CN112695198A - Method for producing hydrogen by combining recovery of waste lithium iron phosphate positive electrode material and electrochemical process - Google Patents
Method for producing hydrogen by combining recovery of waste lithium iron phosphate positive electrode material and electrochemical process Download PDFInfo
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- CN112695198A CN112695198A CN202011402715.1A CN202011402715A CN112695198A CN 112695198 A CN112695198 A CN 112695198A CN 202011402715 A CN202011402715 A CN 202011402715A CN 112695198 A CN112695198 A CN 112695198A
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- iron phosphate
- lithium iron
- waste lithium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
A method for combined recovery of waste lithium iron phosphate anode materials and electrochemical hydrogen production comprises the following steps: (1) mechanically activating, screening and drying the waste lithium iron phosphate anode material to obtain waste lithium iron phosphate anode material powder; (2) mixing the waste lithium iron phosphate positive electrode material powder with a conductive agent and an adhesive, dispersing the mixture in an N-methyl pyrrolidone solution, coating the mixture on a metal conductive matrix, 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, and generating ferric hydroxide precipitate at the positive electrode, namely generating hydrogen at the negative electrode; (4) and after the reaction is finished, filtering the reaction system for solid-liquid separation to obtain a lithium-rich solution, and calcining the filter residue ferric hydroxide precipitate to obtain ferric oxide. The invention realizes the selective separation and recovery of the waste lithium iron phosphate anode material and the preparation of hydrogen by a simple, rapid, low-energy-consumption and environment-friendly method, and finally obtains the iron oxide and the high-purity hydrogen.
Description
Technical Field
The invention relates to the technical field of waste lithium ion battery recovery and electrochemical hydrogen production, in particular to a method for combining waste lithium iron phosphate positive electrode material recovery and electrochemical hydrogen production.
Background
Since the development of the electric vehicle industry, China is the largest global consumption market of lithium iron phosphate. Particularly, the rate of increase is nearly 200% in 2012-2013, and the sales of the lithium iron phosphate in China in 2013 is about 5797 t, which accounts for more than 50% of the global sales. In 2014, 75% of lithium iron phosphate cathode materials are sold to China, the theoretical life of the lithium iron phosphate battery is 7-8 years (calculated by 7 years), and about 9400 t of lithium iron phosphate is expected to be scrapped in 2021, so that if the lithium iron phosphate is not treated by huge waste amount, not only environmental pollution, but also energy waste and economic loss are brought.
LiPF contained in lithium iron phosphate battery6Chemical substances such as organic carbonate and copper are in national hazardous waste list, LiPF6Strong corrosivity, and HF is easily generated by decomposition in water; products decomposed and hydrolyzed by the organic solvent can cause serious pollution to the atmosphere, water and soil and harm to an ecosystem; copper and other heavy metals accumulate in the environment and finally harm human beings through a biological chain; once the phosphorus element enters water bodies such as lakes and the like, the eutrophication of the water bodies is easily caused. Therefore, if the waste lithium iron phosphate batteries are not recycled,is a great harm to the environment and human health.
The existing recovery method of lithium iron phosphate mainly comprises the steps of leaching by a wet method with strong acid and strong oxidant to obtain a solution containing lithium and iron, adding strong base to precipitate iron ions to obtain ferric hydroxide, and calcining the ferric hydroxide to obtain ferric oxide; or solid waste of lithium and iron phosphate is obtained by acid leaching and separation. Neither of these two types of recovery methods is an efficient and clean recovery method, and a large amount of waste liquid and waste residue are generated in the recovery process or the resource utilization is insufficient, so that further improvement is required.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing a simple, quick, low-energy-consumption and environment-friendly method for combining waste lithium iron phosphate positive electrode material recovery and electrochemical hydrogen production.
The technical scheme adopted for solving the technical problems is that the method for combining the recovery of the waste lithium iron phosphate anode material and the electrochemical hydrogen production comprises the following steps:
(1) mechanically activating, screening and drying the waste lithium iron phosphate anode material to obtain waste lithium iron phosphate anode material powder;
(2) mixing the waste lithium iron phosphate anode material powder 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 taking an inert electrode as a negative electrode, generating ferric hydroxide precipitate at the positive electrode, and generating hydrogen at the negative electrode;
(4) after the reaction is finished, filtering the reaction system for solid-liquid separation to obtain a lithium-rich solution, and calcining the filter residue ferric hydroxide precipitate to obtain ferric oxide;
the waste lithium iron phosphate anode material is a lithium iron phosphate anode material disassembled from a waste lithium ion battery or a waste material generated in the production process of the lithium iron phosphate material.
Further, in the step (2), the conductive agent is acetylene black or carbon black.
Further, in the step (2), the binder 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 waste lithium iron phosphate positive electrode material powder to the conductive agent to 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 electrolyte is Li2SO4、Li3PO4、Na2SO4、K2SO4、LiCl、NaCl、KCl、LiNO3、NaNO3、KNO3One or more of LiOH, NaOH and KOH.
Further, in the step (3), the concentration range 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 pH value of the electrolyte solution is 7-13, preferably 8-12, and more preferably 9-11.
Further, in the step (3), the current for charging is 0.0001 to 5A, preferably 0.005 to 2A, more preferably 0.01 to 1A.
Further, in the step (3), the potential difference across the charged electrode is 0.5 to 3.0V, preferably 0.8 to 1.5V.
Further, in the step (3), the number of charging is 2 to 50, preferably 10 to 45, more preferably 20 to 40, and further preferably 25 to 35.
Further, in the step (4), the calcination temperature is 800 ℃ and preferably 300 ℃ and 600 ℃, and the calcination time is 1-24h and preferably 3-20 h.
The invention has the beneficial effects that: in the charging process, a pole piece made of waste lithium iron phosphate positive pole material is used as an anode, an inert electrode is used as a cathode, multiple times of constant-current and constant-voltage charging are carried out, the anode carries out lithium removal reaction, lithium enters the solution to obtain a lithium-rich solution, and the lithium can be separated and recovered from the solution; the lithium-removed iron phosphate is unstable in a solution with a higher pH value and gradually changes to ferric hydroxide, the reaction is stopped when the charging capacity basically reaches the theoretical capacity of the lithium iron phosphate anode material, after the reaction is finished, the reaction system is filtered for solid-liquid separation, a lithium-rich solution is collected, and the obtained ferric hydroxide precipitate is calcined to obtain ferric oxide, so that the comprehensive utilization of the waste lithium iron phosphate material is realized; in addition, the cathode generates hydrogen evolution reaction in the reaction process, so that hydroxide ions consumed in the solution are supplemented, and high-purity hydrogen is obtained, thereby further improving the economic benefit.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The method for combining waste lithium iron phosphate positive electrode material recovery and electrochemical hydrogen production comprises the following steps:
(1) mechanically activating, screening and drying the waste lithium iron phosphate anode material to obtain waste lithium iron phosphate anode material powder;
(2) mixing the waste lithium iron phosphate anode material powder obtained in the step (1) with acetylene black and PTFE according to a mass ratio of 85:10:5, dispersing in an N-methyl pyrrolidone solution, uniformly stirring, coating on a titanium plate, and drying to obtain a pole piece;
(3) and (3) taking the pole piece obtained in the step (2) as a positive electrode, taking a graphite electrode as a negative electrode, adjusting the pH value of the solution to 9 in 2 mol/L LiCl solution, firstly charging to 0.8V at a constant current of 0.01A, then charging to 0.5 mA at a constant voltage under the condition of 0.8V, and then performing constant current and constant voltage charging again for 30 times to generate ferric hydroxide precipitate on the positive electrode and generate hydrogen on the negative electrode.
(4) After the reaction is finished, carrying out filtration solid-liquid separation on the reaction system to obtain a filtrate lithium-rich solution; calcining the filter residue ferric hydroxide precipitate for 3h at 800 ℃ to obtain the ferric oxide.
And respectively carrying out inductively coupled plasma mass spectrometry (ICP) on the filtered electrolyte and the filtered residue, detecting that the removal rate of lithium is 95% and the recovery rate of iron is 90%, and realizing comprehensive utilization of waste lithium iron phosphate material recovery and hydrogen preparation in one step.
Example 2
The method for combining waste lithium iron phosphate positive electrode material recovery and electrochemical hydrogen production comprises the following steps:
(1) mechanically activating, screening and drying the waste lithium iron phosphate anode material to obtain waste lithium iron phosphate anode material powder;
(2) mixing the waste lithium iron phosphate anode material powder obtained in the step (1) with acetylene black and PTFE according to a mass ratio of 85:10:5, dispersing in an N-methyl pyrrolidone solution, uniformly stirring, coating on a titanium plate, and drying to obtain a pole piece;
(3) taking the pole piece obtained in the step (2) as an anode, taking a graphite electrode as a cathode, adjusting the pH value of the solution to 10 in 2 mol/L LiCl solution, firstly charging to 0.8V at a constant current of 0.01A, then charging to 0.5 mA at a constant voltage under the condition of 0.8V, and then performing constant current and constant voltage charging again for 25 times to generate ferric hydroxide precipitate on the anode and generate hydrogen on the cathode;
(4) after the reaction is finished, filtering the reaction system to obtain a filtrate lithium-rich solution; calcining the filter residue ferric hydroxide precipitate for 8 hours at 500 ℃ to obtain the ferric oxide.
And respectively carrying out inductively coupled plasma mass spectrometry (ICP) on the filtered electrolyte and the filtered residue, detecting that the removal rate of lithium is 95% and the recovery rate of iron is 95%, and realizing comprehensive utilization of waste lithium iron phosphate material recovery and hydrogen preparation in one step.
Example 3
The method for combining waste lithium iron phosphate positive electrode material recovery and electrochemical hydrogen production comprises the following steps:
(1) mechanically activating, screening and drying the waste lithium iron phosphate anode material to obtain waste lithium iron phosphate anode material powder;
(2) mixing the waste lithium iron phosphate anode material powder obtained in the step (1) with acetylene black and PTFE according to a mass ratio of 85:10:5, dispersing in an N-methyl pyrrolidone solution, uniformly stirring, coating on a titanium plate, and drying to obtain a pole piece;
(3) taking the pole piece obtained in the step (2) as a positive pole, taking a graphite electrode as a negative pole, adjusting the pH value of the solution to 10 in 2 mol/L LiCl solution, firstly charging to 1.2V at a constant current of 0.01A, then charging to 0.5 mA at a constant voltage under the condition of 1.2V, and repeating the constant current and constant voltage charging for 35 times to generate ferric hydroxide precipitate at the positive pole and generate hydrogen at the negative pole;
(4) after the reaction is finished, filtering the reaction system to obtain a filtrate lithium-rich solution; and calcining the filter residue ferric hydroxide precipitate for 20 hours at 300 ℃ to obtain the ferric oxide.
And respectively carrying out inductively coupled plasma mass spectrometry (ICP) on the filtered electrolyte and the filtered residue, detecting that the removal rate of lithium is 99% and the recovery rate of iron is 98%, and realizing comprehensive utilization of waste lithium iron phosphate material recovery and hydrogen preparation in one step.
Claims (10)
1. A method for combined recovery of waste lithium iron phosphate anode materials and electrochemical hydrogen production is characterized by comprising the following steps:
(1) mechanically activating, screening and drying the waste lithium iron phosphate anode material to obtain waste lithium iron phosphate anode material powder;
(2) mixing the waste lithium iron phosphate anode material powder 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 taking an inert electrode as a negative electrode, generating ferric hydroxide precipitate at the positive electrode, and generating hydrogen at the negative electrode;
(4) after the reaction is finished, filtering the reaction system for solid-liquid separation to obtain a lithium-rich solution, and calcining the filter residue ferric hydroxide precipitate to obtain ferric oxide;
the waste lithium iron phosphate anode material is a lithium iron phosphate anode material disassembled from a waste lithium ion battery or a waste material generated in the production process of the lithium iron phosphate material.
2. The method for combining waste lithium iron phosphate positive electrode material recovery and electrochemical hydrogen production according to claim 1, wherein in the step (2), the conductive agent is acetylene black or carbon black.
3. The method for combined recycling of waste lithium iron phosphate positive electrode materials and electrochemical hydrogen production according to claim 1 or 2, wherein in the step (2), the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose, polyacrylic acid and polyvinyl alcohol.
4. The method for combined recycling of the waste lithium iron phosphate positive electrode material and electrochemical hydrogen production according to any one of claims 1 to 3, wherein in the step (2), the mass ratio of the waste lithium iron phosphate positive electrode material powder to the conductive agent to the adhesive is 75:15:5, 80:10:10, 85:10:5 or 90:5: 5.
5. The method for combined recovery of waste lithium iron phosphate positive electrode materials and electrochemical hydrogen production according to any one of claims 1 to 4, wherein 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.
6. The method for combined recovery and electrochemical hydrogen production of waste lithium iron phosphate positive electrode materials according to any one of claims 1 to 5, wherein in the step (3), the electrolyte is Li2SO4、Li3PO4、Na2SO4、K2SO4、LiCl、NaCl、KCl、LiNO3、NaNO3、KNO3One or more of LiOH, NaOH and KOH; the concentration range of the electrolyte solution is 0.1-5 mol/L, preferably 0.5-3 mol/L, and more preferably 1-2 mol/L.
7. The method for combined recovery and electrochemical hydrogen production of waste lithium iron phosphate cathode materials according to claims 1 to 6, wherein in the step (3), the pH value of the electrolyte solution is 7 to 13, preferably 8 to 12, and more preferably 9 to 11.
8. The method for combined recovery of waste lithium iron phosphate positive electrode materials and electrochemical hydrogen production according to any one of claims 1 to 7, wherein in the step (3), the charging current is 0.0001-5A, preferably 0.005-2A, and more preferably 0.01-1A; the potential difference across the charged electrodes is 0.5-3.0V, preferably 0.8-1.5V.
9. The method for combined recovery and electrochemical hydrogen production of the waste lithium iron phosphate positive electrode material according to any one of claims 1 to 8, wherein in the step (3), the number of charging is 2 to 50, preferably 10 to 45, more preferably 20 to 40, and further preferably 25 to 35.
10. The method for combined recovery and electrochemical hydrogen production of the waste lithium iron phosphate positive electrode material according to any one of claims 1 to 9, wherein in the step (4), the calcination temperature is 200-.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114517302A (en) * | 2022-03-01 | 2022-05-20 | 西安交通大学 | Device and method for coupling lithium extraction and hydrogen production of electricity-assisted photocatalytic lithium iron phosphate waste |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417923A (en) * | 2018-03-07 | 2018-08-17 | 合肥工业大学 | A kind of recycling method of retired lithium iron phosphate battery positive material |
| CN108808150A (en) * | 2018-06-13 | 2018-11-13 | 合肥工业大学 | A kind of method that synthetical recovery recycles waste and old ternary electrode material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417923A (en) * | 2018-03-07 | 2018-08-17 | 合肥工业大学 | A kind of recycling method of retired lithium iron phosphate battery positive material |
| CN108808150A (en) * | 2018-06-13 | 2018-11-13 | 合肥工业大学 | A kind of method that synthetical recovery recycles waste and old ternary electrode material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114517302A (en) * | 2022-03-01 | 2022-05-20 | 西安交通大学 | Device and method for coupling lithium extraction and hydrogen production of electricity-assisted photocatalytic lithium iron phosphate waste |
| CN114517302B (en) * | 2022-03-01 | 2023-11-03 | 西安交通大学 | Device and method for coupling lithium extraction and hydrogen production of electrically-assisted photocatalytic lithium iron phosphate waste |
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Application publication date: 20210423 |