CN111477986B - Method for preparing ternary lithium ion battery precursor by electrolyzing sodium sulfate waste liquid - Google Patents
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention provides a method for preparing a ternary lithium ion battery precursor by electrolyzing sodium sulfate waste liquid, which comprises the following steps: step 1, leaching; step 2, purifying; step 3, electrolysis; step 4, solid-liquid separation; the invention realizes the recycling of liquid phase components, the production process is safe and environment-friendly, no waste residue, waste gas or waste liquid is discharged, and the production running cost is reduced; the method has the advantages that the waste sodium sulfate waste liquid is effectively recycled, meanwhile, the precursor of the anode material of the ternary lithium ion battery is directly produced, and the operation efficiency is high; the obtained product is pure and the phase of the precursor is good by adopting the ion membrane method for electrolysis; besides producing battery materials, the byproducts of hydrogen and oxygen in the electrolysis process can bring certain economic benefits.
Description
Technical Field
The invention relates to the field of waste lithium ion battery recovery, in particular to a method for preparing a ternary lithium ion battery precursor by electrolyzing sodium sulfate waste liquid.
Background
The energy problem is always a big problem which puzzles all countries around the world, fossil fuel brings endless development power and development opportunity to human beings in the past one hundred years, but the gradual exhaustion of non-renewable resources also makes people realize that the effective utilization and excavation of renewable resources need to be expanded. The renewable resources of solar energy, wind energy and water energy are greatly influenced by time and space and cannot be used at any time and any place, and the lithium ion battery gradually becomes an energy storage device popular to people by virtue of unique excellent performance.
Through continuous development of decades, the system of the lithium ion battery is continuously and greatly broken through, the battery capacity, the cycle performance, the rate performance, the battery safety and other aspects are obviously improved, and the current 3C electronic product, military, aviation, medical treatment, industry and new energy automobile fields are not opened. The discovery and rapid development of the lithium ion battery are great progress of the whole human society, and in order to show the outstanding contribution of three people, namely Goodenough, whittngham and Yoshino, in the field of the lithium ion battery, the Nobel chemical prize in 2019 is awarded to the three researchers, so that the society can fully identify and affirm the development of the field of the lithium ion battery. In recent years, with the continuous development of new energy automobiles, the annual demand and usage of lithium batteries are increasing year by year, which indicates that the scrappage of lithium ion batteries is also increasing year by year, if waste lithium ion batteries cannot be properly treated, not only is serious harm caused to the surrounding environment, but also valuable metals such as cobalt, manganese, nickel and lithium in the waste batteries are lost, especially the reserves of metal cobalt resources are gradually exhausted, and the problem of difficult regeneration is faced, and cobalt resource recovery becomes an urgent problem.
In recent years, researchers and enterprises have also developed battery recycling processes by various methods, and in the aspect of fire recycling, patent document CN104611566A discloses a method for recycling valuable metals in waste lithium ion batteries, which comprises the following steps: mixing the waste lithium ion battery and carbon powder, putting the mixture into a rotary kiln for reductive roasting, mixing the roasted product with a slag former, and then putting the mixed material into an electric furnace for smelting. Similarly, chinese patent document CN106129511A discloses a method for recovering lithium metal from waste lithium ion battery materials by reduction roasting, and valuable elements such as cobalt, nickel, manganese, etc. are purified and extracted by oxidation acid leaching to obtain chemical products. The method has large energy consumption for roasting at high temperature, is easy to generate toxic gas, can generate a large amount of organic waste liquid and acid liquid in the recovery process of nickel, cobalt and manganese, and does not accord with the green development concept.
In the wet recovery process of the lithium ion battery, in order to separate valuable metal components in the positive electrode material from the conductive carbon powder, sulfuric acid is often required to be leached, and then sodium hydroxide solution is used as a precipitator to recover the valuable metals, so that a large amount of sodium sulfate waste liquid is inevitably generated in the whole process. For example, chinese patent document CN107117661A discloses a method for preparing ternary hydroxide by recovering nickel, cobalt and manganese from waste lithium ion batteries by liquid phase method, which mainly comprises the following steps: disassembling and crushing, slurrying, leaching, removing copper by an extraction method, removing iron and aluminum by a precipitation method, and preparing the nickel-cobalt-manganese ternary hydroxide. The method solves the problems of high energy consumption and serious pollution of recovery of the lithium ion battery by a pyrogenic process, but the waste ammonia and wastewater containing sodium sulfate or sodium chloride, which are formed by acids such as sulfuric acid, hydrochloric acid and the like and alkalis such as sodium hydroxide, ammonia water and the like introduced in the process, are not effectively treated and recycled, so that the method is not beneficial to environmental protection and long-term development.
Disclosure of Invention
The invention provides a method for preparing a ternary lithium ion battery precursor by electrolyzing sodium sulfate waste liquid, and aims to provide an efficient and environment-friendly wet recovery process, so that the sodium sulfate waste liquid is effectively treated, and the precursor of the ternary cathode material of the lithium ion battery is directly produced.
In order to achieve the above object, an embodiment of the present invention provides a method for preparing a ternary lithium ion battery precursor by electrolyzing a sodium sulfate waste liquid, including the following steps:
step 1, leaching:
leaching a powder material of a waste ternary lithium ion battery into a liquid phase by adopting an acid leaching method, separating to obtain carbon negative electrode powder and leachate containing metal elements, and sintering the carbon negative electrode powder to prepare a negative electrode material for the lithium ion battery;
step 2, purification:
carrying out physical sedimentation and chemical adsorption on the leachate obtained in the step 1, then extracting to remove Li in the solution + Then the mixture is put into a leachate storage tank for heating and temperature rise, and then NiSO is added 4 、CoSO 4 And MnSO 4 Adjusting the ratio of transition metal elements in the leachate to Ni: co: mn = 5;
step 3, electrolysis:
introducing the sodium sulfate waste liquid into an electrolytic cell intermediate tank, simultaneously introducing dilute sulfuric acid and dilute sodium hydroxide solution into an electrolytic cell anode chamber and an electrolytic cell cathode chamber respectively, separating the electrolytic cell anode chamber and the electrolytic cell cathode chamber through an ionic membrane, introducing the leachate and ammonia water obtained in the step 2 into the electrolytic cell cathode chamber when electrolysis is started, obtaining hydroxide precursor precipitates of Ni, co and Mn, a sodium sulfate solution and an ammonium sulfate solution in the electrolytic cell cathode chamber after electrolysis, obtaining a concentrated sulfuric acid solution in the electrolytic cell anode chamber, and conveying the concentrated sulfuric acid solution to the leaching process in the step 1;
step 4, solid-liquid separation:
and carrying out solid-liquid separation on the precursor precipitate, the sodium sulfate solution and the ammonium sulfate solution obtained from the cathode chamber of the electrolytic cell, drying and pre-lithiation sintering on the separated precursor solid to obtain a ternary lithium ion battery precursor, and conveying the solution obtained by solid-liquid separation to the anode chamber of the electrolytic cell or the middle chamber of the electrolytic cell for recycling.
Preferably, in the step 1, a leaching agent for leaching the powder material of the waste ternary lithium ion battery is one of sulfuric acid, hydrochloric acid and nitric acid.
Preferably, in the step 2, the extractant used for extraction is tartaric acid, and the concentration of the transition metal ions in the leachate obtained in the step 2 is 0.5-3 mol/L.
Preferably, in the step 3, the concentration of the dilute sulfuric acid is 0.05-2 mol/L, and the concentration of the sodium hydroxide is 0.05-2 mol/L.
Preferably, in the step 3, the current density of electrolysis is 1.5-4 kA/m 2 (ii) a The concentration of sodium sulfate in the sodium sulfate waste liquid is 1-5 mol/L, and the suitable temperature for electrolysis is 40-80 ℃.
Preferably, in the step 3, the concentration of ammonia water is 0.5mol/L, and the pH value of the cathode chamber in the electrolysis process is 11.5-12.5.
Preferably, the electrolytic cell in the step 3 is a three-chamber electrolytic cell or a two-chamber electrolytic cell; in the double-chamber electrolytic cell, a cation membrane is arranged between a cathode chamber and an anode chamber of the electrolytic cell; in the three-chamber electrolytic cell, a positive ion membrane is arranged between the cathode chamber of the electrolytic cell and the intermediate tank of the electrolytic cell, and an negative ion membrane is arranged between the anode chamber of the electrolytic cell and the intermediate tank of the electrolytic cell.
Preferably, the cation membrane is a Nafion-117 type perfluorinated sulfonic acid ion membrane, and the anion membrane is an AMI-7001 type quaternary ammonium anion membrane; the anode material is a titanium electrode plated with an iridium ruthenium coating, and the cathode material is a nickel cathode plated with a platinum carbon coating.
The scheme of the invention has the following beneficial effects:
(1) The liquid phase components in the production process can be completely recycled, and the production running cost is lower;
(2) The method has the advantages that the waste sodium sulfate waste liquid is effectively recycled, meanwhile, the precursor of the anode material of the ternary lithium ion battery is directly produced, and the operation efficiency is high;
(3) The production process is safe and environment-friendly, and no waste residue, waste gas or waste liquid is discharged;
(4) The obtained product is pure and the phase of the precursor is good by adopting the ion membrane method for electrolysis;
(5) Besides producing battery materials, the byproducts of hydrogen and oxygen in the electrolysis process can bring certain economic benefits.
Drawings
FIG. 1 is a process diagram of the present invention
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1, an embodiment of the present invention provides a method for preparing a precursor of a ternary lithium ion battery by electrolyzing a sodium sulfate waste liquid, including the following steps:
step 1: the method comprises the steps of leaching a positive electrode powder material of a waste ternary lithium ion battery by using a 1.5mol/L sulfuric acid solution, leaching metal elements such as Li, ni, co, mn and the like in the positive electrode material into a liquid phase, separating to obtain carbon negative electrode powder and leachate containing the metal elements such as Li, ni, co, mn and the like, and sintering the carbon negative electrode powder to prepare the high-value negative electrode material for the lithium ion battery.
Step 2: performing physical sedimentation and chemical adsorption on the leachate obtained in the step 1, then extracting by using tartaric acid as an extracting agent to remove Li in the solution + Then adding NiSO into the leaching solution 4 、CoSO 4 And MnSO 4 And adjusting the proportion of transition metal elements in the leachate so that the ratio of Ni to Co to Mn =5 is in a ratio of 2, the total concentration of transition metal ions is 2mol/L, and the total volume of the solution is 3L. The solution was warmed to 60 ℃.
And 3, step 3: electrolyzing by adopting a three-chamber electrolytic cell, wherein a cationic membrane is arranged between a cathode chamber of the electrolytic cell and an intermediate tank of the electrolytic cell, and is a Nafion-117 type perfluorinated sulfonic acid ionic membrane; an anion membrane is arranged between the anode chamber of the electrolytic cell and the middle cell of the electrolytic cell, and the anion membrane is an AMI-7001 type quaternary ammonium anion membrane; the anode material is a titanium electrode plated with an iridium ruthenium coating, and the cathode material is a nickel cathode plated with a platinum carbon coating.
Firstly, pretreating and installing an ionic membrane, introducing a sulfuric acid solution with the concentration of 0.5mol/L into an anode chamber of an electrolytic cell, introducing a sodium sulfate waste liquid with the sulfuric acid concentration of 2mol/L into an intermediate tank of the electrolytic cell, introducing a sodium hydroxide solution with the concentration of 0.5mol/L, an ammonia water solution with the concentration of 0.5mol/L and the leachate obtained in the step 2 into a cathode chamber of the electrolytic cell, wherein the ammonia water is added in the first electrolysis process, and then is not added, so that the ammonia water can be added againObtained by electrolysis of ammonium sulfate solution; the current density in the electrolytic process is 2.5kA/m 2 The electrolysis temperature was 60 ℃. After electrolysis, obtaining hydroxide precursor precipitates of Ni, co and Mn, a sodium sulfate solution and an ammonium sulfate solution in a cathode chamber of the electrolytic cell, obtaining a concentrated sulfuric acid solution in an anode chamber of the electrolytic cell, and conveying the obtained concentrated sulfuric acid solution to the leaching process in the step 1; the hydrogen and oxygen generated in the electrolysis process can be collected, purified and directly sold.
Step four: and after the electrolysis is finished, carrying out suction filtration on the precipitate and the solution in the cathode chamber of the electrolytic cell, and conveying the separated solution to the electrolytic cell for recycling to obtain 493.52g of hydroxide precipitate of nickel, cobalt and manganese, wherein the recovery rate is 90.51% by calculation.
The invention realizes the recycling of liquid phase components, the production process is safe and environment-friendly, no waste residue, waste gas or waste liquid is discharged, and the production running cost is reduced; the method has the advantages that the waste sodium sulfate waste liquid is effectively recycled, meanwhile, the precursor of the anode material of the ternary lithium ion battery is directly produced, and the operation efficiency is high; the obtained product is pure and the phase of the precursor is good by adopting the ion membrane method for electrolysis; besides producing battery materials, the byproducts of hydrogen and oxygen in the electrolysis process can bring certain economic benefits.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A method for preparing a ternary lithium ion battery precursor by electrolyzing sodium sulfate waste liquid is characterized by comprising the following steps:
step 1, leaching:
leaching a powder material of a waste ternary lithium ion battery into a liquid phase by adopting an acid leaching method, separating to obtain carbon negative electrode powder and leachate containing metal elements, and sintering the carbon negative electrode powder to prepare a negative electrode material for the lithium ion battery;
step 2, purification:
carrying out physical sedimentation and chemical adsorption on the leachate obtained in the step 1, then extracting to remove Li in the solution + Then the mixture is put into a leachate storage tank for heating and temperature rise, and then NiSO is added 4 、CoSO 4 And MnSO 4 Adjusting the transition metal element ratio in the leachate to a ratio of Ni to Co to Mn =5 or Ni to Co to Mn = 1;
step 3, electrolysis:
introducing the sodium sulfate waste liquid into an electrolytic cell intermediate tank, simultaneously introducing dilute sulfuric acid and dilute sodium hydroxide solution into an electrolytic cell anode chamber and an electrolytic cell cathode chamber respectively, separating the electrolytic cell anode chamber and the electrolytic cell cathode chamber through an ionic membrane, introducing the leachate and ammonia water obtained in the step 2 into the electrolytic cell cathode chamber when electrolysis is started, obtaining hydroxide precursor precipitates of Ni, co and Mn, a sodium sulfate solution and an ammonium sulfate solution in the electrolytic cell cathode chamber after electrolysis, obtaining a concentrated sulfuric acid solution in the electrolytic cell anode chamber, and conveying the concentrated sulfuric acid solution to the leaching process in the step 1;
step 4, solid-liquid separation:
and carrying out solid-liquid separation on the precursor precipitate, the sodium sulfate solution and the ammonium sulfate solution obtained from the cathode chamber of the electrolytic cell, drying and pre-lithiation sintering on the separated precursor solid to obtain a ternary lithium ion battery precursor, and conveying the solution obtained by solid-liquid separation to the anode chamber of the electrolytic cell or the middle chamber of the electrolytic cell for recycling.
2. The method for preparing the precursor of the ternary lithium ion battery by electrolyzing the sodium sulfate waste liquid as claimed in claim 1, wherein in the step 1, a leaching agent for leaching the powder material of the waste ternary lithium ion battery is one of sulfuric acid, hydrochloric acid and nitric acid.
3. The method for preparing the ternary lithium ion battery precursor according to claim 2, wherein in the step 2, an extracting agent used for extraction is tartaric acid, and the concentration of the transition metal ions in the leachate obtained in the step 2 is 0.5-3 mol/L.
4. The method for preparing the precursor of the ternary lithium ion battery by electrolyzing the sodium sulfate waste liquid according to claim 3, wherein in the step 3, the concentration of the dilute sulfuric acid is 0.05-2 mol/L, and the concentration of the sodium hydroxide is 0.05-2 mol/L.
5. The method for preparing the precursor of the ternary lithium ion battery by electrolyzing the sodium sulfate waste liquid according to claim 4, wherein the current density of electrolysis in the step 3 is 1.5-4 kA/m 2 (ii) a The concentration of sodium sulfate in the sodium sulfate waste liquid is 1-5 mol/L, and the suitable temperature for electrolysis is 40-80 ℃.
6. The method for preparing the ternary lithium ion battery precursor by electrolyzing the sodium sulfate waste liquid as claimed in claim 5, wherein in the step 3, the concentration of ammonia water is 0.5mol/L, and the pH value of the cathode chamber in the electrolysis process is 11.5-12.5.
7. The method for preparing the precursor of the ternary lithium ion battery by electrolyzing the sodium sulfate waste liquid as claimed in claim 6, wherein the electrolytic bath in the step 3 is a three-chamber electrolytic bath or a two-chamber electrolytic bath; in the double-chamber electrolytic cell, a cation membrane is arranged between a cathode chamber and an anode chamber of the electrolytic cell; in the three-chamber electrolytic cell, a positive ion membrane is arranged between the cathode chamber of the electrolytic cell and the intermediate tank of the electrolytic cell, and an negative ion membrane is arranged between the anode chamber of the electrolytic cell and the intermediate tank of the electrolytic cell.
8. The method for preparing the ternary lithium ion battery precursor by electrolyzing the sodium sulfate waste liquid according to claim 7, wherein the cation membrane is a Nafion-117 type perfluorosulfonic acid ion membrane, and the anion membrane is an AMI-7001 type quaternary ammonium anion membrane; the anode material is a titanium electrode plated with an iridium ruthenium coating, and the cathode material is a nickel cathode plated with a platinum carbon coating.
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