Co are 88.42% and 83.95% at the moment respectively.
Comparative example 3:
other conditions and steps are consistent with those of example 1, the plasma ball mill adopted in the dry mechanical activation in example 1 is changed into a planetary ball mill, the planetary ball mill lacks the active excitation effect of high-activity particles in the plasma ball mill, and the structure of the positive electrode active material of the lithium ion battery is difficult to thin and dope, so that the activation of the positive electrode active material of the lithium ion battery and the Co-ball milling with litchi shell powder are insufficient, the leaching effect is reduced, and the leaching rates of metal Li and Co are 91.55% and 88.32% respectively.
Compared with the traditional leaching method, the method for leaching the lithium ion battery anode waste by water leaching after mechanical activation by using the auxiliary distribution of the composite biomass powder has the advantages of environment friendliness, low energy consumption, simple operation flow, high recovery rate and convenience for industrial application.
Claims (8)
1. A method for recycling lithium ion battery positive electrode waste materials by composite biomass powder auxiliary stepwise mechanical activation is characterized in that waste lithium ion battery positive electrode active materials and composite biomass powder are subjected to dry mechanical activation, then organic acid is added for wet mechanical activation, then water is soaked, and solid-liquid separation is carried out after the reaction is completed; the method comprises the following specific steps:
(1) Pretreating waste anode materials of waste lithium ion batteries to obtain an anode active material A, and mixing the anode active material A with composite biomass powder for dry mechanical activation by 0.5-3 h to obtain a mixed material B; wherein the composite biomass powder is one or more of pineapple peel powder, grape peel powder, pomegranate seed powder and litchi rind powder, and the addition amount of the composite biomass powder is 5-25% of the mass of the positive electrode active material;
(2) Mixing the mixed material B with an organic acid solution for wet mechanical activation of 0.5-4 h to obtain a mixed solution C;
(3) Soaking the mixed solution C in deionized water at 25-50deg.C for 0.5-2 h to obtain water soaked residue D and leachate E;
(4) Feeding the water immersed residues D into a dryer for drying, and returning to the step (1) for dry mechanical activation; wherein:
in the step (1), a plasma ball mill is adopted for dry mechanical activation, the discharge voltage of the plasma ball mill is 13 kV-16 kV, and the dry mechanical activation is 1-2 h.
2. The method for recycling lithium ion battery anode waste by using composite biomass powder to assist in stepwise mechanical activation as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the lithium ion battery positive electrode waste is one or more of lithium cobaltate, lithium manganate and lithium nickel cobalt manganate.
3. The method for recycling lithium ion battery anode waste by using composite biomass powder to assist in stepwise mechanical activation as claimed in claim 1, wherein the method comprises the following steps: in the step (1), the addition amount of the composite biomass powder is 10-20% of the mass of the positive electrode active material.
4. The method for recycling lithium ion battery anode waste by using composite biomass powder to assist in stepwise mechanical activation as claimed in claim 1, wherein the method comprises the following steps: in the step (2), a planetary ball mill is adopted for wet mechanical activation, and the rotating speed of the planetary ball mill is 300-550 rpm; wet mechanical activation 1-2 h.
5. The method for recycling lithium ion battery anode waste by using composite biomass powder to assist in stepwise mechanical activation as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the organic acid is citric acid, the concentration of the aqueous solution of citric acid is 0.8 mol/L-1.5 mol/L, and the liquid-solid ratio of the aqueous solution of citric acid to the mixed material B is 1:1-50:1 ml/g.
6. The method for recycling lithium ion battery anode waste by using composite biomass powder to assist in stepwise mechanical activation as claimed in claim 1, wherein the method comprises the following steps: in the step (2), the liquid-solid ratio of the aqueous solution of citric acid to the mixed material B is 5:1-15:1 ml/g.
7. The method for recycling lithium ion battery anode waste by using composite biomass powder to assist in stepwise mechanical activation as claimed in claim 1, wherein the method comprises the following steps: in the step (3), in the water leaching process, the volume ratio of deionized water to the mixed solution C is 1:1-20:1.
8. The method for recycling lithium ion battery anode waste by using composite biomass powder to assist in stepwise mechanical activation as claimed in claim 1, wherein the method comprises the following steps: in the step (3), in the water leaching process, the volume ratio of deionized water to the mixed solution C is 5:1-10:1, the water leaching temperature is 25 ℃, and the water leaching time is 0.5-1 h.
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| CA3144899A1 (en) * | 2019-07-26 | 2021-02-04 | Wolfgang Rohde | Process for the recovery of lithium and other metals from waste lithium ion batteries |
| CN112374553A (en) * | 2020-11-13 | 2021-02-19 | 东北大学 | Method for recycling and regenerating retired lithium ion battery anode material |
| CN112662881A (en) * | 2020-12-14 | 2021-04-16 | 徐州宇帆机电科技有限公司 | Method for preparing industrial cobalt powder by microwave reduction pyrolysis of cobalt acid lithium battery |
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| US20070209480A1 (en) * | 2006-03-13 | 2007-09-13 | Michigan Technological University | Production of iron using environmentally-benign renewable or recycled reducing agents |
| CA3144899A1 (en) * | 2019-07-26 | 2021-02-04 | Wolfgang Rohde | Process for the recovery of lithium and other metals from waste lithium ion batteries |
| CN111430829A (en) * | 2020-03-11 | 2020-07-17 | 中南大学 | Method for recycling and regenerating waste lithium battery anode material under assistance of biomass waste |
| CN112374553A (en) * | 2020-11-13 | 2021-02-19 | 东北大学 | Method for recycling and regenerating retired lithium ion battery anode material |
| CN112662881A (en) * | 2020-12-14 | 2021-04-16 | 徐州宇帆机电科技有限公司 | Method for preparing industrial cobalt powder by microwave reduction pyrolysis of cobalt acid lithium battery |
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