CN111203172A - Method for preparing heavy metal adsorbent by recycling waste lithium ion battery anode material - Google Patents
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Abstract
A method for preparing a heavy metal adsorbent by recycling a waste lithium ion battery anode material comprises the following steps: (1) disassembling the waste lithium ion battery, and unfolding the waste lithium ion battery into coiled aluminum foil; (2) recovering the lithium ion battery anode material obtained by disassembly and obtaining a water body heavy metal adsorbent precursor material; (3) the adsorbent precursor material is modified. The heavy metal adsorbent prepared by the method is used for adsorbing and treating the water body polluted by Cu, Cd, Zn or Pb heavy metals, and can be regenerated. The invention widens the resource utilization approach of the waste lithium ion battery, and from the perspective of 'treating waste by waste', the waste lithium ion battery is used as a heavy metal adsorbent for polluted water body by recovering and treating the positive electrode material based on the special crystal structure attribute of the metal oxide which the waste lithium ion battery has, and no related method and application report is seen at present.
Description
Technical Field
The invention relates to a method for preparing a water body heavy metal adsorbent by recycling a positive electrode material of a waste lithium ion battery, belonging to the technical field of preparation of water body heavy metal adsorbents.
Background
After being taken by human body, the heavy metal exists in the form of ions and is combined with macromolecular compounds such as protein, fat and the like in the body, and the formed chelate has higher toxicity. Heavy metals (such as mercury, lead, copper, zinc, cadmium and the like) in the polluted water body have the characteristics of biological enrichment, persistence, amplification and the like, and are one of the ecological environmental problems which are widely concerned at present.
The current common treatment methods for heavy metal pollution of water bodies comprise a chemical precipitation method, an electrolysis method, an ion exchange method, a heavy metal ion adsorption method and the like. Although the precipitation method is simple to operate and wide in application, the precipitation method has certain limitation in use, can only be applied to heavy metal ions (such as lead, silver, iron, copper, manganese and the like) which can generate water-insoluble precipitate substances with a precipitator, and the added chemical substances are easy to cause secondary pollution. The electrolysis method is to carry out chemical reaction through an electrolytic cell, reduce heavy metal ions, and deposit the obtained heavy metal simple substance on a cathode or an anode, thereby removing heavy metal pollutants in a water body. However, when the amount of wastewater to be treated is large, the power consumption and the electrode metal consumption are large, and the separated precipitate is not easy to treat and utilize. The ion exchange method is based on the ion exchange principle, and the heavy metal ions to be removed are exchanged from the water, so that the aim of removing the heavy metal ions in the water is fulfilled. However, the ion exchange method often generates waste liquid in the process of treating wastewater, and has large consumption of ion exchangers and high operation cost.
The adsorption method is a method for removing heavy metal ions in a water body by adsorbing an adsorbent with a large specific surface area and a special internal structure. Common adsorbents include activated carbon adsorbents and inorganic ceramsite adsorbents, but the adsorbents have high application cost and are difficult to regenerate.
In recent years, with the increasing shortage of fossil resources in the world and the urgent need for ecological environment protection, the development of electric vehicles instead of fuel vehicles has attracted much attention. The rapid development of the power battery industry, particularly the mass production and wide application of lithium ion batteries, has led to a proliferation of the number of waste batteries. If the waste lithium ion battery cannot be timely, effectively and reasonably treated, serious resource waste can be caused, and environmental problems are caused, the current development of the lithium ion battery industry faces to solve the following problems: and (4) reasonably utilizing and disposing the waste lithium ion battery.
At present, the treatment of the waste lithium ion battery is to recover heavy metals in the positive electrode by methods of acid leaching, biological leaching, solvent extraction, chemical precipitation, electrochemical treatment and the like, but the processes are long, and the problems of incomplete recovery, high recovery cost, secondary pollution and the like exist.
CN110563046A discloses a method for recycling anode materials of waste lithium ion batteries, which comprises the steps of sequentially carrying out mixed organic acid treatment, solid-liquid separation, solid collection, washing, drying, crushing and calcination on the anode materials obtained by separating the waste lithium ion batteries to obtain an anode active material manganese oxide. But the recovery process is complex, especially the calcination working section consumes long time and the recovery cost is higher.
CN110144461A discloses a comprehensive recovery method of waste lithium ion battery positive plates, which comprises the steps of calcining positive plate leftover materials and scrapped positive plates in a vacuum furnace, then rapping and screening to obtain positive active substances, adding the positive active substances into sulfuric acid leachate to carry out secondary leaching, and filtering and separating to obtain leaching residue carbon and leachate containing nickel, cobalt, manganese and lithium; adding activated carbon into the leachate for adsorption deoiling and desiliconization, supplementing nickel carbonate, cobalt carbonate, manganese carbonate or lithium carbonate into filter residues to obtain a precursor, and performing ball milling, sintering, crushing, grinding and screening on the precursor to obtain the nickel cobalt lithium manganate positive electrode material. The recovery process of the waste lithium ion battery positive plate is complex, the cost is high, acid and alkali extraction is needed, and secondary pollution is easy to generate.
Disclosure of Invention
Aiming at the current situation that the recovery way of the waste lithium ion battery is single and the recovery cost is higher. The invention provides a method for preparing a heavy metal adsorbent by recovering a positive electrode material of a waste lithium ion battery, which has the advantages of simple process, low cost and good utilization effect from the viewpoint of 'treating waste by waste and changing waste into valuable', can realize the recovery treatment of the positive electrode material of the waste lithium ion battery, and can be used as a water body heavy metal adsorbent.
The invention discloses a method for preparing a heavy metal adsorbent by recycling a waste lithium ion battery anode material, which comprises the following steps:
(1) disassembling the waste lithium ion battery:
obtaining a battery pack from the shell of the waste lithium ion battery, and taking out a connecting wire and a welding spot of the battery pack to obtain a lithium ion single battery; discharging each single cell; putting the discharged lithium ion single cell into a saturated NaCl solution to short-circuit the positive electrode and the negative electrode of the lithium ion single cell, finally completely discharging the lithium ion single cell, then disassembling the single cell, unfolding a coiled aluminum foil, wherein attachments (black solid attachments) on the aluminum foil are positive electrode materials of the lithium ion battery;
the discharging process of each single battery cell is as follows: and (3) connecting the positive electrode and the negative electrode of each single cell with a small bulb of 3-5W for discharging until the small bulb is extinguished (not lighted).
The complete discharge of the single cell refers to detecting the voltage of the discharged lithium ion single cell, and ensuring that the voltage of the single cell is less than 0.3V (namely, the discharge process is considered to be finished).
The process of disassembling the monocell is to cut off the sealing ring at the positive end of the cell, disassemble the top gasket, cut off the aluminum shell wrapped outside, tear the transparent film, unfold the coiled aluminum foil, and the aluminum foil is attached to the positive active material (metal oxide material) of the lithium ion cell.
(2) And (3) recovering the lithium ion battery anode material obtained by disassembly:
cutting the aluminum foil with the positive active material into pieces, immersing the pieces in dimethyl sulfoxide (DMSO), oscillating in a water bath at constant temperature, dissolving an electrode binder (polyvinylidene fluoride (PVDF)) in the dimethyl sulfoxide, performing microwave ultrasonic treatment, completely separating the positive active material on the aluminum foil, taking out the aluminum foil, and washing and recovering the aluminum foil by using clear water to obtain a clean aluminum foil;
oscillating the dimethyl sulfoxide mixed solution dissolved with the electrode binder after taking out the aluminum foil under the condition of keeping the water bath constant temperature at 80 +/-5 ℃, filtering by adopting a filter membrane with the aperture of 0.45 mu m to obtain a positive active material (filtration and retention substance), cleaning the positive active material by using 70% ethanol and deionized water in sequence, and drying to obtain a water body heavy metal adsorbent precursor material;
the side length of the fragments is 0.2-1 cm. The mass ratio of the fragments to dimethyl sulfoxide is 1: 10 to 15. The oscillation time is 1-2 hours. The microwave ultrasonic time is 10-30 minutes. The drying temperature is 80-100 ℃.
Because the solubility of PVDF in DMSO is reduced at low temperature, the filtered mixed solution is kept stand and cooled to 0-10 ℃, if the PVDF exceeds the saturation degree in the mixed solution, the PVDF is separated out from the solvent, then a filter membrane with the aperture of 0.45 mu m is adopted for filtering, separating and recovering the PVDF, and the separated DMSO mixed solution can be continuously returned to the front end of the process to be used as the solvent of the PVDF in the electrode active material; if the PVDF does not exceed the saturation degree in the mixed solution, the mixed solution can be directly returned to the front end of the process to be used as a solvent of the PVDF in the electrode active material, and the solvent is recycled for recycling the electrode active material.
(3) Adsorbent precursor material modification:
under the condition of room temperature, adding the obtained water body heavy metal adsorbent precursor material into a DTPA (diethyltriaminepentaacetic acid) solution with the mass concentration of 0.1%, and carrying out ultrasonic treatment to form a precursor material mixed solution which is uniformly dispersed;
and slowly dropwise adding the precursor material mixed solution into an alkali solution of glutaraldehyde, reacting at room temperature, washing the obtained static precipitation product with deionized water and ethanol, and drying to obtain the modified water body heavy metal adsorbent.
The water body heavy metal adsorbent precursor material is prepared from the following raw materials in parts by weight of 1g: 5ml of DTPA solution was added in a mass to volume ratio. The ultrasonic time is 10-30 minutes. The precursor material mixed solution is prepared by mixing the following raw materials in a ratio of 1: adding the mixture into an alkali solution of glutaraldehyde in a volume ratio of 4-5. The alkali solution of the glutaraldehyde is prepared by mixing 20-30% of glutaraldehyde solution and 0.01M NaOH according to the volume ratio of 1: 20-30. The reaction time at room temperature is 10-12 hours. The drying is carried out in an oven at 60-80 ℃ for 24 hours.
The heavy metal adsorbent prepared by the method is used for adsorbing and treating heavy metal polluted water bodies of Cu, Cd, Zn or Pb:
for heavy metal-related industrial wastewater, when in static adsorption, the pH of the wastewater is firstly adjusted to 6-8, and the dosage of the adsorbent, namely ① water heavy metal Cu, is determined according to the concentration of the heavy metal in the water2+、Pb2+、Cd2+Or Zn2+When the concentration is lower than 50mg/L, the adsorbent is added into the water body according to the proportion of 1g to 1000ml (when adsorption balance is achieved, the removal rates of four metals in the water body can respectively reach more than 85%, 50% and 50%), (②) water body heavy metal Cu2+、Pb2+、Cd2+Or Zn2+When the concentration is 50-100mg/L, the adsorbent is added into the water body according to the proportion of 1g to 500ml (after the adsorption balance is reached, the removal rates of four metals in the water body can respectively reach more than 85%, 60% and 50%), ③ water body heavy metal Cu2+、Pb2+、Cd2+Or Zn2+When the concentration is more than 100mg/L, the concentration is counted as n times of 100mg/L, n is a positive integer, and the adsorbent is added into the water body according to the proportion of ng to 500ml (after the adsorption balance is achieved, the adsorption removal rates of four metals in the water body can respectively reach more than 80%, 50% and 50%).
The dynamic adsorption mode can be adopted during actual engineering application, the adsorption columns are adopted to operate in series according to the actual concentration of heavy metals in the sewage and the purification requirement of polluted water, and the operation is carried out for 12 hours according to the retention time of single-column adsorption until the discharge standard is reached. After the adsorbent is saturated, the adsorbent can be taken out for regeneration.
The regeneration process of the adsorbent comprises the following steps:
(1) separating, washing and collecting the heavy metal adsorbent which is saturated in adsorption through vacuum filtration, drying, soaking in 1mol/L HCl solution for desorption for 24 hours, washing the desorbed adsorbent with distilled water until no heavy metal Cu is detected in the solution2+、Pb2+、Cd2+、Zn2+；
(2) Adding the desorbed adsorption material into 0.1mol/L NaOH regeneration liquid, oscillating for regeneration for 2 hours, removing the regeneration liquid after regeneration is finished, washing the adsorbent with deionized water to be neutral, and drying for later use.
The invention widens the resource utilization approach of the waste lithium ion battery, and the method and the application report related to the method are not seen at present on the basis of the special crystal structure attribute of the metal oxide of the waste lithium ion battery and the recovery and preparation of the heavy metal adsorbent for the polluted water body by the anode material from the viewpoint of 'treating waste by waste'.
The invention has the following characteristics:
1. the water body heavy metal adsorbent is prepared from the anode material of the waste lithium ion battery, so that the waste is treated by the waste, the waste is changed into the valuable, and the resource utilization way of the waste lithium ion battery is widened.
2. The adsorbent prepared by the anode material of the waste lithium ion battery has high efficiency of removing heavy metal in water and large adsorption capacity; can be recycled; the adsorption capacity of the adsorbent is compared with that of other conventional water heavy metal adsorbents, and the following table shows the adsorption capacity.
Comparison table of adsorption capacity of adsorbent prepared by waste lithium ion battery anode and other adsorbents
Reference 1: peter et al, 2012, Dual Efficiency Of Nano-Structured TiO2/Zeolyte Systems In Removal Of Copper(II)And Lead(II)Ions From AqueousSolution Under Visible Light,in:Lazar,M.D.(Ed.)Processes in Isotopes andMolecules.Amer Inst Physics,Melville,pp.139-143。
Reference 2: zheng et al, 2012), Preparation of cellular derivative from stand and matters application for a cadmium ion adsorption from aqueous solution. Carbohydr. Polymer.90 (2), 1008-.
Reference 3: bahaidi et al, 2018, Development of a closed point extraction differentiation of a cadmium and lead in a solid sample using a flame atomic emission spectrometry, desalin, Water treat.124, 193-201.
Reference 4: feng et al, 2017, Simple aspect of easy handling mill-sized pore attulates/polymer beads for latent measure removal. journal of Colloid and Interface Science 502, 52-58.
Reference 5: zeng et al, 2015, Adsorption of Cd (II), Cu (II) and Ni (II) ion by cross-linking chips/restore nano-hybrid composite microsheres. Carbohydr. Polym.130, 333-343.
Reference 6: sun et al, 2016. Characterisation of cyclic acid-modified shells and application for aqueous lead (II) removal. Water, Air, & SoilPollution 227(9), 298.
Reference 7: mouni et al, 2011, Adsorption of Pb (II) from aqueous solutions using activated carbon stationary from Apricot stone.Desalination276(1-3), 148-.
Reference 8: pap et al, 2017. inactivation of free processing induced water as green activated carbon for the treatment of heavy metals and chlorophenols regulated water. journal of cleaning process 162, 958-.
Reference 9: argun et al, 2009 Removal of Cd (II), Pb (II), Cu (II) and Ni (II) from water using modified pine stick: depletion 249(2), 519-527.
3. The adsorbent is applied to the adsorption of heavy metals in water, and has simple process and strong practicability.
Drawings
FIG. 1 is an electron micrograph of an adsorbent prepared from a used lithium ion battery in example 1.
Fig. 2 is an electron microscope image of the adsorbent prepared from the used lithium ion battery after adsorbing Pb ions in example 1.
Fig. 3 is an X-ray diffraction analysis of the adsorbent prepared from the used lithium ion battery before and after adsorption of Pb ions in example 1. In the figure: LFP: lithium iron phosphate; MSLFP: adsorption 1 prepared based on waste lithium iron phosphate battery cathode material#(ii) a LFP-Pb: adsorbing Pb by lithium iron phosphate; MSLFP-Pb: adsorbent 1#After adsorbing Pb
Fig. 4 is an analysis of the regeneration performance of the adsorbent prepared from the used lithium ion battery in example 1.
Fig. 5 is an adsorption isotherm of an adsorbent prepared from a used lithium ion battery in the process of adsorbing Cu ions in example 1.
FIG. 6 is an electron micrograph of the adsorbent prepared from the used lithium ion battery in example 2.
Fig. 7 is an electron microscope image of the adsorbent prepared from the used lithium ion battery after adsorbing Pb ions in example 2.
Fig. 8 is an X-ray diffraction analysis of the adsorbent prepared from the used lithium ion battery before and after adsorption of Pb ions in example 2. In the figure: LMO: lithium manganate; MSLMO: adsorption 2 prepared based on waste lithium manganate ion battery cathode material#(ii) a LMO-Pb: after the lithium manganate material adsorbs Pb; MSLMO-Pb: adsorbent 2#After adsorbing Pb.
Fig. 9 is an analysis of the regeneration performance of the adsorbent prepared from the used lithium ion battery in example 2.
Fig. 10 is an adsorption isotherm of an adsorbent prepared from a used lithium ion battery in the process of adsorbing Cu ions in example 2.
Detailed Description
Example 1
The method for preparing the cathode material based on the waste lithium iron phosphate lithium ion batteryAdjuvant 1#
(1) Disassembling the waste lithium ion battery:
the method comprises the steps of firstly cutting an aluminum-plastic shell of a waste lithium ion battery by a knife to obtain a battery pack consisting of battery monocells, taking out connecting wires and welding points to obtain the lithium ion battery monocells, connecting positive and negative electrodes of each monocell with a small bulb of 3-5W to discharge until the small bulb is not lighted, then putting the lithium ion battery monomer discharged by the small bulb into a saturated NaCl solution to enable the positive and negative electrodes of the lithium ion battery monomer to be in short circuit, and finally enabling the lithium ion battery monomer to be completely discharged. And detecting the voltage of the discharged lithium ion battery monomer by using a universal meter, and after the voltage of the monomer is ensured to be less than 0.3V, considering that the discharging process is finished, and disassembling the battery monomer. Cutting off the sealing ring at the positive end of the battery, then detaching the top gasket, cutting off the aluminum shell wrapped outside, tearing off the transparent film, unfolding the coiled aluminum foil, wherein the attachment (black solid attachment) state on the aluminum foil is the positive active material of the lithium ion battery.
(2) And (3) recovering the lithium ion battery anode material obtained by disassembly:
cutting the aluminum foil with the expanded positive active material into fragments with the side length of 0.2-1cm, immersing the fragments in dimethyl sulfoxide (DMSO) (the mass ratio of the fragments to the DMSO is 1: 10), oscillating the fragments at the constant temperature of 85 ℃ in a water bath for 1 hour, dissolving an electrode binder polyvinylidene fluoride (PVDF) in a DMSO solution, then performing microwave ultrasonic treatment for 10 minutes to completely separate the positive active material on the aluminum foil, taking out the aluminum foil, and washing the aluminum foil with clear water to recover the clean aluminum foil. Filtering the DMSO mixed solution by adopting a filter membrane with the aperture of 0.45 mu m under the condition of keeping the temperature of the DMSO mixed solution at 85 ℃ to obtain a filtering trapped substance-anode active material, washing the active material for 3 times by using 70% ethanol and deionized water in sequence, and drying at the temperature of 80-100 ℃ to obtain the water body heavy metal adsorbent precursor material.
(3) Modification of sorbent precursor materials:
and (3) mixing the obtained precursor material of the heavy metal adsorbent in the water body in a ratio of 1g: 5ml of DTPA solution with the mass concentration of 0.1 percent is added into the mixture by mass volume ratio, and the mixture is subjected to ultrasonic treatment for 10 minutes to form precursor material mixed liquor with uniform dispersion. Slowly dripping 1 part of precursor material mixed solution into 5 parts of aqueous alkali of glutaraldehyde (the volume ratio of 30% glutaraldehyde to 0.01M NaOH is 1:30), reacting at room temperature for 12 hours, washing the obtained static precipitation product with deionized water and ethanol for several times, and drying in an oven at 80 ℃ for 24 hours to obtain the modified water heavy metal adsorbent # 1.
Adding 0.5g adsorbent # 1 into four groups of 250ml heavy metal Cu with concentration of 100mg/L at 25.5 deg.C2+、Pb2+、Cd2+、Zn2+In solution (pH 7.0). Placing the mixture in a constant-temperature water bath oscillator to oscillate and adsorb at the rotating speed of 120 rpm. The adsorbent No. 1 was measured to be heavy metal Cu2+、Pb2+、Cd2+And Zn2+The adsorption capacities of (A) were 42.5, 43.0, 27.5 and 31.0mg/g, respectively. Under these conditions, the adsorbent 1# was aligned with Cu2+、Pb2+、Cd2+、Zn2+The removal rate of the catalyst reaches 85%, 86%, 55% and 62%.
FIG. 1 shows an electron microscope image of adsorbent # 1 prepared by using a waste lithium iron phosphate lithium ion battery in the present example; FIG. 2 is an electron microscope image of an adsorbent prepared from a waste lithium iron phosphate lithium ion battery after adsorbing Pb ions; fig. 3 is an X-ray diffraction analysis of the adsorbent prepared from the spent lithium iron phosphate lithium ion battery before and after adsorption of Pb ions in example 1; FIG. 4 is an analysis of the regeneration performance of the adsorbent prepared from the used lithium iron phosphate lithium ion battery in example 1; fig. 5 is an adsorption isotherm of an adsorbent prepared from a lithium iron phosphate lithium ion battery used in the process of adsorbing Cu ions in example 1.
The adsorbent saturated by adsorption is regenerated according to the following process:
(1) separating, washing and collecting the heavy metal adsorbent which is saturated in adsorption by using a vacuum filtration device, drying, soaking in 1mol/L HCl solution for desorption for 24 hours, washing the desorbed adsorbent with distilled water for several times until no heavy metal Cu is detected in the solution2+、Pb2+、Cd2+、Zn2+；
(2) Adding the desorbed adsorption material into 0.1mol/L NaOH regeneration liquid, oscillating for regeneration for 2 hours, removing the regeneration liquid after regeneration is finished, washing the adsorbent with deionized water to be neutral, and drying for later use.
Example 2
This example prepares adsorbent 2 based on waste lithium manganate ion battery cathode material#
(1) Disassembling the waste lithium ion battery:
the method comprises the steps of firstly cutting an aluminum-plastic shell of a waste lithium ion battery by a knife to obtain a battery pack consisting of battery monocells, taking out connecting wires and welding points to obtain the lithium ion battery monocells, connecting positive and negative electrodes of each monocell with a small bulb of 3-5W to discharge until the small bulb is not lighted, then putting the lithium ion battery monomer discharged by the small bulb into a saturated NaCl solution to enable the positive and negative electrodes of the lithium ion battery monomer to be in short circuit, and finally enabling the lithium ion battery monomer to be completely discharged. And detecting the voltage of the discharged lithium ion battery monomer by using a universal meter, and disassembling the battery monomer after ensuring that the voltage of the monomer is less than 0.3V.
(2) And (3) recovering the lithium ion battery anode material obtained by disassembly:
cutting the aluminum foil with the expanded positive active material into fragments with the side length of 0.2-1cm, immersing the fragments in dimethyl sulfoxide (DMSO) (the mass ratio of the fragments to the DMSO is 1: 15), oscillating the fragments at the constant temperature of 80 ℃ in a water bath for 2 hours, dissolving electrode binder polyvinylidene fluoride (PVDF) in the DMSO, then performing microwave ultrasonic treatment for 30 minutes to completely separate the positive active material on the aluminum foil, taking out the aluminum foil, and washing the aluminum foil with clear water to recover the clean aluminum foil. Filtering the DMSO mixed solution by adopting a filter membrane with the aperture of 0.45 mu m under the condition of keeping the temperature of the DMSO mixed solution at 80 ℃ to obtain a filtering trapped substance-anode active material, washing the active material for a plurality of times by using 70% ethanol and deionized water in sequence, and drying at the temperature of 80-100 ℃ to obtain the water body heavy metal adsorbent precursor material.
(3) Modification of sorbent precursor materials:
and (3) mixing the obtained precursor material of the heavy metal adsorbent in the water body in a ratio of 1g: 5ml of DTPA solution with the mass concentration of 0.1 percent is added into the mixture by the mass volume ratio, and the mixture is subjected to ultrasonic treatment for 15 minutes to form precursor material mixed liquor with uniform dispersion. Slowly dripping 1 part of precursor material mixed solution into 4 parts of aqueous alkali of glutaraldehyde (the volume ratio of 20% glutaraldehyde to 0.01M NaOH is 1:20), reacting at room temperature for 10 hours, washing the obtained static precipitation product with deionized water and ethanol for several times, and drying in an oven at 60 ℃ for 24 hours to obtain the modified water heavy metal adsorbent 2 #.
Adding 0.5g adsorbing material No. 2 into four groups of 250ml heavy metal Cu with concentration of 100mg/L at 24.5 deg.C2+、Pb2+、Cd2+、Zn2+In solution (pH 6.5). Placing the mixture in a constant-temperature water bath oscillator to oscillate and adsorb at the rotating speed of 110 rpm. The adsorbent 2# is tested to be heavy metal Cu2+、Pb2+、Cd2+And Zn2+The adsorption capacities of (A) were 41.0, 42.5, 26.5 and 28.0mg/g, respectively. Under these conditions, the adsorbent 2# was aligned with Cu2+、Pb2+、Cd2+、Zn2+The removal rate of the catalyst reaches 82%, 85%, 53% and 56%.
FIG. 6 shows an electron micrograph of adsorbent # 2 prepared from the waste lithium manganate ion battery of this example; fig. 7 is an electron microscope image of the adsorbent prepared from the waste lithium iron manganese oxide lithium ion battery after adsorbing Pb ions; fig. 8 is an X-ray diffraction analysis of the adsorbent prepared from the lithium iron manganese oxide spent lithium ion battery before and after adsorption of Pb ions in example 2; FIG. 9 is an analysis of the regeneration performance of the adsorbent prepared from the waste lithium iron manganate lithium ion battery in example 2; fig. 10 is an adsorption isotherm of the adsorbent prepared from the waste lithium iron manganate lithium ion battery in the process of adsorbing Cu ions in example 2.
The adsorbent saturated in adsorption was regenerated as in example 1.
Example 3
The present embodiment is different from embodiment 1 in that:
in the step (2), in the process of recovering the lithium ion battery anode material obtained by disassembling, the mass ratio of the fragments to the dimethyl sulfoxide is 1: 12. the shaking time was 1.5 hours. The microwave ultrasonic time is 20 minutes.
In the modification process of the adsorbent precursor material in the step (3), the ultrasonic time is 30 minutes. The precursor material mixed solution is prepared by mixing the following raw materials in a ratio of 1: 4.5 volume ratio to glutaraldehyde solution. The alkali solution of the glutaraldehyde is prepared by mixing 25% glutaraldehyde solution and 0.01M NaOH according to the volume ratio of 1: 25. The reaction time was 11 hours at room temperature. The drying is carried out for 24 hours in an oven at 70 ℃.
This example produced adsorbent # 3.
Adding 1.0g adsorbent # 3 into four groups of 250ml heavy metal Cu with concentration of 200mg/L at 28 deg.C2+、Pb2+、Cd2+、Zn2+In solution (pH 8.0). Placing the mixture in a constant-temperature water bath oscillator to oscillate and adsorb at the rotating speed of 120 rpm. The adsorbent 3# is measured to be heavy metal Cu2+、Pb2+、Cd2+And Zn2+The adsorption capacities of (A) were 40.5, 41.0, 26.5 and 26.0mg/g, respectively. Under these conditions, the adsorbent 3# was aligned with Cu2+、Pb2+、Cd2+、Zn2+The removal rate of the catalyst reaches 81%, 82%, 53% and 52%.
Claims (8)
1.A method for preparing a heavy metal adsorbent by recycling a waste lithium ion battery anode material is characterized by comprising the following steps: the method comprises the following steps:
(1) disassembling the waste lithium ion battery:
obtaining a battery pack from the shell of the waste lithium ion battery, and taking out a connecting wire and a welding spot of the battery pack to obtain a lithium ion single battery; discharging each single cell; putting the discharged lithium ion single cell into a saturated NaCl solution to short-circuit the anode and the cathode of the lithium ion single cell, finally completely discharging the lithium ion single cell, then disassembling the single cell, unfolding a coiled aluminum foil, wherein the attachment state on the aluminum foil is the anode material of the lithium ion battery;
(2) and (3) recovering the lithium ion battery anode material obtained by disassembly:
cutting the aluminum foil with the positive active material into pieces, immersing the pieces in dimethyl sulfoxide, oscillating in water bath at constant temperature, dissolving an electrode binder (polyvinylidene fluoride (PVDF)) in the dimethyl sulfoxide, performing microwave ultrasonic treatment to completely separate the positive active material on the aluminum foil, taking out the aluminum foil, washing with clean water and recovering to obtain a clean aluminum foil;
oscillating the dimethyl sulfoxide mixed solution dissolved with the electrode binder after taking out the aluminum foil under the condition of keeping the water bath constant temperature at 80 +/-5 ℃, filtering by adopting a filter membrane with the aperture of 0.45 mu m to obtain a positive active material, cleaning the positive active material by using 70% ethanol and deionized water in sequence, and drying to obtain a water body heavy metal adsorbent precursor material;
(3) adsorbent precursor material modification:
adding the obtained water body heavy metal adsorbent precursor material into a DTPA solution with the mass concentration of 0.1%, and performing ultrasonic treatment to form a precursor material mixed solution which is uniformly dispersed;
and slowly dropwise adding the precursor material mixed solution into an alkali solution of glutaraldehyde, reacting at room temperature, washing the obtained static precipitation product with deionized water and ethanol, and drying to obtain the modified water body heavy metal adsorbent.
2. The method for preparing the heavy metal adsorbent by recycling the anode material of the waste lithium ion battery as claimed in claim 1, wherein the discharging process of each single cell in the step (1) is as follows: and connecting the positive electrode and the negative electrode of each single cell with a small bulb of 3-5W for discharging until the small bulb is extinguished.
3. The method for preparing the heavy metal adsorbent by recycling the anode material of the waste lithium ion battery as claimed in claim 1, wherein the step (1) of completely discharging the single battery refers to detecting the voltage of a discharged lithium ion single battery and ensuring that the voltage of the single battery is less than 0.3V.
4. The method for preparing the heavy metal adsorbent by recycling the anode material of the waste lithium ion battery as claimed in claim 1, wherein the process of disassembling the single cells in the step (1) comprises the steps of cutting off the sealing ring at the anode end of the battery, disassembling the top gasket, cutting off the aluminum shell wrapped outside, tearing off the transparent film, and unfolding the coiled aluminum foil, wherein the aluminum foil is attached to the anode active material of the lithium ion battery.
5. The method for preparing the heavy metal adsorbent by recycling the anode material of the waste lithium ion battery as claimed in claim 1, wherein the side length of the fragments in the step (2) is 0.2-1cm, and the mass ratio of the fragments to the dimethyl sulfoxide is 1: 10-15, the oscillation time is 1-2 hours, the microwave ultrasonic time is 10-30 minutes, and the drying temperature is 80-100 ℃.
6. The method for preparing the heavy metal adsorbent by recycling the anode material of the waste lithium ion battery as claimed in claim 1, wherein the weight ratio of the precursor material of the heavy metal adsorbent in the water body in the step (3) is 1g: 5ml of DTPA solution is added in the mass-volume ratio, the ultrasonic time is 10-30 minutes, and the precursor material mixed solution is prepared by mixing the following components in a proportion of 1: adding the mixture into an alkali solution of glutaraldehyde in a volume ratio of 4-5, wherein the alkali solution of glutaraldehyde is formed by mixing a 20-30% glutaraldehyde solution and 0.01M NaOH in a volume ratio of 1:20-30, the reaction time is 10-12 hours at room temperature, and the drying is carried out in an oven at 60-80 ℃ for 24 hours.
7. The heavy metal adsorbent prepared by the method of claims 1-6 is used for adsorption treatment of heavy metal polluted water bodies of Cu, Cd, Zn or Pb:
for heavy metal-related industrial wastewater, when in static adsorption, the pH of the wastewater is firstly adjusted to 6-8, and the dosage of the adsorbent, namely ① water heavy metal Cu, is determined according to the concentration of the heavy metal in the water2+、Pb2+、Cd2+Or Zn2+When the concentration is lower than 50mg/L, the adsorbent is added into the water body according to the proportion of 1g to 1000ml, ② the heavy metal Cu in the water body2+、Pb2+、Cd2+Or Zn2+When the concentration is 50-100mg/L, the adsorbent is added into the water body according to the proportion of 1g to 500ml, ③ the heavy metal Cu in the water body2+、Pb2+、Cd2+Or Zn2+When the concentration is more than 100mg/L, counting as n times of 100mg/L, wherein n is a positive integer, and adding the adsorbent into the water body according to the proportion of ng to 500 ml;
and taking out the adsorbent after the adsorbent is adsorbed and saturated for regenerating the adsorbent.
8. The heavy metal adsorbent of claim 7 is used for adsorption treatment of heavy metal polluted water bodies of Cu, Cd, Zn or Pb, and is characterized in that the regeneration process of the adsorbent is as follows:
(1) separating, washing and collecting the heavy metal adsorbent which is saturated in adsorption through vacuum filtration, drying, soaking in 1mol/L HCl solution for desorption for 24 hours, washing the desorbed adsorbent with distilled water until no heavy metal Cu is detected in the solution2+、Pb2+、Cd2+、Zn2+；
(2) Adding the desorbed adsorption material into 0.1mol/L NaOH regeneration liquid, oscillating for regeneration for 2 hours, removing the regeneration liquid after regeneration is finished, washing the adsorbent with deionized water to be neutral, and drying for later use.
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