CN112768798A - Method for preventing impurity metal from being separated out in process of recycling waste lithium battery cathode - Google Patents
Method for preventing impurity metal from being separated out in process of recycling waste lithium battery cathode Download PDFInfo
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Abstract
The invention discloses a method for preventing impurity metals from being separated out in a process of recycling a negative electrode of a waste lithium battery. Which comprises the following steps: 1. crushing and screening the waste lithium battery negative electrode; 2. soaking the undersize product in a mixed solution containing perchloric acid, nitric acid and potassium permanganate, washing, introducing a mixed gas of carbon dioxide and oxygen, filtering, washing and drying, then soaking in concentrated sulfuric acid, washing, introducing a mixed gas of carbon dioxide and oxygen, filtering, washing and drying; 3. mixing the oversize product with the product of the step 2; 4. and (3) reacting the mixture with iron oxide at high temperature in a mixed gas of carbon monoxide and nitrogen to obtain the porous graphite loaded zero-valent iron-copper bimetallic. The method recovers the waste lithium battery cathode by the method of crushing, screening, acid washing, oxidizing, settling and coupling carbothermic reduction reaction, so that the method does not contain impurity metals of lithium, nickel, cobalt, manganese and lead, constructs products with high dispersibility, electron transfer capability and reaction activity, and realizes the treatment of waste by waste.
Description
Technical Field
The invention relates to a method for recycling waste lithium batteries, in particular to a method for preventing impurity metals from being separated out in the process of recycling the negative electrodes of the waste lithium batteries.
Background
Lithium batteries (LIBs) have been used in many areas of life, and the rapid upgrade of LIBs-related products has resulted in the generation of huge quantities of waste LIBs, which, if not effectively recycled, would result in waste of resources and energy, and also cause a series of environmental problems. The recovery of the waste LIBs is mainly concentrated on recovering metal materials in the waste LIBs, the high-quality negative electrode graphite is rarely recycled, most of the waste LIBs are discarded again after the metal materials are recovered or are burnt as a carbon source in the metal recovery process, and therefore a large amount of high-quality graphite resources are wasted. The conductivity of the graphite is one hundred times higher than that of common nonmetal, the density is high, the electrochemical performance is stable, the graphite can resist acid, alkali and organic solvent corrosion, and the graphite also has good thermal conductivity and plasticity. However, lithium is deposited on the surface of the negative electrode when the lithium battery is overcharged. In addition, the cathode material is dissolved by overcharge and reaction of the electrolyte during overcharge, so that nickel, cobalt, manganese, lead, and the like pass through the separator and are finally deposited on the surface of the cathode. The invention discloses a method for recovering a lithium battery negative electrode material, which is named as 'a method for recovering a lithium battery negative electrode material' with the application number of 201610879320.8 and discloses a method for recovering a lithium battery negative electrode material. The invention with the name of application No. 201911132255.2 discloses a method for recovering copper powder from waste lithium batteries, and discloses a method for recovering copper powder from waste lithium batteries. However, the graphite powder obtained by these methods contains impurities such as lithium, nickel, cobalt, manganese and the like, so that a high-quality product cannot be obtained, and the subsequent utilization of the recovered product is affected.
The invention discloses a recovery method of waste lithium ion battery negative electrode materials, with the title of 201811069884.0, which comprises the steps of carbonizing a binder by performing primary heat treatment on a negative electrode sheet, decomposing an SEI (solid electrolyte interphase) film in negative electrode powder by performing secondary heat treatment to obtain activated negative electrode powder, removing lithium in the activated negative electrode powder by acid washing, and performing reduction treatment on an acid washing product to obtain the negative electrode powder. The invention discloses a method for recovering waste lithium ion battery negative electrode materials, which is named as 'a method for recovering waste lithium ion battery negative electrode materials' with the name of 202010166434.4. The invention with the application number of 201811051656.0 discloses a method for recycling and regenerating all components of a waste lithium ion battery negative electrode, which comprises the steps of carrying out ultrasonic treatment on a mixture of a waste lithium ion battery negative electrode sheet and water to obtain a copper foil and a graphite dispersion liquid, drying the copper foil for recycling, mixing the graphite dispersion liquid with an organic acid for acid leaching to obtain graphite and a lithium-containing leachate, drying the graphite for recycling, evaporating and concentrating the lithium-containing leachate, dropwise adding a carbonate saturated solution, precipitating, separating and drying to obtain lithium carbonate. However, these methods generate harmful gases and cannot completely remove impurity metals.
The technology of degrading pollutants by utilizing zero-valent iron materials is widely used, and the invention with the application number of 201911139130.2 is named as a preparation method for preparing a zero-valent iron catalyst by utilizing red mud and bituminous coal, and discloses a method for preparing a zero-valent iron catalyst by utilizing red mud and bituminous coalThe preparation method of the zero-valent iron catalyst from the bituminous coal comprises the steps of respectively drying Bayer process red mud and the bituminous coal to obtain the red mud and the bituminous coal, mechanically and uniformly mixing the red mud and the bituminous coal, putting the mixture into a sealed iron-chromium alloy reactor, and carrying out pyrolysis drying treatment to obtain the zero-valent iron catalyst. The invention with the application number of 201911290236.2 discloses a pyrolytic carbon loaded zero-valent iron (ZVI) composite material and a preparation method and application thereof, and the preparation method and application thereof are characterized in that natural hematite powder and crushed pine biomass are mixed, water is added for ultrasonic dispersion, drying is carried out, the mixed raw material is placed in a tubular furnace for jointly pyrolyzing the pine biomass and the natural hematite (the main component is Fe)2O3) Of Fe2O3Reducing to ZVI and generating composite material PC/ZVI. The invention with the application number of 202010318304.8 is named as a long-term stable biochar-zero-valent iron composite material and a one-step preparation method thereof, and discloses a long-term stable biochar-zero-valent iron composite material and a one-step preparation method thereof. The invention with the application number of 201910205128.4 is named as 'a high-adsorptivity porous carbon loaded zero-valent iron catalyst and a preparation method and application thereof', and discloses a high-adsorptivity porous carbon loaded zero-valent iron catalyst and a preparation method and application thereof. However, these methods do not solve the problems of easy passivation of the zero-valent iron surface and low reactivity.
The invention discloses a preparation method of a Fe-Cu bimetallic tourmaline synergistic microorganism Cr (VI) removing filler, which is 201911042901.6 and discloses a preparation method of a Fe-Cu bimetallic tourmaline synergistic microorganism Cr (VI) removing filler. The invention with the title of application number of 201710642014.7 discloses a vulcanization modified Fe-Cu bimetallic material, a preparation method and a method for removing chromium-containing wastewater, and discloses a vulcanization modified Fe-Cu bimetallic material, a preparation method and a method for removing chromium-containing wastewater. However, these methods do not solve the problems of poor mobility of zero-valent iron in water and poor electron transfer ability.
Disclosure of Invention
The invention aims to solve the problems that graphite powder obtained by the existing waste lithium battery recovery process contains impurities of lithium, nickel, cobalt, manganese and lead, high-quality products cannot be obtained and subsequent utilization of the products is affected, and problems that zero-valent iron materials are low in reaction activity, easy to passivate the surface and weak in electron transfer capacity, and by coupling the mechanical crushing and screening, acid washing, oxidation and sedimentation treatment and the carbothermic reduction reaction, waste lithium battery cathode materials are recovered efficiently, and high value-added composite material products are obtained. The technical scheme of the invention is specifically introduced as follows.
A method for preventing impurity metals from being separated out in the process of recycling the negative electrode of a waste lithium battery utilizes mechanical crushing and screening and acid washing, oxidation and sedimentation treatment coupled with carbothermic reduction reaction and comprises the following steps:
step 1, crushing the disassembled negative electrode of the waste lithium battery, and screening by using a sieve with the aperture of 0.09mm-0.18 mm;
step 3, grinding the oversize product in the step 1 in a ball mill for 4-24 hours, and mixing the ground product with the product obtained in the step 2 according to the mass ratio of 1:100-30: 100;
and 4, mixing the mixture obtained in the step 3 with an iron oxide according to a mass ratio of 1:1-1:10, putting the mixture into a tubular furnace, and adding carbon monoxide: the volume ratio of nitrogen is 1: 1-10: 1 mixed gas flow of 10-500cm3Heating at 900-; the porous graphite load zero-valent iron-copper bimetallic does not contain impurity metals of lithium, nickel, cobalt, manganese and lead.
In the invention, in the step 2, the volume ratio of the carbon dioxide to the oxygen is 2: 1-1: 4.
in the invention, in the step 4, the granularity of the iron oxide is less than 0.5 mm.
In the invention, in the step 4, the iron oxide is ferric oxide or ferroferric oxide, and the iron oxide is used as a pore-forming agent and a carbothermic reducing agent.
Compared with the prior art, the invention has the beneficial effects that:
the method can realize high-quality recovery of the cathode of the waste lithium battery, avoid the influence on the subsequent recycling link caused by leaving impurity metals such as lithium, nickel, cobalt, manganese and lead in the cathode material in the recovery process, and improve the reaction activity of the zero-valent iron material. The invention can primarily remove impurities such as lithium, nickel, cobalt, manganese and lead in undersize materials by utilizing the treatment of mixed acid prepared by perchloric acid and concentrated nitric acid and potassium permanganate and obtain graphite with a certain pore passage, and residual trace impurities such as lithium, nickel, cobalt, manganese and lead can be further dissolved and precipitated and removed by utilizing the mixed gas of carbon dioxide and oxygen introduced after the treatment and washing of concentrated sulfuric acid, and porous graphite with better pore structure can be obtained. The treated mixture on the screen and under the screen is put into a tubular furnace to be heated with iron oxide in the mixed gas atmosphere of carbon monoxide and nitrogen, so that the graphite can be further subjected to pore-forming by utilizing the solid-solid reaction of iron oxide and carbon and the solid-gas reaction of iron oxide and carbon monoxide in the reduction process of the iron oxide, the generated zero-valent iron-copper bimetallic can be firmly loaded on the porous graphite, and the generated porous graphite loaded zero-valent iron-copper bimetallic can be used as an efficient water treatment reagent for repairing polluted water.
Drawings
FIG. 1 is a flow chart of the treatment process of example 1 of the present invention.
Figure 2 XRD results of graphite after treatment of example 1 of the present invention.
FIG. 3 is an SEM image of the surface morphology of untreated graphite.
FIG. 4 is an SEM image of the porous graphite loaded with zero-valent iron-copper bimetallic in example 1 of the present invention.
FIG. 5 is an SEM image of the porous graphite loaded zero-valent iron-copper bimetallic material obtained in example 2 of the present invention.
FIG. 6 is an SEM image of the porous graphite loaded zero-valent iron-copper bimetallic material obtained in example 3 of the present invention.
Detailed Description
The present invention will be further described with reference to specific embodiments, which are intended to be illustrative only, and the following examples and descriptions are provided only to illustrate the principle of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the present invention, which fall within the scope of the claimed invention, but the scope of the present invention is not limited thereto.
Example 1
The embodiment provides a method for preventing impurity metals of lithium, nickel, cobalt, manganese and lead from being separated out in the process of recycling a cathode of a waste lithium battery, ferric oxide is used as a carbothermic reducing agent and a pore-forming agent, and the specific recycling method comprises the following steps:
step 1, crushing the disassembled negative electrode of the waste lithium battery, and screening by using a sieve with the aperture of 0.18 mm;
mixed gas of carbon dioxide and oxygen is introduced after treatment and washing of mixed acid and potassium permanganate prepared from perchloric acid and concentrated nitric acid and concentrated sulfuric acid, residual trace impurities of lithium, nickel, cobalt, manganese and lead can be further dissolved and precipitated to be removed, porous graphite with a better pore structure can be obtained, and XRD (X-ray diffraction) results of the treated graphite are shown in figure 2 and only contain pure graphite.
Step 3, grinding the oversize product in the step 1 in a ball mill for 24 hours, and mixing the ground product with the product obtained in the step 2 according to the mass ratio of 5: 100;
and 4, mixing the mixture obtained in the step 3 with iron oxide with the granularity of less than 0.5mm according to the mass ratio of 1:1, putting the mixture into a tube furnace, and reacting the mixture in the presence of carbon monoxide: the volume ratio of nitrogen is 1:1 mixed gas flow of 20cm3Heating at 900 ℃ for 2h at the time of/min to obtain the porous graphite loaded zero-valent iron-copper bimetallic, wherein the porous graphite loaded zero-valent iron-copper bimetallic does not contain impurity metals of lithium, nickel, cobalt, manganese and lead, and the mass fractions of graphite, iron and copper are respectively 56%, 41% and 3%.
Controlling the granularity of the ferric oxide to be less than 0.5mm can ensure that the obtained porous graphite loaded with the zero-valent iron-copper bimetal reacts more fully in the preparation process, controlling the addition amount of the ferric oxide can regulate and control the zero-valent iron content of the final product, and under the temperature of 900 ℃ and above, the porous graphite and the carbon monoxide and the ferric oxide generate the carbothermic reduction reaction to generate the zero-valent iron and continuously pore-form the graphite, so that the zero-valent iron-copper bimetal is firmly loaded on the porous graphite.
As shown in FIG. 4, the SEM image of the material obtained in this example showed that the graphite after recovery had wrinkles on the surface, enlarged interlayer spacing, numerous slits, and a specific surface area of 0.9m or more, as compared with the graphite without recovery (FIG. 3)2The/g is increased to 2m2In terms of/g, which is more advantageous for foulingAnd (4) adsorbing the dye. Meanwhile, the micron-sized zero-valent iron and copper are firmly and uniformly distributed on the surface of the porous graphite, so that the agglomeration effect of the zero-valent iron is weakened, the galvanic cell effect formed by the micron-sized zero-valent iron and the copper can promote electron transfer, the reaction activity of the zero-valent iron is improved, and the degradation effect on pollutants is higher.
When 0.3g of the material obtained in example 1 is used for treating 100mL of 4-chlorophenol simulated wastewater with the concentration of 5mg/L, the removal rate can reach 75% after 18 h.
Example 2
The embodiment provides a method for preventing impurity metals of lithium, nickel, cobalt, manganese and lead from being separated out in the process of recycling a cathode of a waste lithium battery, ferric oxide is used as a carbothermic reducing agent and a pore-forming agent, and the specific recycling method comprises the following steps:
step 1, crushing the disassembled negative electrode of the waste lithium battery, and screening by using a sieve with the aperture of 0.09 mm;
the graphite with certain pore canal can be obtained preliminarily by treating the mixed acid prepared from perchloric acid and concentrated nitric acid and potassium permanganate. The mixed gas of carbon dioxide and oxygen is introduced after the concentrated sulfuric acid is treated and washed, so that the residual trace impurity metals of lithium, nickel, cobalt, manganese and lead can be further dissolved and precipitated to be removed, and the porous graphite with a better pore structure can be obtained.
Step 3, grinding the oversize product in the step 1 in a ball mill for 10 hours, and mixing the ground product with the product obtained in the step 2 according to the mass ratio of 10: 100;
step 4, mixing the mixture obtained in the step 3 with the particle size of less than 0.5mixing mm ferroferric oxide according to the mass ratio of 1:1, and putting the mixture into a tubular furnace to react in a carbon monoxide: the volume ratio of nitrogen is 1:1 mixed gas flow of 10cm3Heating at 1000 ℃ for 2h at the time of/min to obtain the porous graphite loaded zero-valent iron-copper bimetallic, wherein the porous graphite loaded zero-valent iron-copper bimetallic does not contain impurity metals of lithium, nickel, cobalt, manganese and lead, and the mass fractions of graphite, iron and copper are 52%, 42% and 6% respectively.
Controlling the particle size of the ferric oxide to be less than 0.5mm can ensure that the obtained porous graphite loaded with the zero-valent iron-copper bimetal reacts more fully in the preparation process, controlling the addition amount of the ferric oxide can regulate and control the zero-valent iron content of the final product, and at the temperature of 900 ℃ and above, the porous graphite and the carbon monoxide and the ferric oxide undergo a carbothermic reduction reaction to generate zero-valent iron and simultaneously continue to pore the graphite, so that the zero-valent iron-copper bimetal is firmly loaded on the porous graphite, as shown in fig. 5.
Compared with the graphite (FIG. 3) which is not recovered, the recovered graphite has wrinkles on the surface, enlarged interlayer spacing, numerous slits and specific surface area of 0.9m2The/g is increased to 3m2In terms of/g, this is more favorable for the adsorption of contaminants. Meanwhile, in the obtained composite material, micron-sized zero-valent iron and copper are firmly and uniformly distributed on the surface of the porous graphite, so that the agglomeration effect of the zero-valent iron is weakened, the galvanic cell effect formed by the micron-sized zero-valent iron and the copper can promote electron transfer, the reaction activity of the zero-valent iron is improved, and the composite material has a higher degradation effect on pollutants.
When 0.3g of the material obtained in the example 2 is used for treating 100mL of 4-chlorophenol simulated wastewater with the concentration of 5mg/L, the removal rate can reach 83% after 18 h.
Example 3
The embodiment provides a method for preventing impurity metals of lithium, nickel, cobalt, manganese and lead from being separated out in the process of recycling a cathode of a waste lithium battery, ferric oxide is used as a carbothermic reducing agent and a pore-forming agent, and the specific recycling method comprises the following steps:
step 1, crushing the disassembled negative electrode of the waste lithium battery, and screening by using a sieve with the aperture of 0.09 mm;
the graphite with certain pore canal can be obtained preliminarily by treating the mixed acid prepared from perchloric acid and concentrated nitric acid and potassium permanganate. The mixed gas of carbon dioxide and oxygen is introduced after the concentrated sulfuric acid is treated and washed, so that the residual trace impurity metals of lithium, nickel, cobalt, manganese and lead can be further dissolved and precipitated to be removed, and the porous graphite with a better pore structure can be obtained.
Step 3, grinding the oversize product in the step 1 in a ball mill for 5 hours, and mixing the ground product with the product obtained in the step 2 according to the mass ratio of 5: 100;
and 4, mixing the mixture obtained in the step 3 with iron oxide with the granularity of less than 0.5mm according to the mass ratio of 1:2, putting the mixture into a tube furnace, and reacting the mixture in the presence of carbon monoxide: the volume ratio of nitrogen is 1:1 mixed gas flow of 10cm3Heating at 1000 ℃ for 2h at the time of/min to obtain the porous graphite loaded zero-valent iron-copper bimetallic, wherein the porous graphite loaded zero-valent iron-copper bimetallic does not contain impurity metals of lithium, nickel, cobalt, manganese and lead, and the mass fractions of graphite, iron and copper are respectively 37%, 59% and 4%.
Controlling the particle size of the ferric oxide to be less than 0.5mm can ensure that the obtained porous graphite loaded with the zero-valent iron-copper bimetal reacts more fully in the preparation process, controlling the addition amount of the ferric oxide can regulate and control the zero-valent iron content of the final product, and at the temperature of 900 ℃ and above, the porous graphite and the carbon monoxide and the ferric oxide undergo a carbothermic reduction reaction to generate zero-valent iron and continue to form pores on the graphite, so that the zero-valent iron-copper bimetal is firmly loaded on the porous graphite, as shown in fig. 6.
With unrefined graphiteFIG. 3) shows that the surface of the graphite after recovery had wrinkles, the interlayer spacing was increased, a large number of slits were present, and the specific surface area was from 0.9m2The/g is increased to 6m2In terms of/g, this is more favorable for the adsorption of contaminants. Meanwhile, in the obtained composite material, micron-sized zero-valent iron and copper are firmly and uniformly distributed on the surface of the porous graphite, so that the agglomeration effect of the zero-valent iron is weakened, the galvanic cell effect formed by the micron-sized zero-valent iron and the copper can promote electron transfer, the reaction activity of the zero-valent iron is improved, and the composite material has a higher degradation effect on pollutants.
When 0.3g of the material obtained in example 3 is used for treating 100mL of 4-chlorophenol simulated wastewater with the concentration of 5mg/L, the removal rate can reach 91% after 18 h.
Claims (4)
1. A method for preventing impurity metals from being separated out in the process of recycling the negative electrode of a waste lithium battery is characterized by comprising the following steps: the method comprises the following steps:
step 1, crushing the disassembled negative electrode of the waste lithium battery, and screening by using a sieve with the aperture of 0.09mm-0.18 mm;
step 2, soaking the undersize materials in the step 1 in acidic oxidizing solution with 2-6 times of volume for 0.1-4h, washing, and then utilizing a gas distribution device to distribute gas for 50-300cm3Introducing mixed gas of carbon dioxide and oxygen at a speed of/min, filtering, washing, drying, soaking in 1.5-4 times volume of 70% -98% sulfuric acid for 0.1-8h, washing, and cleaning with gas distribution device at a volume of 50-150cm3Introducing mixed gas of carbon dioxide and oxygen at a speed of/min, filtering, washing and drying to prevent impurity metals including lithium, nickel, cobalt, manganese and lead from being mixed; wherein: the acidic oxidizing solution is prepared by mixing 50-72 wt% of perchloric acid and 43-68 wt% of nitric acid in equal volume and adding potassium permanganate; in the acidic oxidizing solution, the concentration of potassium permanganate is between 20 and 150 g/L;
step 3, grinding the oversize product in the step 1 in a ball mill for 4-24 hours, and mixing the ground product with the product obtained in the step 2 according to the mass ratio of 1:100-30: 100;
and 4, mixing the mixture obtained in the step 3 with an iron oxide according to a mass ratio of 1:1-1:10, putting the mixture into a tubular furnace, and adding carbon monoxide: nitrogen gasThe volume ratio is 1: 1-10: 1 mixed gas flow of 10-500cm3Heating at 900-; the porous graphite load zero-valent iron-copper bimetallic does not contain impurity metals of lithium, nickel, cobalt, manganese and lead.
2. The method for preventing impurity metals from being precipitated in the process of recycling negative electrodes of waste lithium batteries according to claim 1, wherein in the step 2, the volume ratio of carbon dioxide to oxygen is 2: 1-1: 4.
3. the method for preventing the precipitation of impurity metals in the process of recycling negative electrodes of spent lithium batteries according to claim 1, wherein: in step 4, the particle size of the iron oxide is less than 0.5 mm.
4. The method for preventing the precipitation of impurity metals in the process of recycling negative electrodes of spent lithium batteries according to claim 1, wherein: in step 4, the iron oxide is ferric oxide or ferroferric oxide.
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Cited By (2)
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| CN115287075A (en) * | 2022-07-15 | 2022-11-04 | 濮阳天地人环保科技股份有限公司 | Soil remediation catalyst prepared by recycling waste lithium battery material lithium iron phosphate and using method thereof |
| CN115945057A (en) * | 2022-12-19 | 2023-04-11 | 上海第二工业大学 | Application method for targeted degradation of VOCs (volatile organic compounds) by using waste battery and zero-valent iron composite material |
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