CN112551600A - Method for preparing hydrogen by recovering waste lithium ion battery anode material in combined electrochemical manner - Google Patents
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Abstract
The method for preparing hydrogen by combining the recovery of the anode material of the waste lithium ion battery and electrochemistry comprises the following steps: (1) ball-milling, sieving and drying the waste anode material to obtain recovered powder of secondary agglomerated particles of the waste anode material; (2) mixing the recovered powder of the secondary agglomerated particles of the waste positive electrode material with a conductive agent and an adhesive, coating, and drying to obtain a pole piece; (3) charging in an electrolyte solution by taking the pole piece as a positive electrode and an inert electrode as a negative electrode; (4) after the reaction is finished, collecting primary particles of the waste positive electrode material on the positive electrode piece; (5) and mixing the waste positive electrode material primary particles serving as a precursor with lithium salt, and calcining at high temperature to obtain the positive electrode material. The invention realizes the organic combination of recycling of waste cathode materials, synthesis of primary particles of the cathode materials, electrochemical hydrogen production and re-preparation of high-performance cathode materials by a simple, efficient, environment-friendly and low-cost treatment method.
Description
Technical Field
The invention relates to a method for recycling waste lithium ion batteries and electrochemically producing hydrogen, in particular to a method for producing hydrogen by combining recycling positive electrode materials of waste lithium ion batteries and electrochemically producing hydrogen.
Background
"reuse of waste materials" is a new problem accompanied by a rapid consumption of natural resources and a rapid increase in waste materials. It is predicted that by 2030, globally scrapped lithium ion batteries will reach over 1100 million tons, compared to less than 5% of the discarded batteries that can be recycled. If the waste battery is not well solved, it is not only harmful to the health development of human beings, but also destroys the natural ecological environment. Heavy metals such as Co, Mn, Ni and the like can seriously damage soil and underground water, electrolytes (mainly LiPF)6) And water molecules in the air can produce harmful hydrogen fluoride gas. Meanwhile, the shortage of raw materials of lithium ion batteries also makes the trend of recycling waste materials generate more urgent sense.
The waste anode material secondary agglomerated particles are recycled to prepare an advanced and high-performance anode material, so that waste is turned into wealth, the organic combination of the preparation process of the lithium ion battery anode material and the recycling process of the waste lithium ion anode material is realized, and the method has great significance to the field of lithium ion batteries.
At present, the common technologies for recycling the waste lithium ion battery anode material are heat treatment lithium supplement and hydrothermal treatment lithium supplement to prepare a new anode material, or the waste anode material is subjected to pyrogenic process or wet process lithium removal, and the obtained nickel-cobalt-manganese compound is used as a precursor to prepare the new anode material, but the new anode material prepared by the methods is difficult to achieve the expected target in terms of electrochemical performance and has higher treatment cost.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a method for preparing hydrogen by combining electrochemical recycling of waste lithium ion battery anode materials, which is simple, efficient, environment-friendly and low in treatment cost.
The technical scheme adopted for solving the technical problems is that the method for preparing hydrogen by combining the recovery of the anode material of the waste lithium ion battery with electrochemistry comprises the following steps:
(1) ball-milling, sieving and drying the waste anode material to obtain recovered powder of secondary agglomerated particles of the waste anode material;
(2) mixing the recovered powder of the secondary agglomerated particles of the waste positive electrode material obtained in the step (1) with a conductive agent and an adhesive, dispersing the mixture in an N-methyl pyrrolidone solution, uniformly stirring, coating the mixture on a metal conductive substrate, and drying to obtain a pole piece;
(3) charging in an electrolyte solution by taking the pole piece obtained in the step (2) as a positive electrode and an inert electrode as a negative electrode, dispersing secondary agglomerated particles of the waste positive electrode material on the positive electrode into primary particles to obtain primary particles of the waste positive electrode material, and generating hydrogen by the negative electrode;
(4) after the reaction is finished, collecting primary particles of the waste positive electrode material on the positive electrode piece, carrying out inductively coupled plasma mass spectrometry (ICP), and detecting the removal amount of lithium and the molar ratio of nickel, cobalt and manganese;
(5) mixing the waste and old positive electrode material primary particles collected in the step (4) as a precursor with lithium salt, pre-sintering, and then heating and calcining to obtain a positive electrode material;
the waste anode material is an anode material disassembled from a waste lithium ion battery or a waste material generated in the production process of the anode material; the positive electrode material is LiNixCoyMn1-x-yO2、LiCoO2、Li4Mn5O12And LiNixCoyAl1-x- yO2Wherein 0 is less than or equal to x, y< 1、0≤ x+ y < 1。
Further, in the step (1), the sieving is performed by a sieve of 50-400 meshes, preferably 100-200 meshes.
Further, in the step (2), the conductive agent is carbon black or acetylene black.
Further, in the step (2), the adhesive is one or more of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), polyacrylic acid (PAA), and polyvinyl alcohol (PVA).
Further, in the step (2), the mass ratio of the recovered powder of the waste cathode material secondary agglomerated particles to the conductive agent and the adhesive is 75:15:5, 80:10:10, 85:10:5 or 90:5: 5.
Further, in the step (2), the metal conductive substrate is one or more of a titanium sheet, a titanium mesh, a stainless steel sheet, a stainless steel mesh and a nickel mesh.
Further, in the step (3), the inert electrode is a metal electrode or a carbon electrode which cannot be embedded with lithium.
Further, in the step (3), the electrolyte is Li2SO4、LiCl、LiNO3、LiOH、Li2CO3One or more of (a).
Further, in the step (3), the concentration of the electrolyte solution is 0.1-5 mol/L, preferably 0.5-3 mol/L, and more preferably 1-2 mol/L.
Further, in the step (3), the current for charging is 0.0001 to 0.2A, preferably 0.001 to 0.1A, more preferably 0.01 to 0.5A.
Further, in the step (3), the potential difference across the charged electrode is 0.1 to 3.0V, preferably 0.3 to 2.5V.
Further, in the step (5), the molar ratio of the waste positive electrode material primary particles to the lithium salt is 1: 1.00-1.06, preferably 1: 1.02-1.05.
Further, in the step (5), the lithium salt is LiOH or Li2SO4、Li2CO3、LiNO3One or more of them.
Further, in the step (5), the atmosphere for pre-sintering and calcining is air or oxygen.
Further, in the step (5), the temperature of the pre-sintering is 400-; the pre-sintering time is 3-8 h, preferably 4-5 h.
Further, in the step (5), the rate of temperature rise is 2-5 ℃/min, preferably 3 ℃/min.
Further, in the step (5), the temperature of the calcination is 650-900 ℃, preferably 750-850 ℃; the calcination time is 5-24 h, preferably 10-15 h.
The principle of the invention is as follows: the positive electrode material primary particles have good mechanical strength and pressure resistance due to the unique microscopic morphology, so that the positive electrode material primary particles are not easy to break in the electrode rolling and charging and discharging processes, the generation and the spread of microcracks caused by phase change of the positive electrode material in the charging and discharging processes of the battery can be reduced to a certain extent, the contact interface of an active material and electrolyte is reduced, and the cycle gas generation is reduced.
During the charging process, the lithium removal reaction of the positive electrode occurs, and the secondary particles of the waste positive electrode material are gradually dispersed into primary particles due to the lithium removal reaction and the infiltration of the aqueous solution, which can be further explained as follows: in the charging process, due to the fact that the current density and the charging state are not uniform due to the fact that the electrode material is not uniform in composition, local overcharge is caused, local Li is excessively desorbed, the interlayer spacing of the anode material is enlarged, new rock salt and a non-ordered spinel phase are formed, mechanical stress is generated, micron-sized secondary spherical particles are broken and dispersed into primary particles, and primary particles of the waste anode material are obtained; the negative electrode generates hydrogen evolution reaction to generate high-purity hydrogen, which is beneficial to the enrichment of lithium ions in the electrolyte solution and the recovery of lithium.
And when the charged capacity basically reaches the theoretical capacity of the anode material, stopping the reaction, collecting active substances on the anode plate, namely primary particles of the waste anode material after the reaction is finished, mixing the active substances with lithium salt by taking the primary particles as precursors, and preparing the anode material again after high-temperature calcination.
Compared with the prior art, the invention has the beneficial effects that: the method effectively combines four aspects of recycling waste cathode materials, synthesizing primary particles of the cathode materials, electrochemically producing hydrogen and preparing the high-performance cathode materials again, is simple, efficient and environment-friendly, relieves the resource pressure of the lithium ion battery industry and the environmental pressure of battery solid waste which is difficult to treat, and has low treatment cost.
Drawings
FIG. 1 is an SEM photograph of a reclaimed powder of secondary agglomerate grains of a used positive electrode material obtained in example 1 of the present invention;
FIG. 2 is an SEM photograph of a reclaimed powder of secondary agglomerate grains of a used positive electrode material obtained in example 1 of the present invention;
fig. 3 is an SEM image of primary particles of a waste cathode material obtained in example 1 of the present invention;
fig. 4 is an SEM image of the used cathode material primary particles obtained in example 1 of the present invention.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1
The method for preparing hydrogen by combining waste lithium ion battery anode materials and electrochemistry comprises the following steps:
(1) waste LiNi0.8Co0.1Mn0.1O2Ball-milling the materials, sieving the materials by a 100-mesh sieve, and drying to obtain recovered powder of the secondary agglomerated particles of the waste anode materials, wherein the morphology of the recovered powder is shown in figures 1 and 2;
(2) mixing the recovered powder of the secondary agglomerated particles of the waste positive electrode material obtained in the step (1) with acetylene black and PVDF according to a mass ratio of 80:10:10, dispersing in an N-methyl pyrrolidone solution, uniformly stirring, and drying to obtain a pole piece;
(3) taking the pole piece obtained in the step (2) as a positive electrode, taking a graphite electrode as a negative electrode, and adding 1 mol/L Li2SO4In the solution, charging to 1.8V at a constant current of 0.02A, then charging to 0.1 mA at a constant voltage under the condition of 1.8V, dispersing secondary agglomerated particles of the waste anode material on the anode into primary particles to obtain primary particles of the waste anode material, wherein the morphology of the primary particles of the waste anode material is shown in figures 3 and 4, and hydrogen is generated at the cathode;
(4) after the reaction is finished, collecting primary particles of the waste positive electrode material on the positive electrode piece, and carrying out inductively coupled plasma mass spectrometry (ICP), wherein the calculated lithium release amount is 98%, and the molar ratio of nickel, cobalt and manganese is 0.78:0.10: 0.12;
(5) taking the primary particles of the waste anode material collected in the step (4) as a precursor according to the mol ratio of 1:1.02 to LiOH.H2And O, mixing, heating to 450 ℃ at the heating rate of 3 ℃/min under the oxygen atmosphere, keeping the temperature for 4 h, heating to 750 ℃, keeping the temperature for 15h, and cooling to obtain the anode material.
And (3) testing the electrochemical performance of the obtained cathode material: the positive electrode material obtained in step (5) of this example was coated and tabletted, assembled into a half cell (negative electrode was lithium plate), and subjected to electrochemical performance test using blue electricity.
The electrochemical performance test method of the cathode material obtained in each of the following examples is the same as the electrochemical performance test method of the cathode material obtained in this example.
The electrochemical performance test result of the cathode material obtained in the embodiment shows that the voltage range is 3.0-4.3V, and the current density is 0.1C (1C = 200 mA g)-1) Next, the first-turn discharge capacity of the positive electrode material of this example was 201.3 mAh g-1The cycle retention after 100 cycles was 91%.
Example 2
The method for preparing hydrogen by combining waste lithium ion battery anode materials and electrochemistry comprises the following steps:
(1) waste LiNi0.8Co0.1Mn0.1O2Ball-milling the material, sieving with a 200-mesh sieve, and drying to obtain recovered powder of the secondary agglomerated particles of the waste anode material;
(2) mixing the recovered powder of the secondary agglomerated particles of the waste positive electrode material obtained in the step (1) with acetylene black and PVDF according to a mass ratio of 80:10:10, dispersing in an N-methyl pyrrolidone solution, uniformly stirring, and drying to obtain a pole piece;
(3) taking the pole piece obtained in the step (2) as a positive electrode, taking a graphite electrode as a negative electrode, and adding 1 mol/L Li2SO4In the solution, charging to 2.0V at a constant current of 0.02A, then charging to 0.1 mA at a constant voltage under the condition of 2.0V, dispersing secondary agglomerated particles of the waste anode material on the anode into primary particles to obtain primary particles of the waste anode material, and generating hydrogen at the cathode;
(4) after the reaction is finished, collecting primary particles of the waste positive electrode material on the positive electrode piece, and carrying out inductively coupled plasma mass spectrometry (ICP), wherein the calculated lithium release amount is 99%, and the molar ratio of nickel, cobalt and manganese is 0.79:0.10: 0.11;
(5) taking the primary particles of the waste anode material collected in the step (4) as a precursor, and mixing the precursor and the LiNO according to the molar ratio of 1:1.033Mixing, heating to 450 ℃ at the heating rate of 3 ℃/min under the oxygen atmosphere, keeping the temperature for 4 h, heating to 800 ℃ again, keeping the temperature for 15h, and cooling to obtain the cathode material.
The electrochemical performance test result of the cathode material obtained in the embodiment shows that the voltage range is 3.0-4.3V, and the current density is 0.1C (1C = 200 mA g)-1) Next, the first-cycle discharge capacity of the positive electrode material of this example was 202.2 mAh g-1The cycle retention after 100 cycles was 93%.
Example 3
The method for preparing hydrogen by combining waste lithium ion battery anode materials and electrochemistry comprises the following steps:
(1) waste LiNi0.8Co0.15Al0.05O2Ball-milling the material, sieving the material by a 150-mesh sieve, and drying to obtain recovered powder of the secondary agglomerated particles of the waste anode material;
(2) mixing the recovered powder of the secondary agglomerated particles of the waste positive electrode material obtained in the step (1) with acetylene black and PVDF according to a mass ratio of 80:10:10, dispersing in an N-methyl pyrrolidone solution, uniformly stirring, and drying to obtain a pole piece;
(3) taking the pole piece obtained in the step (2) as a positive electrode, taking a graphite electrode as a negative electrode, and adding 1 mol/L Li2SO4In the solution, charging to 2.0V at a constant current of 0.03A, then charging to 0.1 mA at a constant voltage under the condition of 2.0V, dispersing secondary agglomerated particles of the waste anode material on the anode into primary particles to obtain primary particles of the waste anode material, and generating hydrogen at the cathode;
(4) after the reaction is finished, collecting primary particles of the waste positive electrode material on the positive electrode piece, and carrying out inductively coupled plasma mass spectrometry (ICP), wherein the calculated lithium release amount is 99%, and the molar ratio of nickel, cobalt and aluminum is 0.8:0.16: 0.04;
(5) taking the primary particles of the waste anode material collected in the step (4) as a precursor according to the mol ratio of 1:1.04 to LiNO3Mixing, heating to 450 ℃ at the heating rate of 3 ℃/min under the oxygen atmosphere, preserving heat for 4 h, heating to 780 ℃ and preserving heat for 15h, and cooling to obtain the cathode material.
The electrochemical performance test result of the cathode material obtained in the embodiment shows that the voltage range is 3.0-4.3V, and the current density is 0.1C (1C = 200 mA g)-1) Next, the first-cycle discharge capacity of the positive electrode material of this example was 196.6 mAh g-1The cycle retention after 100 cycles was 95%.
Example 4
The method for preparing hydrogen by combining waste lithium ion battery anode materials and electrochemistry comprises the following steps:
(1) waste LiNi0.6Co0.2Mn0.2O2Ball-milling the material, sieving with a 200-mesh sieve, and drying to obtain recovered powder of the secondary agglomerated particles of the waste anode material;
(2) mixing the recovered powder of the secondary agglomerated particles of the waste positive electrode material obtained in the step (1) with acetylene black and PVDF according to a mass ratio of 80:10:10, dispersing in an N-methyl pyrrolidone solution, uniformly stirring, and drying to obtain a pole piece;
(3) taking the pole piece obtained in the step (2) as a positive electrode, taking a graphite electrode as a negative electrode, and adding 1 mol/L Li2SO4In the solution, charging to 1.9V at a constant current of 0.02A, then charging to 0.1 mA at a constant voltage under the condition of 1.9V, dispersing secondary agglomerated particles of the waste anode material on the anode into primary particles to obtain primary particles of the waste anode material, and generating hydrogen at the cathode;
(4) collecting primary particles of the waste positive electrode material on the positive electrode piece after the reaction is finished, and carrying out inductively coupled plasma mass spectrometry (ICP), wherein the calculated lithium removal amount is 98%, and the molar ratio of nickel, cobalt and manganese is 0.61:0.18: 0.21;
(5) taking the primary particles of the waste anode material collected in the step (4) as a precursor according to the mol ratio of 1:1.05 to LiOH.H2O mixtureAnd (3) heating to 450 ℃ at the heating rate of 3 ℃/min under the oxygen atmosphere, preserving heat for 4 h, heating to 850 ℃ again, preserving heat for 15h, and cooling to obtain the anode material.
The electrochemical performance test result of the cathode material obtained in the embodiment shows that the voltage range is 3.0-4.3V, and the current density is 0.1C (1C = 165 mA g)-1) Next, the first-cycle discharge capacity of the positive electrode material of this example was 167.4 mAh g-1The cycle retention after 100 cycles was 94%.
Claims (10)
1. The method for preparing hydrogen by combining electrochemical recycling of the anode material of the waste lithium ion battery is characterized by comprising the following steps of:
(1) ball-milling, sieving and drying the waste anode material to obtain recovered powder of secondary agglomerated particles of the waste anode material;
(2) mixing the recovered powder of the secondary agglomerated particles of the waste positive electrode material obtained in the step (1) with a conductive agent and an adhesive, dispersing the mixture in an N-methyl pyrrolidone solution, uniformly stirring, coating the mixture on a metal conductive substrate, and drying to obtain a pole piece;
(3) charging in an electrolyte solution by taking the pole piece obtained in the step (2) as a positive electrode and an inert electrode as a negative electrode, dispersing secondary agglomerated particles of the waste positive electrode material on the positive electrode into primary particles to obtain primary particles of the waste positive electrode material, and generating hydrogen by the negative electrode;
(4) after the reaction is finished, collecting primary particles of the waste positive electrode material on the positive electrode piece, carrying out inductively coupled plasma mass spectrometry, and detecting the removal amount of lithium and the molar ratio of nickel, cobalt and manganese;
(5) mixing the waste and old positive electrode material primary particles collected in the step (4) as a precursor with lithium salt, pre-sintering, and then heating and calcining to obtain a positive electrode material;
the waste anode material is an anode material disassembled from a waste lithium ion battery or a waste material generated in the production process of the anode material; the positive electrode material is LiNixCoyMn1-x-yO2、LiCoO2、Li4Mn5O12And LiNixCoyAl1-x-yO2Wherein 0 is less than or equal to x, y< 1、0≤ x+ y < 1。
2. The method for preparing hydrogen by combining waste lithium ion battery anode materials and electrochemistry according to claim 1, wherein in the step (1), the screening is performed by a screen of 50-400 meshes, preferably 100-200 meshes.
3. The method for producing hydrogen by combining waste lithium ion battery cathode materials and electrochemistry according to claim 1 or 2, characterized in that in the step (2), the conductive agent is acetylene black or carbon black; the adhesive is one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose, polyacrylic acid and polyvinyl alcohol; the mass ratio of the recovered powder of the secondary agglomerated particles of the waste anode material to the conductive agent to the adhesive is 75:15:5, 80:10:10, 85:10:5 or 90:5: 5; the metal conductive substrate is one or more of a titanium sheet, a titanium mesh, a stainless steel sheet, a stainless steel mesh and a nickel mesh.
4. The method for producing hydrogen by combining waste lithium ion battery cathode materials with electrochemistry according to any one of claims 1 to 3, wherein in the step (3), the inert electrode is a metal electrode or a carbon electrode which cannot embed lithium.
5. The method for producing hydrogen by combining electrochemical methods with the recycled positive electrode materials of waste lithium ion batteries according to any one of claims 1 to 4, wherein in the step (3), the electrolyte is Li2SO4、Na2SO4、K2SO4、LiCl、NaCl、KCl、LiNO3、NaNO3、KNO3One or more of LiOH, NaOH and KOH; the concentration of the electrolyte solution is 0.1-5 mol/L, preferably 0.5-3 mol/L, and more preferably 1-2 mol/L.
6. The method for producing hydrogen by combining waste lithium ion battery cathode materials with electrochemistry according to any one of claims 1 to 5, characterized in that in the step (3), the charging current is 0.0001-0.2A, preferably 0.001-0.1A, more preferably 0.01-0.5A; the potential difference across the charged electrodes is 0.1-3.0V, preferably 0.3-2.5V.
7. The method for producing hydrogen by combining waste lithium ion battery positive electrode materials with electrochemistry according to any one of claims 1 to 6, characterized in that in the step (5), the molar ratio of the waste positive electrode material primary particles to the lithium salt is 1: 1.00-1.06, preferably 1: 1.02-1.05; the lithium salt is LiOH or Li2SO4、Li2CO3、LiNO3One or more of them.
8. The method for producing hydrogen by combining waste lithium ion battery cathode materials with electrochemistry according to any one of claims 1 to 7, wherein in the step (5), the atmosphere of pre-sintering and calcining is air or oxygen.
9. The method for recycling the anode material of the waste lithium ion battery to combine with electrochemical hydrogen production according to any one of claims 1 to 8, wherein in the step (5), the pre-sintering temperature is 400-; the pre-sintering time is 3-8 h, preferably 4-5 h.
10. The method for preparing hydrogen by combining the recycled waste lithium ion battery anode material with electrochemistry according to any one of claims 1 to 9, characterized in that in the step (5), the temperature rise rate is 2-5 ℃/min, preferably 3 ℃/min; the calcining temperature is 650-900 ℃, preferably 750-850 ℃; the calcination time is 5-24 h, preferably 10-15 h.
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| CN113265704A (en) * | 2021-05-17 | 2021-08-17 | 合肥工业大学 | Method for preparing flake single crystal ternary electrode material with exposed {010} crystal face by regenerating waste lithium ion battery |
| CN113437377A (en) * | 2021-06-15 | 2021-09-24 | 昆明理工大学 | Single crystallization regeneration method for waste ternary positive electrode material |
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