CN114196821A - Efficient leaching method of waste lithium iron phosphate cathode material - Google Patents
Efficient leaching method of waste lithium iron phosphate cathode material Download PDFInfo
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- CN114196821A CN114196821A CN202111454515.5A CN202111454515A CN114196821A CN 114196821 A CN114196821 A CN 114196821A CN 202111454515 A CN202111454515 A CN 202111454515A CN 114196821 A CN114196821 A CN 114196821A
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- iron phosphate
- lithium iron
- waste lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
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- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A high-efficiency leaching method of waste lithium iron phosphate anode materials relates to a leaching method of waste lithium iron phosphate. The invention aims to solve the technical problems of long recycling process and high cost of the existing waste lithium iron phosphate material. The waste lithium iron phosphate anode material and oxalic acid are subjected to ball milling together by adopting a mechanochemical method, so that the waste lithium iron phosphate anode material has a good recovery effect on different types and different states of waste lithium iron phosphate batteries, and no requirement is imposed on the self state of the waste lithium iron phosphate anode material; the leaching rate of the lithium element in the lithium iron phosphate anode material recovered by the mechanochemical method is up to 100 percent, while the leaching rate of the iron element is only 12.97 percent, so that the method reduces the amount of alkaline solvent needed for later recovery of the lithium and iron elements.
Description
Technical Field
The invention relates to a leaching method of waste lithium iron phosphate.
Background
The secondary battery energy storage system is paid much attention and attention by energy departments and energy enterprises of various countries as an effective energy storage mode, and occupies a core position in the current energy storage industry. The mass energy density and the volume ratio energy of the lithium iron phosphate batteries are improved by the blade batteries and the CPT technology, so that the market share of the lithium iron phosphate batteries is greatly increased, and the treatment of the waste lithium iron phosphate batteries is delayed in time.
Although the recycling technology of the lithium iron phosphate battery has been developed for many years, some enterprises have already adopted the existing research and development technology to enter the industrialization stage, but there is still room for improvement in the aspects of environmental protection, flow simplification, cost reduction and the like. In the hydrometallurgy process, the steps of leaching, impurity removal, purification and the like are mostly adopted, wherein large enterprises such as Guinmei and the like adopt sulfuric acid in the leaching step, hydrochloric acid is adopted by Shenzhen jia Bin, Wuhanjiereite and the like as leachate, and the strong acid has the defects of high metal recovery rate, equipment corrosion, generation of a large amount of waste acid and waste alkali, long process flow and the like. And part of enterprises entering the recovery field later, such as Hunan Bangpu, adopt a high-temperature regeneration technology process, the process is simple, the flow is short, the high-temperature energy consumption is high, the national strategic demand significance of carbon neutralization is not met, the pretreatment process is strict, and otherwise impurities can cause great influence on the performance of the synthetic material.
Disclosure of Invention
The invention provides a high-efficiency leaching method of a waste lithium iron phosphate positive electrode material, aiming at solving the technical problems of long recycling process and high cost of the existing waste lithium iron phosphate material.
The efficient leaching method of the waste lithium iron phosphate anode material is carried out according to the following steps:
carrying out heat treatment on a waste lithium iron phosphate positive electrode material in an inert atmosphere, wherein the heat treatment temperature is 600-650 ℃, the heat treatment time is 60-65 min, stripping the waste lithium iron phosphate positive electrode material from an aluminum foil, grinding to obtain waste lithium iron phosphate powder, placing the waste lithium iron phosphate powder and oxalic acid in a ball mill for ball milling, and then placing the waste lithium iron phosphate powder and the oxalic acid in deionized water for soaking for 0.5-1 h to obtain a leaching solution of lithium ions and a small amount of iron ions;
the mass ratio of the oxalic acid to the ground waste lithium iron phosphate powder is (0.5-5) to 1;
the volume ratio of the ground waste lithium iron phosphate powder to deionized water is 1g (30-35 mL).
The invention has the following beneficial effects:
1. the waste lithium iron phosphate anode material and oxalic acid are subjected to ball milling together by adopting a mechanochemical method, so that the waste lithium iron phosphate anode material has a good recovery effect on different types and different states of waste lithium iron phosphate batteries, and no requirement is imposed on the self state of the waste lithium iron phosphate anode material;
2. the leaching rate of the lithium element in the lithium iron phosphate anode material recovered by the mechanochemical method is up to 100 percent (the error of a test system is within 2 percent in an inductively coupled plasma atomic emission spectrum test), and the leaching rate of the iron element is only 12.97 percent, so that the amount of alkaline solvent required for later-stage recovery of the lithium and iron elements is reduced;
3. the chemicals used in the process of recovering the waste lithium iron phosphate material are mainly deionized water, oxalic acid and an alkaline solvent, are common industrial raw materials with low cost, and are mainly subjected to ball milling and heat treatment, so that the method is easy to realize in industrial production, and has good industrial potential.
Detailed Description
The first embodiment is as follows: the embodiment is a high-efficiency leaching method of a waste lithium iron phosphate anode material, which is specifically carried out according to the following steps:
carrying out heat treatment on a waste lithium iron phosphate positive electrode material in an inert atmosphere, wherein the heat treatment temperature is 600-650 ℃, the heat treatment time is 60-65 min, stripping the waste lithium iron phosphate positive electrode material from an aluminum foil (the heat treatment aims at disabling a binder and facilitating stripping), grinding to obtain waste lithium iron phosphate powder, placing the waste lithium iron phosphate powder and oxalic acid in a ball mill for ball milling, and then placing the waste lithium iron phosphate powder and the oxalic acid in deionized water for soaking for 0.5-1 h to obtain a leaching solution of lithium ions and a small amount of iron ions;
the mass ratio of the oxalic acid to the ground waste lithium iron phosphate powder is (0.5-5) to 1;
the volume ratio of the ground waste lithium iron phosphate powder to deionized water is 1g (30-35 mL).
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the grinding is done with a mortar. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the heat treatment temperature is 600 ℃, and the heat treatment time is 60 min. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the ball milling parameters are as follows: the mass ratio of the balls to the materials is 20:1, the rotating speed is 300 r/min-500 r/min, and the ball milling time is 1 h-3 h. The rest is the same as one of the first to third embodiments.
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: soaking in deionized water for 0.5 hr. The rest is the same as the fourth embodiment.
The invention was verified with the following tests:
test one: the test is a high-efficiency leaching method of a waste lithium iron phosphate anode material, and is specifically carried out according to the following steps:
carrying out heat treatment on a waste lithium iron phosphate positive electrode material in a nitrogen atmosphere, wherein the heat treatment temperature is 600 ℃, the heat treatment time is 1h, stripping the waste lithium iron phosphate positive electrode material from an aluminum foil, grinding the waste lithium iron phosphate positive electrode material by using a mortar to obtain waste lithium iron phosphate powder, placing the waste lithium iron phosphate powder and oxalic acid in a ball mill for ball milling, and then placing the waste lithium iron phosphate powder and oxalic acid in deionized water for soaking for 0.5h to obtain a leaching solution of lithium ions and a small amount of iron ions;
the mass ratio of the oxalic acid to the ground waste lithium iron phosphate powder is 1: 1;
the volume ratio of the ground waste lithium iron phosphate powder to deionized water is 1g:30 mL;
the ball milling parameters are as follows: the mass ratio of the balls to the materials is 20:1, the rotating speed is 370r/min, and the ball milling time is 1.2 h.
The test has the following beneficial effects:
1. the test adopts a mechanochemical method to ball mill the waste lithium iron phosphate anode material and the oxalic acid together, has better recovery effect on waste lithium iron phosphate batteries of different types and different states, and has no requirement on the self state of the waste lithium iron phosphate anode material;
2. the leaching rate of lithium element in the leaching solution of the test is up to 100% (in the inductively coupled plasma atomic emission spectrum test, the error of the test system is within 2%), while the leaching rate of iron element is only 12.97%, and the method reduces the amount of alkaline solvent needed by later-stage recovery of iron element;
3. in the test, the medicines used in the process of recovering the waste lithium iron phosphate material are mainly deionized water, oxalic acid and an alkaline solvent, are common industrial raw materials with low cost, and the adopted operations are mainly ball milling and heat treatment, so that the method is easy to realize in industrial production, and has good industrialization potential.
Claims (5)
1. The efficient leaching method of the waste lithium iron phosphate anode material is characterized by comprising the following steps of:
carrying out heat treatment on a waste lithium iron phosphate positive electrode material in an inert atmosphere, wherein the heat treatment temperature is 600-650 ℃, the heat treatment time is 60-65 min, stripping the waste lithium iron phosphate positive electrode material from an aluminum foil, grinding to obtain waste lithium iron phosphate powder, placing the waste lithium iron phosphate powder and oxalic acid in a ball mill for ball milling, and then placing the waste lithium iron phosphate powder and the oxalic acid in deionized water for soaking for 0.5-1 h to obtain a leaching solution of lithium ions and a small amount of iron ions;
the mass ratio of the oxalic acid to the ground waste lithium iron phosphate powder is (0.5-5) to 1;
the volume ratio of the ground waste lithium iron phosphate powder to deionized water is 1g (30-35 mL).
2. The efficient leaching method for the waste lithium iron phosphate positive electrode material as claimed in claim 1, wherein the grinding is performed by using a mortar.
3. The efficient leaching method for the waste lithium iron phosphate positive electrode material as claimed in claim 1, wherein the heat treatment temperature is 600 ℃, and the heat treatment time is 60 min.
4. The efficient leaching method for the waste lithium iron phosphate positive electrode material as claimed in claim 1, wherein the ball milling parameters are as follows: the mass ratio of the balls to the materials is 20:1, the rotating speed is 300 r/min-500 r/min, and the ball milling time is 1 h-3 h.
5. The efficient leaching method for the waste lithium iron phosphate positive electrode material as claimed in claim 1, wherein the waste lithium iron phosphate positive electrode material is soaked in deionized water for 0.5 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111454515.5A CN114196821A (en) | 2021-12-01 | 2021-12-01 | Efficient leaching method of waste lithium iron phosphate cathode material |
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| CN202111454515.5A CN114196821A (en) | 2021-12-01 | 2021-12-01 | Efficient leaching method of waste lithium iron phosphate cathode material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101708149B1 (en) * | 2016-05-20 | 2017-02-20 | (주)이엠티 | A Method For Recovering Lithium Compound From An Anode Material In Spent Lithium Batteries By Wet-Milling |
| CN109022803A (en) * | 2018-09-05 | 2018-12-18 | 合肥国轩电池材料有限公司 | The recovery method of elemental lithium during a kind of waste phosphoric acid lithium iron battery is positive |
| CN111370800A (en) * | 2020-03-03 | 2020-07-03 | 湖南雅城新材料有限公司 | Method for recovering waste lithium iron phosphate anode material |
| CN111455176A (en) * | 2020-03-05 | 2020-07-28 | 湖南雅城新材料有限公司 | Method for recovering waste lithium cobaltate positive electrode material |
-
2021
- 2021-12-01 CN CN202111454515.5A patent/CN114196821A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101708149B1 (en) * | 2016-05-20 | 2017-02-20 | (주)이엠티 | A Method For Recovering Lithium Compound From An Anode Material In Spent Lithium Batteries By Wet-Milling |
| CN109022803A (en) * | 2018-09-05 | 2018-12-18 | 合肥国轩电池材料有限公司 | The recovery method of elemental lithium during a kind of waste phosphoric acid lithium iron battery is positive |
| CN111370800A (en) * | 2020-03-03 | 2020-07-03 | 湖南雅城新材料有限公司 | Method for recovering waste lithium iron phosphate anode material |
| CN111455176A (en) * | 2020-03-05 | 2020-07-28 | 湖南雅城新材料有限公司 | Method for recovering waste lithium cobaltate positive electrode material |
Non-Patent Citations (2)
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| ERSHA FAN等: "Selective Recovery of Li and Fe from Spent Lithium-Ion Batteries by an Environmentally Friendly Mechanochemical Approach", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, pages 1 - 3 * |
| 张英杰;许斌;梁风;段建国;孟奇;郝涛;董鹏;: "废旧磷酸铁锂电池正极材料的回收研究现状", 人工晶体学报, no. 05, pages 800 - 808 * |
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