CN115739108B

CN115739108B - Resource utilization method of waste lithium ion battery

Info

Publication number: CN115739108B
Application number: CN202211550091.7A
Authority: CN
Inventors: 牛琳; 赵晓丽; 吴丰昌; 雷啟焘
Original assignee: Institute of Eco Environmental and Soil Sciences of Guangdong Academy of Sciens
Current assignee: Institute of Eco Environmental and Soil Sciences of Guangdong Academy of Sciens
Priority date: 2022-12-05
Filing date: 2022-12-05
Publication date: 2023-06-06
Anticipated expiration: 2042-12-05
Also published as: CN115739108A

Abstract

The invention provides a resource utilization method of waste lithium ion batteries, which relates to the field of waste battery recycling, and comprises the following steps: s1, preparing a catalyst from waste lithium ion batteries: disassembling and soaking the waste lithium ion battery to obtain a mixed solution containing transition metal elements; then mixing with activated carbon to obtain a mixture; calcining the mixture to obtain a catalyst; s2, mixing the prepared catalyst with an oxidant and a pollutant water body to be treated for catalytic reaction, and removing pollutants. The utilization method reflects the environmental protection concept of treating waste with waste, prepares transition metal in the waste lithium ion battery as a catalyst, is applied to the removal of antibiotic pollutants, realizes the complete mineralization of the pollutants, and solves the problem of potential secondary pollution.

Description

Resource utilization method of waste lithium ion battery

Technical Field

The invention belongs to the field of waste battery recycling, and particularly relates to a resource utilization method of waste lithium ion batteries.

Background

The water environment pollution problem is now a global environment problem, which threatens the health of human body and the safety of ecological system at any time. Researches show that antibiotics are commonly detected in water bodies, and the antibiotics have the characteristics of biotoxicity, environmental persistence, bioaccumulation and the like, are not easy to degrade in water environments and are difficult to effectively remove.

Adsorption, catalysis, biodegradation, membrane separation, etc. techniques are used to remove antibiotics. Adsorption technology such as activated carbon has the characteristics of high adsorption capacity and large specific surface area, but only transfers the adsorbent from the water environment to the adsorbent, so that the problem of secondary pollution is likely to exist; the biodegradation technology has the characteristics of simple operation and low cost, but has the problems of long pollutant removal time, retreatment of microorganisms and the like; the membrane separation technology has the characteristics of long service life, wide application range, high recovery rate of effective components and the like, but the membrane is easy to pollute, and the removal efficiency is reduced. The catalytic technology is widely applied due to the characteristics of simple operation, high efficiency, complete mineralization of pollutants, no secondary pollution and the like.

The core of the catalytic technology is the catalyst. Most of the catalyst raw materials are from chemicals at present, and if the catalyst raw materials are from waste, a win-win strategy of treating waste by waste can be realized. The lithium ion battery has the characteristics of high energy density, long cycle life, low pollution and the like, and is widely applied to electronic products. The cathode material of the lithium ion battery consists of transition metal and lithium element. If the transition metal element in the cathode material of the waste lithium ion battery can be utilized, the treatment problem of the waste lithium ion battery is solved, and the recycling utilization of the waste lithium ion battery is realized.

Chinese patent No. 110144461A discloses a comprehensive recovery method of waste lithium battery positive plates, which comprises the steps of placing the positive electrode scraps and the waste positive plates into a vacuum furnace for calcination, then vibrating and screening to obtain positive electrode active substances, adding the positive electrode active substances into sulfuric acid leaching solution for secondary leaching, and filtering and separating to obtain leached slag carbon and leaching solution containing nickel, cobalt, manganese and lithium; adding activated carbon into the leaching solution to perform adsorption deoiling and desilication, 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 anode material. The recovery of the waste lithium battery positive plate has the advantages of reasonable process, low separation cost, no pollution, no toxicity and the like. But the recovery process is complex and the cost is high.

Chinese patent No. CN113134363a discloses a biochar catalyst for treating antibiotic organic waste water, its preparation method and degradation method of antibiotic-containing organic waste water. The catalyst comprises a carrier and transition metal, wherein the carrier is a biochar carrier, the transition metal is one or more of cobalt, iron, manganese, copper, zinc and silver, and the transition metal is loaded on the carrier, dried and calcined to prepare the catalyst. The highest 96.62% removal of the norfloxacin antibiotic was achieved. However, the invention utilizes transition metal not in the waste batteries, and does not reasonably treat waste by waste for the waste lithium ion batteries.

Therefore, how to utilize the waste lithium ion battery to strategically synthesize the catalyst with good performance, low cost and green stability is a key problem of efficiently degrading pollutants.

Disclosure of Invention

Aiming at the problems existing in the prior art, the invention provides a method for utilizing waste lithium ion batteries, which is environment-friendly and utilizes waste resources, and the application method embodies the concept of treating waste with waste; the transition metal in the waste lithium ion battery is prepared into a catalyst, and the catalyst is applied to the removal of antibiotic pollutants and has the characteristics of high catalytic activity, high removal rate of pollutants, large specific surface area and good cycling stability.

In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:

in one aspect, the invention provides a method for utilizing waste lithium ion batteries, which comprises the following steps:

s1, preparing a catalyst from waste lithium ion batteries;

s101, disassembling and soaking a waste lithium ion battery to obtain a mixed solution containing transition metal elements;

s102, mixing the mixed solution in the step S101 with activated carbon, and stirring at 60-80 ℃ to obtain a mixture;

s103, calcining the mixture at 600-800 ℃ for 1-4 hours to obtain a catalyst;

s2, mixing the prepared catalyst with an oxidant and a pollutant water body to be treated for catalytic reaction, and removing pollutants.

Preferably, in step S101, the lithium ion battery is at least one selected from a ternary lithium battery, a lithium cobaltate battery and a lithium iron phosphate battery.

Preferably, in the step S101, the soaking is carried out, the used solution is NaCl, the concentration is 15-20wt%, and the solid-to-liquid ratio of the battery to the solution is 10-25g/L; the soaking time is 10-20 days, and the soaking temperature is 20 ℃.

Preferably, in step S101, the kind of the transition metal is related to the kind of the lithium ion battery, including Ni, mn, co, fe.

Further preferably, the molar ratio of the transition metal is related to the kind of lithium ion battery, and in the present invention, the kind and the molar ratio of the transition metal are not limited.

Preferably, in step S102, the activated carbon is activated carbon in a general sense; is prepared by pyrolysis and activation processing of raw materials containing carbon, and is a generic name of carbon materials with developed void structure, larger specific surface area and rich surface chemical groups and stronger specific adsorption capacity; the raw material can be at least one of shell, coconut shell, straw, bone, wood and coal raw material; the activated carbon is not particularly limited, and activated carbon conventionally used by those skilled in the art may be used.

Preferably, in the step S102, the solid-to-liquid ratio of the activated carbon to the mixed solution is 10-25g/L.

Further preferably, the solid-to-liquid ratio of the activated carbon to the mixed solution is 20g/L.

Preferably, in step S102, the temperature of the stirring is 80 ℃ until the solution evaporates, and the mixture is obtained by drying.

Preferably, in step S103, the calcining temperature is 700-800 ℃, the calcining time is 1-3h, and nitrogen is introduced for calcining.

Further preferably, the calcination temperature is 800 ℃, the calcination time is 2 hours, and nitrogen is introduced for calcination.

Preferably, in step S2, the oxidizing agent is at least one selected from the group consisting of peroxodisulfates and Peroxodisulfates (PDS).

Further preferably, the oxidizing agent is Potassium Monopersulfate (PMS).

Preferably, in step S2, the concentration of the oxidizing agent is 0.2-1mM.

Further preferably, the concentration of the oxidizing agent is 0.5mM.

Preferably, in step S2, the contaminant is selected from at least one of antibiotics, organic dyes, bisphenol a.

Further preferably, the contaminant is selected from at least one of an antibiotic, an organic dye.

Still more preferably, the contaminant is an antibiotic.

Still more preferably, the antibiotic is at least one selected from the group consisting of sulfathiazole, sulfadiazine, tetracycline, norfloxacin, ofloxacin.

Preferably, in step S2, the concentration of the contaminant is 5-15mg/L.

Preferably, in step S2, the concentration of the catalyst is 0.2-0.6g/L.

Still more preferably, the catalyst concentration is 0.4g/L.

Preferably, in step S2, the reaction temperature of the catalytic reaction is 20-35 ℃, the reaction time is 30-60min, and the catalytic reaction is carried out on a shaking table at 200-400 rpm.

On the other hand, the invention provides a waste lithium ion battery catalyst which is prepared by the utilization method.

Finally, the invention provides the application of the utilization method in catalyst preparation and removal of antibiotic pollutants in water bodies.

Compared with the prior art, the invention has the following beneficial effects:

(1) The method utilizes the catalyst prepared by the waste lithium ion battery to realize complete mineralization of pollutants under the condition of catalytic reaction, thoroughly removes new pollutants from water environment, and solves the problem of potential secondary pollution;

(2) The catalyst is prepared from waste lithium ion batteries, so that the cost of raw materials of the catalyst is reduced;

(3) The utilization method and the application solve the problems of difficult treatment and high hazard of the waste lithium ion batteries, creatively combine the waste lithium ion batteries with pollutant treatment, realize the treatment of waste by waste in the true sense, and realize the win-win strategy of environmental protection and resource utilization.

Drawings

FIG. 1 is an SEM image of the activated carbon of the present invention.

Detailed Description

The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way. The following is merely exemplary of the scope of the claimed invention and one skilled in the art can make various changes and modifications to the invention of the present application in light of the disclosure, which should also fall within the scope of the claimed invention.

The invention is further illustrated by means of the following specific examples. The various chemical reagents used in the examples of the present invention were obtained by conventional commercial means unless otherwise specified.

In the examples described below, the activated carbon was purchased from the microphone manufacturer with CAS number 7440-44-0 and particle size of 8-16 mesh.

In the following examples, the method for determining the concentration of the contaminant in the mixed solution by High Performance Liquid Chromatography (HPLC) is as follows: the concentration of sulfathiazole was determined by high performance liquid chromatography-ultraviolet (Dionex SUMMIT PDA, 100 ultraviolet detector), C18 column (4.6 mm. Times.150 mm, particle size 5 μm, agilent, USA), ultraviolet detection wavelength 284nm. The mobile phase was acetonitrile, water (20:80, v/v) and 0.05% acetic acid at a flow rate of 1.0mL/min.

In the following examples, the degradation rate of the contaminants was calculated by: degradation%o = (concentration of pre-catalytic contaminants-concentration of post-catalytic contaminants)/concentration of pre-catalytic contaminants × 100%.

Example 1

S1, preparing a catalyst from waste lithium ion batteries:

s101, disassembling a waste ternary lithium battery, then soaking the waste ternary lithium battery in 20wt% NaCl solution, wherein the solid-to-liquid ratio is 20g/L, and soaking the waste ternary lithium battery at 20 ℃ for 15 days to obtain a mixed solution containing transition metal elements; in the embodiment, the source of the lithium battery is a ternary lithium battery of 532 model; the transition metal is Ni, mn, co, and the mole ratio of Ni, mn and Co is 4:2:1.

s102, mixing the mixed solution in the step S101 with commercial active carbon, and continuously stirring at 80 ℃ until the solution is evaporated, wherein the solid-to-liquid ratio is 20g/L. And then dried in an oven at 60 c to obtain a mixture.

And S103, placing the dried mixture in a tube furnace (the condition is 800 ℃ for 2 hours), and introducing nitrogen for calcination to obtain the catalyst. S2, mixing the prepared catalyst with 100mL of oxidant and pollutant water to be treated: the concentration of the antibiotic pollutant sulfathiazole is 10mg/L (prepared by ultrapure water), 0.4g/L of catalyst and 0.5mM of potassium monopersulfate are added, and the mixed solution is placed on a constant temperature shaking table (300 rpm) at 25 ℃ for catalytic reaction for 1h. During the reaction, 1mL of the reacted catalytic solution was taken every 10min, mixed with 1mL of 20mM sodium thiosulfate, the concentration of the contaminants in the mixed solution was measured by High Performance Liquid Chromatography (HPLC), and the degradation rate of the contaminants was calculated.

Example 2

Unlike example 1, the contaminant concentration in step S2 was 5mg/L, the catalyst concentration was 0.2g/L, and the PMS concentration was 0.3mM.

Example 3

Unlike example 1, the contaminant concentration in step S2 was 15mg/L, the catalyst concentration was 0.6g/L, and the PMS concentration was 0.5mM.

Example 4

Unlike example 1, the calcination temperature in step S103 was 600 ℃ and the calcination time was 4 hours.

Example 5

Unlike example 1, the calcination temperature in step S103 was 700 ℃ and the calcination time was 1h.

Example 6

Unlike example 1, the waste ternary lithium battery is replaced with a mixture of a lithium iron phosphate battery and a lithium cobalt oxide battery in step S101, and the mass ratio of the lithium iron phosphate battery to the lithium cobalt oxide battery is 1:1.

Comparative example 1

Unlike example 1, the spent ternary lithium battery was replaced with a lead acid battery in step S101.

Comparative example 2

Unlike example 1, in step S103, the temperature of the calcination was 500 ℃.

Comparative example 3

Unlike example 1, in step S2, the oxidizing agent is hydrogen peroxide.

Comparative example 4

Unlike example 1, in step S2, the concentration of potassium monopersulfate was 0.1mM.

Test 1

Specific surface area test: the nitrogen adsorption isotherms were assessed by a specific surface and porosity analyzer (Quadrasorb EVO, quantachrome Instruments, america) at 77.3K.

And (3) testing the cycle performance: the catalysts prepared in examples 1 to 6 and comparative examples 1 to 4 were subjected to a removal test of antibiotic sulfathiazole, and after 5 cycles of use, the concentration of contaminants in the mixed solution was measured by High Performance Liquid Chromatography (HPLC), and the degradation rate of the contaminants was calculated.

The catalysts prepared in examples 1 to 6 and comparative examples 1 to 4, which have the effect on the degradation rate of sulfathiazole, which is an anti-bacterial contaminant, and the cycle performance, and the specific surface area results of the prepared catalysts are shown in Table 1.

TABLE 1

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As can be seen from table 1, the waste lithium ion batteries are fully recycled for the second time, so that the catalyst is prepared, and the specific surface area of the catalyst is large; the catalyst is used for carrying out catalytic degradation on pollutants in the water body, the degradation rate can reach 100%, and the complete degradation of the pollutants is achieved; after 5 times of recycling, the degradation rate is still kept above 89%, the highest degradation rate can reach 98%, and the recycling performance is good.

Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.

Claims

1. The method for utilizing the waste lithium ion battery is characterized by comprising the following steps:

s1, preparing a catalyst from waste lithium ion batteries;

s103, calcining the mixture at 600-800 ℃ for 1-4 hours to obtain a catalyst;

s2, mixing the prepared catalyst with an oxidant and a pollutant water body to be treated for catalytic reaction, and removing pollutants;

in the step S101, the soaking is carried out, the used solution is NaCl solution, the concentration is 15-20wt%, and the solid-liquid ratio of the battery to the solution is 10-25g/L; the transition metal species is related to the lithium ion battery species, including Ni, mn, co, fe;

in the step S2, the oxidant is at least one selected from peroxymonosulfate and peroxydisulfate, and the concentration is 0.2-1mM; the concentration of the catalyst is 0.2-0.6g/L; the pollutant is at least one selected from antibiotics, organic dyes and bisphenol A; the reaction temperature of the catalytic reaction is 20-35 ℃, the reaction time is 30-60min, and the catalytic reaction is carried out on a shaking table at 200-400 rpm.

2. The utilization method according to claim 1, wherein in step S102, the solid-to-liquid ratio of the activated carbon to the mixed solution is 10 to 25g/L; the temperature of the stirring was 80 ℃ until the solution evaporated, and the mixture was dried.

3. The method according to claim 1, wherein in step S103, the calcination is performed at a temperature of 700 to 800 ℃ for a calcination time of 1 to 3 hours with nitrogen.