CN112216894A - Method for preparing lithium ion sieve composite material by recycling negative electrode of waste lithium ion battery - Google Patents
Method for preparing lithium ion sieve composite material by recycling negative electrode of waste lithium ion battery Download PDFInfo
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Abstract
The invention relates to a method for preparing a lithium ion sieve composite material by using a recovered negative electrode of a waste lithium ion battery, belonging to the field of recovery and reuse of the negative electrode of the waste lithium ion battery. The preparation method of the lithium ion sieve composite material comprises the following steps: crushing and screening the waste lithium ion battery to obtain mixed recovered powder, adding the mixed recovered powder into sulfuric acid and hydrogen peroxide, leaching and filtering to obtain filter residue; washing the filter residue with water, drying, preparing 5-50 g/L slurry, adding a manganese salt, an oxidant and an auxiliary agent, uniformly mixing, and adding a lithium hydroxide solution to obtain brown slurry; carrying out hydrothermal reaction on the brown slurry to obtain a brown solid; washing and drying the brown solid, and roasting at 300-600 ℃ for 0.5-4 h in an oxygen-containing atmosphere to obtain a lithium salt adsorbent precursor; and eluting lithium from the brown lithium salt adsorbent precursor with acid to obtain the lithium ion sieve composite material. The lithium ion sieve composite material has good filtering performance and lithium extraction efficiency, is easy to filter and recover, and has low manganese dissolution rate.
Description
Technical Field
The invention relates to a method for preparing a lithium ion sieve composite material by using a recovered negative electrode of a waste lithium ion battery, belonging to the field of recovery and reuse of the negative electrode of the waste lithium ion battery.
Background
With the rapid development of lithium ion batteries, the number of batteries to be scrapped is also increased rapidly, and how to properly dispose the waste lithium ion batteries becomes an important problem in the development of new energy industries. At present, a lithium ion power battery assembled by a new energy automobile mainly adopts lithium iron phosphate or lithium nickel cobalt manganese oxide as a positive electrode material and natural/artificial graphite as a negative electrode material. The current resource recovery mainly focuses on elements such as nickel, cobalt, manganese, lithium, copper and the like with high economic value, but the recovery and reuse mode of the negative electrode material is lacked. In addition, after the leachate of the valuable metal is purified and decontaminated, the leachate is often directly supplied to the synthesis of the precursor of the rear-end cathode material, but the synthesis of the precursor is influenced by the existence of lithium, so the preferential extraction of the lithium is also solved.
A lithium ion sieve is a material that has a selective adsorption of lithium. Generally, a lithium-containing lithium ion sieve precursor is synthesized by a template method, and then lithium is stripped from the precursor material to obtain the lithium ion sieve. The selective adsorption of the lithium ion sieve on lithium is realized under the condition of coexistence of multiple ions by utilizing the size effect, the memory effect and the sieving effect of molecules. Currently developed lithium ion sieve adsorbing materials mainly include manganese-based, titanium-based, aluminum salts, and the like. The lithium ion sieve can be prepared by a solid-phase sintering method, a hydrothermal method, a sol-gel method and the like. However, most of the lithium ion sieve adsorbents synthesized by the methods are powdery, difficult to filter and serious in dissolution loss, and are not suitable for industrial packed column separation devices. The improved method is mainly to granulate the lithium ion sieve or to load the lithium ion sieve on a proper carrier material. For the carrier material, it is often desirable to have the following properties: (1) the carrier material can be effectively combined with the lithium ion sieve; (2) the carrier material has good filtering performance; (3) can adapt to the environment of lithium adsorption and extraction. Therefore, finding a suitable carrier material has become a technical problem to be solved.
Disclosure of Invention
The invention solves the first technical problem by providing a method for preparing a lithium ion sieve composite material by using a recycled cathode of a waste lithium ion battery.
The method for preparing the lithium ion sieve composite material by recycling the negative electrode of the waste lithium ion battery comprises the following steps:
a. crushing and screening the waste lithium ion battery to obtain mixed recycled powder of the anode material and the cathode material; adding the mixed and recovered powder into a sulfuric acid solution and H2O2Leaching with a solution; filtering the leaching solution to obtain a solution containing valuable metal elements and filter residue; wherein the negative electrode material is graphite;
b. washing filter residues with water, drying, preparing 5-50 g/L slurry with water, adding a manganese salt, an oxidant and an auxiliary agent, uniformly mixing, and adding a lithium hydroxide solution to obtain brown slurry; wherein the addition amount of manganese salt is 0.5-3 mol per liter of slurry, and the molar ratio of manganese salt, oxidant, auxiliary agent and lithium hydroxide is 1: 0.5-2: 0.5-4: 1-4;
c. carrying out hydrothermal reaction on the obtained brown slurry at 120-220 ℃ for 2-24 h to obtain a brown solid;
d. washing the obtained brown solid, and drying at 60-100 ℃; drying, then placing in an oxygen-containing atmosphere, and roasting at the temperature of 300-600 ℃ for 0.5-4 h to obtain a lithium salt adsorbent precursor;
e. and (3) carrying out acid elution on the brown lithium salt adsorbent precursor to obtain the lithium ion sieve composite material.
In one embodiment, in step a, the particle size of the mixed reclaimed powder is <0.3 mm.
In one embodiment, in step a, the reclaimed powder, sulfuric acid solution and H are mixed2O2The mass ratio of the solution is 1:1: 0.1-1: 3:0.5, wherein the concentration of the sulfuric acid solution is 1-4 mol/L; h2O2The concentration of the solution is 25-35 wt%.
In one embodiment, in step b, the oxidizing agent is potassium persulfate, ammonium persulfate, or sodium persulfate; the adjuvant is oxalate, citrate, ammonia water, ethylenediamine, EDTA, DCyTA, DTPA, EGTA or HEDTA; the manganese salt is a divalent manganese salt; preferably, the manganese salt is manganese sulfate or manganese oxalate.
In one embodiment, in the step b, the filter residue is prepared into 10-40 g/L slurry; preferably, the filter residue is prepared into 10-20 g/L slurry; more preferably, the filter residue is prepared as a 20g/L slurry.
In one embodiment, in the step b, the molar ratio of the manganese salt, the oxidant, the auxiliary agent and the lithium hydroxide is 1: 0.5-1.5: 0.5-2: 1-2; preferably, the addition amount of the manganese salt is 0.5-1.5 mol per liter of slurry, and the molar ratio of the manganese salt, the oxidant, the auxiliary agent and the lithium hydroxide is 1:0.5: 0.5-1: 1-2; more preferably, the addition amount of the manganese salt is 0.5mol per liter of slurry, and the molar ratio of the manganese salt, the oxidant, the auxiliary agent and the lithium hydroxide is 1:0.5:1: 2.
In one embodiment, in step c, the reaction temperature is 120-180 ℃ and the reaction time is 12-24 h; preferably, the reaction temperature is 120-140 ℃; more preferably, the reaction temperature is 140 ℃ and the reaction time is 12 h.
In one embodiment, in the step d, the roasting temperature is 500-600 ℃, and the roasting time is 0.5-2 hours; preferably, the roasting temperature is 500-550 ℃, and the roasting time is 1.5-2 h; more preferably, the roasting temperature is 500 ℃ and the roasting time is 2 hours.
In one embodiment, in step e, the acid washing is performed by using 0.1 to 1mol/L sulfuric acid solution.
The lithium ion sieve composite material prepared by the invention can be recycled for multiple times.
The recovery method of the lithium ion sieve composite material comprises the following steps: eluting the lithium ion sieve composite material after adsorption by using a pickling agent to obtain a lithium-containing solution and the pickled lithium ion sieve composite material; the lithium ion sieve composite material after acid washing is directly used for the adsorption of the next lithium-containing solution. Preferably, the pickling agent is a 0.1-1 mol/L sulfuric acid solution.
The invention has the beneficial effects that:
1. the lithium ion sieve graphite composite material prepared by the hydrothermal method has good filtering performance and lithium extraction efficiency, and the saturated adsorption capacity to lithium is more than 20.7 mg/g.
2. The lithium ion sieve composite material is granular, has good formability, is easy to filter and recycle, and has extremely low mass loss and manganese dissolution rate of less than or equal to 1 percent after being repeatedly used for ten times.
3. The method reasonably utilizes the waste lithium batteries, not only prepares the cathode material into the efficient lithium ion sieve material which can be recycled for multiple times, but also recovers the valuable metals of the anode material, and preferentially extracts the lithium before the nickel, the cobalt and the manganese are used for preparing the ternary precursor.
Detailed Description
The method for preparing the lithium ion sieve composite material by recycling the negative electrode of the waste lithium ion battery comprises the following steps:
a. crushing and screening the waste lithium ion battery to obtain mixed recycled powder of the anode material and the cathode material; adding the mixed and recovered powder into a sulfuric acid solution and H2O2Leaching with a solution; filtering the leaching solution to obtain a solution containing valuable metal elements and filter residue; wherein the negative electrode material is graphite;
b. washing filter residues with water, drying, preparing 5-50 g/L slurry with water, adding a manganese salt, an oxidant and an auxiliary agent, uniformly mixing, and adding a lithium hydroxide solution to obtain brown slurry; wherein the addition amount of manganese salt is 0.5-3 mol per liter of slurry, and the molar ratio of manganese salt, oxidant, auxiliary agent and lithium hydroxide is 1: 0.5-2: 0.5-4: 1-4;
c. carrying out hydrothermal reaction on the obtained brown slurry at the temperature of 120-220 ℃ for 2-24 h to obtain a brown solid;
d. washing the obtained brown solid, and drying at 60-100 ℃; drying, and roasting at 300-600 ℃ for 0.5-4 h in an oxygen-containing atmosphere to obtain a lithium salt adsorbent precursor;
e. and (3) carrying out acid elution on the brown lithium salt adsorbent precursor to obtain the lithium ion sieve composite material.
The cathode material can be a cathode material of a lithium ion battery commonly used in the art, such as an oxide material rich in lithium, nickel, manganese, cobalt, iron, and phosphorus. The mixed and recycled powder can be ternary battery powder, lithium iron phosphate battery powder, lithium cobaltate battery powder and lithium manganate battery powder.
The traditional manganese lithium ion sieve is mostly powdery, has too fine particles, poor mechanical strength and high dissolution rate, and liquid is not easy to pass through when the column operation is carried out. To address this series of problems, lithium ion sieve materials are often pelletized, or compounded with other materials.
The anode and cathode powder of the waste lithium ion battery can be recycled to obtain the anode graphite material with good filtering performance and strong solution dispersibility after oxidation and acid leaching treatment. The surface of the recovered graphite contains hydrophilic groups-OH, -COOH, etc., and is easily bonded to the manganese-based oxide. This patent passes through hydrothermal method reaction, at recovery graphite surface normal position growth manganese oxide, decomposes through oxidant (like persulfate) and produces oxygen, reacts under airtight space hyperoxia, high pressure, promotes graphite surface hydrophilic group and increases, and bivalent manganese oxidation is +3, +4 valences to with OH-A precipitate formed. And drying and roasting the hydrothermal product to obtain a lithium salt adsorbent precursor with high crystallinity, and carrying out acid washing to remove lithium to obtain the target adsorbent.
Sulfuric acid solution and H2O2The solution functions to provide an environmental system for the oxidative acid leaching. The system can increase the hydrophilic groups on the surface of graphite, so that the graphite has the characteristics of graphite oxide, and has better dispersibility and excellent filtering performance in aqueous solution. Therefore, if this step (i.e., the oxidation acid leaching treatment of graphite) is not performed, the load strength is affected and the manganese dissolution rate is increased.
The specific method for obtaining the mixed recycled powder of the cathode material and the anode material can be as follows: crushing the waste lithium ion battery, removing a diaphragm by air separation, then screening, removing large-particle substances (mainly copper, aluminum, broken diaphragm and the like), and collecting powder with the particle size of less than 0.3 mm.
In one embodiment, in step a, the particle size of the mixed reclaimed powder is <0.3 mm.
In the step b, the step of preparing 5-50 g/L of slurry by using water means that 5-50 g of filter residue is added into 1L of water.
In step d, the roasting is carried out under the oxygen condition because manganese and lithium form a regular layered compound on the surface of the carbon material, and Mn can be oxidized by oxygen2+Meanwhile, oxygen has a promoting effect on the crystal form transformation of the regular lamellar compound, which is not possessed by the inert atmosphere. If the non-oxidizing atmosphere is adopted for roasting, the saturation adsorption capacity of the finally obtained lithium ion sieve composite material to lithium ions is reduced and is lower than that of the lithium ion sieve composite material obtained after roasting treatment in the oxidizing atmosphere.
Wherein the oxygen-containing atmosphere is an oxygen-containing atmosphere, and the oxygen content in the oxygen-containing atmosphere is 13-30%. In one embodiment of the present invention, the oxygen-containing atmosphere is an air atmosphere.
And d, roasting to obtain a granular material with the granularity of 20-40 meshes.
In one embodiment, in step a, the reclaimed powder, sulfuric acid solution and H are mixed2O2The mass ratio of the solution is 1:1: 0.1-1: 3:0.5, wherein the concentration of the sulfuric acid solution is 1-4 mol/L; h2O2The concentration of the solution is 25-35 wt%. Preferably, H2O2The concentration of the solution was 30 wt%.
In one embodiment, in step b, the oxidizing agent is potassium persulfate, ammonium persulfate, or sodium persulfate; the adjuvant is oxalate, citrate, ammonia water, ethylenediamine, EDTA, DCyTA, DTPA, EGTA or HEDTA; the manganese salt is a divalent manganese salt; preferably, the manganese salt is manganese sulfate or manganese oxalate.
In one embodiment, in the step b, the filter residue is prepared into 10-40 g/L slurry; preferably, the filter residue is prepared into 10-20 g/L slurry; more preferably, the filter residue is prepared as a 20g/L slurry.
In order to improve the adsorption capacity of the lithium ion sieve composite material, in one embodiment, in the step b, the molar ratio of the manganese salt, the oxidant, the auxiliary agent and the lithium hydroxide is 1: 0.5-1.5: 0.5-2: 1-2; preferably, the addition amount of the manganese salt is 0.5-1.5 mol per liter of slurry, and the molar ratio of the manganese salt, the oxidant, the auxiliary agent and the lithium hydroxide is 1:0.5: 0.5-1: 1-2; more preferably, the addition amount of the manganese salt is 0.5mol per liter of slurry, and the molar ratio of the manganese salt, the oxidant, the auxiliary agent and the lithium hydroxide is 1:0.5:1: 2.
In order to improve the adsorption capacity of the lithium ion sieve composite material, in one embodiment, in the step c, the reaction temperature is 120-180 ℃, and the reaction time is 12-24 hours; preferably, the reaction temperature is 120-140 ℃; more preferably, the reaction temperature is 140 ℃ and the reaction time is 12 h.
In order to improve the adsorption capacity of the lithium ion sieve composite material, in one embodiment, in the step d, the roasting temperature is 500-600 ℃, and the roasting time is 0.5-2 hours; preferably, the roasting temperature is 500-550 ℃, and the roasting time is 1.5-2 h; more preferably, the roasting temperature is 500 ℃ and the roasting time is 2 hours.
In one embodiment, in step e, the acid washing is performed by using 0.1 to 1mol/L sulfuric acid solution.
The lithium ion sieve composite material prepared by the invention can be recycled for multiple times.
The recovery method of the lithium ion sieve composite material comprises the following steps: eluting the lithium ion sieve composite material after adsorption by using a pickling agent to obtain a lithium-containing solution and the pickled lithium ion sieve composite material; the lithium ion sieve composite material after acid washing is directly used for the adsorption of the next lithium-containing solution. Wherein the acid washing is carried out by adopting 0.1-1 mol/L sulfuric acid solution.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
The test methods used in the following examples:
the test method for the saturated adsorption capacity of the lithium ion sieve composite material comprises the following steps:
taking the valuable metal solution prepared in the first example, in the solution: ni 45g/L, Co 18g/L, Mn and 50g/L, Li2The O concentration was 20g/L and the pH of the solution was 5.0.
Specific test process of saturated adsorption:
step a: 100g of the lithium ion sieve composite material is filled into a filter column.
Step b: and (3) passing the valuable metal element solution prepared in the first example through a filter column containing a lithium ion sieve composite material until the content of the Li element in the filtrate passing through the adsorption column is consistent with that of the initial solution.
Step c: taking out the lithium ion sieve composite material, drying, digesting the lithium ion sieve composite material by 10mol/L sulfuric acid solution, measuring the content of lithium in the digestion solution, and measuring the volume V of the digestion solutiond(unit is mL) and lithium ion concentration C (unit is mg/mL), and then the saturated adsorption quantity C of the lithium ion sieve composite material to lithium is calculated*(unit is mg/g):
secondly, the method for circularly testing the dissolution loss rate of manganese comprises the following steps:
step a: 100g of the lithium ion sieve composite material is filled into a filter column.
Step b: enabling 100mL of the valuable metal element solution prepared in the first example to pass through a filter column containing a lithium ion sieve composite material to obtain a delithiated nickel-cobalt-manganese solution; eluting the filter column with acid pickling agent to obtain lithium-containing solution; the pickling process comprises the following steps: the pickling agent is 0.1M dilute sulfuric acid solution; the acid washing amount Vml of the acid washing agent is 3 times of the filling volume of the adsorbent, and the acid washing is carried out until the lithium content in the eluent is lower than 1 ppm;
step c: and c, repeating the step b 9 times to obtain the lithium ion sieve composite material after acid washing.
Step d: determination of manganese content x in original lithium ion sieve composite material by inductively coupled plasma emission spectrometry (ICP method)1(％)。After 10 times of circulation, the manganese content in the lithium ion sieve composite material is x2(%). Measuring the mass m of the lithium ion sieve composite material after 10 times of circulation by using a balance2(g)。
Calculating the dissolution loss rate of manganese:
example one:
(1) crushing, screening and collecting waste lithium ion batteries<0.3mm powder; wherein, the recovered powder less than 0.3mm mainly comprises a positive electrode material and a negative electrode material; the negative electrode material is graphite; adding the recovered powder into sulfuric acid solution and H2O2Solution, wherein the recovered powder, sulfuric acid solution and H are mixed2O2The mass ratio of the solution is 1:2:0.3, wherein the concentration of the sulfuric acid solution is 3 mol/L; h2O2The concentration of the solution was 30 wt%.
Stirring and leaching; filtering the leaching solution to obtain a solution (Li, Ni, Co, Mn) containing valuable metal elements and filter residue; wherein, in the solution containing the valuable metal elements: ni 45g/L, Co 18g/L, Mn and 50g/L, Li2The concentration of O is 20g/L, and the pH value of the solution is 5.0; washing the filter residue with water, and drying.
(2) Preparing 20g/L slurry from the obtained filter residue in a polytetrafluoroethylene reaction kettle, adding a certain amount of manganese sulfate, ammonium persulfate and ammonium oxalate, and uniformly stirring; slowly dropwise adding a lithium hydroxide solution, and controlling the molar ratio of manganese sulfate, ammonium persulfate, ammonium oxalate and lithium hydroxide to be 1:0.5:1:2, wherein the addition amount of manganese salt is 0.5mol per liter of slurry.
(3) Carrying out hydrothermal reaction on the obtained brown slurry at 140 ℃ for 12h to obtain brown solid LixMny (OH)2The @ C complex;
(4) filtering and washing the obtained brown solid, and drying at 80 ℃ for 2 h; drying, and roasting at 500 ℃ for 2h in an oxygen-containing atmosphere to obtain a lithium salt adsorbent precursor;
(5) washing the obtained brown lithium salt adsorbent precursor with 0.5M sulfuric acid solution to obtain MnO2A lithium ion adsorbent composited with graphite;
(6) the solution (Li) containing valuable metal elements obtained in the step (1)2The concentration of O is 20g/L, the pH value is 5.0), and the solution passes through a filter column containing the lithium ion adsorbent obtained in the step (5), so that a lithium-removed nickel-cobalt-manganese solution can be obtained, and the solution can be used for preparing a precursor of a positive electrode material; the filter column can be eluted by a pickling agent to obtain a lithium-containing solution, wherein the pickling agent is a 0.1M dilute sulfuric acid solution.
The saturated adsorption capacity of the lithium ion adsorbent prepared in the example is 25.2mg/g through testing; the circulation is carried out for ten times, and the dissolution loss rate of manganese is less than or equal to 1 percent.
Example two:
(1) taking a waste lithium ion battery which is completely the same as the first example, and obtaining a solution (Li, Ni, Co, Mn) containing valuable metal elements and filter residues according to the method of the first example; washing the filter residue with water and drying;
(2) preparing the obtained filter residue into 10g/L slurry in a polytetrafluoroethylene reaction kettle, adding a certain amount of manganese oxalate, ammonium persulfate and ammonium oxalate, and uniformly stirring; slowly dropwise adding a lithium hydroxide solution, and controlling the molar ratio of the manganese oxalate, the ammonium persulfate, the ammonium oxalate and the lithium hydroxide to be 1:0.5:0.5:1, wherein the addition amount of the manganese salt is 1.5mol per liter of slurry.
(3) Carrying out hydrothermal reaction on the obtained brown slurry at 120 ℃ for 24 hours to obtain LixMny (OH)2The @ C complex;
(4) filtering and washing the obtained brown solid, and drying at 80 ℃ for 2 h; drying, and roasting at 550 ℃ for 1.5h in an oxygen-containing atmosphere to obtain a lithium salt adsorbent precursor;
(5) washing the obtained brown lithium salt adsorbent precursor with 0.5M sulfuric acid solution to obtain MnO2A lithium ion adsorbent composited with graphite;
(6) the solution (Li) containing valuable metal elements obtained in the step (1)2The concentration of O is 20g/L, the pH value is 5.0), and the solution passes through a filter column containing the lithium ion adsorbent obtained in the step (5), so that a lithium-removed nickel-cobalt-manganese solution can be obtained, and the solution can be used for preparing a precursor of a positive electrode material; the filtering column can be eluted by a pickling agent to obtain a lithium-containing solution, and the pickling agent is a 0.1M dilute sulfuric acid solution;
the saturated adsorption capacity of the lithium ion adsorbent is 23.6mg/g through tests; the circulation is carried out for ten times, and the dissolution loss rate of manganese is less than or equal to 1 percent.
Example three:
(1) taking a waste lithium ion battery which is completely the same as the first example, and obtaining a solution (Li, Ni, Co, Mn) containing valuable metal elements and filter residues according to the method of the first example; washing the filter residue with water and drying;
(2) preparing the obtained filter residue into 40g/L slurry in a polytetrafluoroethylene reaction kettle, adding a certain amount of manganese oxalate, sodium persulfate and sodium citrate, and uniformly stirring; slowly dropwise adding a lithium hydroxide solution, and controlling the molar ratio of the manganese oxalate, the sodium persulfate, the sodium citrate and the lithium hydroxide to be 1:1.5:2:2, wherein the addition amount of the manganese salt is 3mol per liter of slurry.
(3) Carrying out hydrothermal reaction on the obtained brown slurry at 180 ℃ for 24 hours to obtain LixMny (OH)2The @ C complex;
(4) filtering and washing the obtained brown solid, and drying for 2 hours in vacuum at 80 ℃; drying, and roasting at 600 ℃ for 0.5h in an oxygen-containing atmosphere to obtain a lithium salt adsorbent precursor;
(5) washing the obtained brown lithium salt adsorbent precursor with 0.5M sulfuric acid solution to obtain MnO2A lithium ion adsorbent composited with graphite;
(6) the solution (Li) containing valuable metal elements obtained in the step (1)2The concentration of O is 20g/L, the pH value is 5.0), and the solution passes through a filter column containing the lithium ion adsorbent obtained in the step (5), so that a lithium-removed nickel-cobalt-manganese solution can be obtained, and the solution can be used for preparing a precursor of a positive electrode material; the filtering column can be eluted by a pickling agent to obtain a lithium-containing solution, and the pickling agent is a 0.1M dilute sulfuric acid solution;
the test shows that the saturated adsorption capacity of the composite adsorbent is 20.7 mg/g; the circulation is carried out for ten times, and the dissolution loss rate of manganese is less than or equal to 1 percent.
Claims (10)
1. The method for preparing the lithium ion sieve composite material by recycling the negative electrode of the waste lithium ion battery is characterized by comprising the following steps of:
a. crushing and screening the waste lithium ion battery to obtain mixed recycled powder of the anode material and the cathode material; adding the mixed and recovered powder into a sulfuric acid solution and H2O2Leaching with a solution; filtering the leaching solution to obtain a solution containing valuable metal elements and filter residue; wherein the negative electrode material is graphite;
b. washing filter residues with water, drying, preparing 5-50 g/L slurry with water, adding a manganese salt, an oxidant and an auxiliary agent, uniformly mixing, and adding a lithium hydroxide solution to obtain brown slurry; wherein the addition amount of manganese salt is 0.5-3 mol per liter of slurry, and the molar ratio of manganese salt, oxidant, auxiliary agent and lithium hydroxide is 1: 0.5-2: 0.5-4: 1-4;
c. carrying out hydrothermal reaction on the obtained brown slurry at 120-220 ℃ for 2-24 h to obtain a brown solid;
d. washing the obtained brown solid, and drying at 60-100 ℃; drying, then placing in an oxygen-containing atmosphere, and roasting at the temperature of 300-600 ℃ for 0.5-4 h to obtain a lithium salt adsorbent precursor;
e. and (3) carrying out acid elution on the brown lithium salt adsorbent precursor to obtain the lithium ion sieve composite material.
2. The method for preparing the lithium ion sieve composite material by using the recycled negative electrode of the waste lithium ion battery as claimed in claim 1, wherein in the step a, the particle size of the mixed recycled powder is less than 0.3 mm.
3. The method for preparing the lithium ion sieve composite material by using the recycled negative electrode of the waste lithium ion battery as claimed in claim 1, wherein in the step a, the recycled powder, the sulfuric acid solution and H are mixed2O2The mass ratio of the solution is 1:1: 0.1-1: 3:0.5, wherein the concentration of the sulfuric acid solution is 1-4 mol/L; h2O2The concentration of the solution is 25-35 wt%.
4. The method for preparing the lithium ion sieve composite material by using the recycled negative electrode of the waste lithium ion battery as claimed in claim 1, wherein in the step b, the oxidant is potassium persulfate, ammonium persulfate or sodium persulfate; the adjuvant is oxalate, citrate, ammonia water, ethylenediamine, EDTA, DCyTA, DTPA, EGTA or HEDTA; the manganese salt is a divalent manganese salt; preferably, the manganese salt is manganese sulfate or manganese oxalate.
5. The method for preparing the lithium ion sieve composite material by using the recycled negative electrode of the waste lithium ion battery as claimed in claim 1, wherein in the step b, the filter residue is prepared into 10-40 g/L of slurry; preferably, the filter residue is prepared into 10-20 g/L slurry; more preferably, the filter residue is prepared as a 20g/L slurry.
6. The method for preparing the lithium ion sieve composite material by using the recycled negative electrode of the waste lithium ion battery as claimed in claim 1, wherein in the step b, the molar ratio of the manganese salt to the oxidant to the auxiliary agent to the lithium hydroxide is 1: 0.5-1.5: 0.5-2: 1-2; preferably, the addition amount of the manganese salt is 0.5-1.5 mol per liter of slurry, and the molar ratio of the manganese salt, the oxidant, the auxiliary agent and the lithium hydroxide is 1:0.5: 0.5-1: 1-2; more preferably, the addition amount of the manganese salt is 0.5mol per liter of slurry, and the molar ratio of the manganese salt, the oxidant, the auxiliary agent and the lithium hydroxide is 1:0.5:1: 2.
7. The method for preparing the lithium ion sieve composite material by using the recycled negative electrode of the waste lithium ion battery as claimed in claim 1, wherein in the step c, the reaction temperature is 120-180 ℃, and the reaction time is 12-24 hours; preferably, the reaction temperature is 120-140 ℃; more preferably, the reaction temperature is 140 ℃ and the reaction time is 12 h.
8. The method for preparing the lithium ion sieve composite material by using the recycled negative electrode of the waste lithium ion battery as claimed in claim 1, wherein in the step d, the roasting temperature is 500-600 ℃, and the roasting time is 0.5-2 h; preferably, the roasting temperature is 500-550 ℃, and the roasting time is 1.5-2 h; more preferably, the roasting temperature is 500 ℃ and the roasting time is 2 hours.
9. The method for preparing the lithium ion sieve composite material by using the recycled negative electrode of the waste lithium ion battery as claimed in claim 1, wherein in the step e, the acid washing is performed by using a 0.1-1 mol/L sulfuric acid solution.
10. The recovery method of the lithium ion sieve composite material is characterized in that the lithium ion sieve composite material after adsorption is eluted by a pickling agent to obtain a lithium-containing solution and the pickled lithium ion sieve composite material; the lithium ion sieve composite material after acid washing is directly used for the adsorption of the next lithium-containing solution; preferably, the pickling agent is a 0.1-1 mol/L sulfuric acid solution.
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| CN115092964B (en) * | 2022-06-17 | 2023-05-12 | 南京工业大学 | Recycling recycling method of powdery waste manganese lithium ion sieve |
| CN116786078A (en) * | 2023-05-25 | 2023-09-22 | 苏州博睿特环保科技有限公司 | Lithium iron silicate modified spodumene slag lithium ion sieve, precursor thereof and preparation method thereof |
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