CN110029225B - Method for recycling valuable metal from waste ternary lithium ion battery anode material - Google Patents
Method for recycling valuable metal from waste ternary lithium ion battery anode material Download PDFInfo
- Publication number
- CN110029225B CN110029225B CN201910367297.8A CN201910367297A CN110029225B CN 110029225 B CN110029225 B CN 110029225B CN 201910367297 A CN201910367297 A CN 201910367297A CN 110029225 B CN110029225 B CN 110029225B
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- ternary lithium
- anode material
- waste ternary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
- C22B1/02—Roasting processes
-
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method for recovering valuable metals from a waste ternary lithium ion battery anode material comprises the steps of firstly putting raw materials into a tubular furnace with oxygen introduced for medium-temperature oxidizing roasting, controlling the roasting temperature at 700 ℃ during medium-temperature oxidizing roasting and the roasting time at 60min to obtain a roasted product, wherein the content of carbon in the roasted product is reduced by more than 98%. And dissolving the roasted product in an ammonia-ammonium salt system with the ammonia concentration of 5mol/L, putting the ammonia-ammonium salt system into an autoclave, adding hydrazine hydrate serving as a reducing agent, and reacting in the autoclave for 120 min. The method for recovering valuable metals from the waste ternary lithium ion battery anode material has the advantages of simple equipment, low investment and operation cost, easiness in popularization, remarkable reduction of process energy consumption and high recovery rate of valuable metals, and the leaching rates of Li, Ni, Co and Mn in the battery powder respectively reach 99.79%, 91.86%, 90.54% and 92.96%.
Description
Technical Field
The invention relates to fire metallurgy and hydrometallurgy processes in the field of metallurgy, in particular to a method for effectively recovering valuable metals in a waste ternary lithium ion battery anode material.
Technical Field
The lithium ion battery mainly comprises an anode, a cathode, a diaphragm, electrolyte and an outer package. The main component of the ternary lithium ion battery anode material sold on the market at present is LiNixCoyMn1-x-yO2And the batteries are usually crushed and sieved after reaching the service life, and battery powder containing nickel, cobalt, manganese and lithium and a small amount of valuable elements such as aluminum, copper and iron is obtained in the process. The metal resources contained in the lithium ion battery are rich, so that the method has important significance for recycling the resources of the waste lithium ion battery.
Currently, the mainstream method for dissolving and leaching the anode material of the waste ternary lithium ion battery is an acid leaching process. The acid leaching method generally adopts inorganic acids of HCl and HNO3、H2SO4Etc. as leaching agent and adding H2O2、Na2SO3The reducing agent directly dissolves and leaches the electrode material (in remote places, the LiNi is recovered from the waste lithium ion battery by adopting a sulfuric acid-reducing agent leaching process0.6Mn0.2Co0.2O2Rare metals and cemented carbides, 2017(6): 14-23). Although acid leaching has the advantage of high metal dissolution rate, an acid system has high corrosion to equipment, and impurity ions enter the solution to increase the subsequent removal difficulty.
Bioleaching is a new approach that some scholars propose based on environmental protection requirements. The metals are made to enter the solution in the form of ions by the oxidation of bacteria and then selectively recovered respectively. Compared with the traditional acidic leaching system, the bioleaching method has the advantages of low cost, environmental protection and the like, but the leaching rate of the main metal cobalt is relatively low, and long bioleaching time is required, so that the industrial large-scale application has certain limitation.
Some researchers have also proposed leaching of waste lithium ion battery positive electrode materials under an ammoniacal system (zheng dawn flood. basic research on recovery of power battery positive electrode waste based on selective leaching of ammonia-ammonium salt system [ D ]. beijing: university of chinese academy of sciences, 2017). However, the leaching rate of valuable metals in the ammoniacal system is low, and the leaching rate of cobalt is 80.7 percent. And the leaching time is longer.
Disclosure of Invention
In order to overcome the defects of the process for treating the anode material of the waste ternary lithium ion battery by the traditional method, the invention provides a method capable of effectively recovering valuable metals in the anode material of the waste ternary lithium ion battery. The technical scheme adopted for achieving the purpose is as follows: firstly, roasting a waste ternary lithium ion battery anode material in an oxygen atmosphere to volatilize carbon in the form of carbon dioxide; then, the obtained roasted product is subjected to pressure leaching in an ammonia-ammonium sulfate system, and a proper amount of reducing agent is added to adjust the valence state of the metal elements in the system, so that the valuable metals such as lithium, nickel, cobalt, manganese and the like contained in the roasted product are promoted to enter the solution, and the purposes of separation from impurity elements such as iron and the like and subsequent recycling of the valuable metals are achieved.
The specific technological process and technical parameters are as follows:
(1) oxidizing roasting
After the anode material of the waste ternary lithium ion battery is placed into a tube furnace, oxygen is continuously introduced into the tube furnace at the speed of 60-300 mL/min for 10-30 min at normal temperature, then a temperature controller of the tube furnace is started to heat up, the temperature is raised to 400-800 ℃, and oxidizing roasting is continuously carried out for 15-75 min, so that carbon in the anode material of the waste ternary lithium ion battery is volatilized in the form of oxides and enters a subsequent absorption bottle. And after the reaction is finished, stopping introducing oxygen and starting cooling, and obtaining a roasted product after the temperature in the furnace is reduced to the normal temperature.
(2) Pressure reduction leaching
Adding the obtained roasting product into a mixed solution of ammonia-ammonium sulfate and hydrazine hydrate according to a liquid-solid ratio (the ratio of liquid volume mL to solid weight g) of 5-10: 1, wherein the concentration of the ammonium sulfate in the mixed solution is 1-6 mol/L, the concentration of ammonia water in the mixed solution is 0.36-1.8 mol/L, the volume ratio of the hydrazine hydrate in the mixed solution is 1.6-6.4%, controlling the reaction temperature to be 100-160 ℃, reacting for 30-150 min, filtering and washing to obtain leaching slag and leaching liquid containing lithium, nickel, cobalt, manganese, iron, aluminum, copper and the like
The oxygen, the ammonium sulfate, the ammonia water and the hydrazine hydrate are all industrial reagents.
The invention is suitable for treating the secondary resource recovery of the anode material of the waste ternary lithium ion battery, and the valuable metal components of the invention range from (percent) Li 5.0-10.0, Ni 25.0-35.0, Co 10.0-20.0, Mn 10.0-20.0, Fe 0.1-1.0, Al 0.1-1.0, Cu 0.01-1.0 and C1.0-5.0.
Compared with the traditional technology for recovering the secondary resources of the anode material of the waste ternary lithium ion battery, the invention has the following advantages: 1. oxygen is introduced in the roasting process to oxidize and decompose organic matters in the anode material of the waste ternary lithium ion battery, so that the separation of valuable metals from carbon elements in the anode material of the waste ternary lithium ion battery is realized, and the carbon volatilization rate in the oxidizing roasting process can reach more than 98 percent; 2. the pressure reduction leaching of an ammonia-ammonium sulfate system can efficiently leach lithium, nickel, cobalt and manganese in a roasted product, and the leaching rates of the ammonia-ammonium sulfate system can respectively reach 99%, 91%, 90% and more than 91%; 3. hydrazine hydrate is used as a reducing agent, so that the reducibility is strong, and the leaching rate of valuable metals can be effectively improved; 4. compared with the traditional acid leaching and biological leaching processes, the ammonia system has strong selectivity on metal ions, and meanwhile, the corrosion of equipment is low; 5. the invention has simple process flow, low labor intensity and environmental protection.
Drawings
FIG. 1: the invention is a process flow diagram.
Detailed Description
Example 1
The anode material of the waste ternary lithium ion battery comprises the following main components in percentage by weight: li 5.20, Ni 28.83, Co 11.40, Mn 14.67, Fe 0.13, Al 0.51, Cu 0.03, C1.09; technical grade oxygen of which O2The content is more than or equal to 99.5 percent; technical grade ammonium sulfate, wherein (NH)4)2SO4The content is more than or equal to 99 percent; technical grade ammonia water, NH3·H2The content of O is 25-28%; technical grade hydrazine hydrate, wherein N2H4·H2The O content was 80%.
Weighing 10.00g of the waste ternary lithium ion battery anode material with the components, adding the waste ternary lithium ion battery anode material into a quartz crucible, placing the quartz crucible into a tubular furnace, sealing the tubular furnace and starting to introduce oxygen, controlling the flow rate of the introduced oxygen to be 300mL/min, introducing oxygen at normal temperature for 10min, starting to heat the tubular furnace to 700 ℃, reacting for 60min, cooling, stopping introducing the oxygen when the temperature in the furnace is reduced to the normal temperature, and opening the tubular furnace to obtain 9.78g of a roasted product, wherein the main components are marked as (%): li 5.31, Ni 29.47, Co 11.65, Mn 15.00, Fe 0.13, Al 0.53, Cu 0.03 and C0.01. The carbon volatilization rate was 99.10%.
And taking 5g of the obtained roasted product, adding the roasted product into a mixed solution of ammonia-ammonium sulfate and hydrazine hydrate according to a liquid-solid ratio (the ratio of liquid volume mL to solid weight g) of 8:1, wherein the concentration of the ammonium sulfate in the mixed solution is 5mol/L, the concentration of ammonia water in the mixed solution is 1.08mol/L, the volume ratio of the hydrazine hydrate in the mixed solution is 1.6%, controlling the reaction temperature to be 100 ℃, and obtaining leachate and leaching residues through filtering and washing after 120min of reaction. The obtained leaching residue is dried and then weighed to be 0.35g, and the main components of the leaching residue are calculated by weight percent (%): li 0.16, Ni 34.27, Co 15.74, Mn 15.09, Fe 1.83, Al 0.35 and Cu 0.42. The leaching rates of lithium, nickel, cobalt, manganese, iron, aluminum and copper are respectively 99.79%, 91.86%, 90.54%, 92.96%, 1.75%, 95.42% and 2.44%.
Example 2
The anode material of the waste ternary lithium ion battery comprises the following main components in percentage by weight: li 5.31, Ni 28.84, Co 11.35, Mn 14.68, Fe 0.13, Al 0.51, Cu 0.04, C1.21; technical grade oxygen of which O2The content is more than or equal to 99.5 percent; technical grade ammonium sulfate, wherein (NH)4)2SO4The content is more than or equal to 99 percent; technical grade ammonia water, NH3·H2The content of O is 25-28%; technical grade hydrazine hydrate, wherein N2H4·H2The O content was 80%.
Weighing 100.00g of the waste ternary lithium ion battery anode material with the components, adding the waste ternary lithium ion battery anode material into a quartz crucible, placing the quartz crucible into a tubular furnace, sealing the tubular furnace and starting to introduce oxygen, controlling the flow rate of the introduced oxygen to be 200mL/min, introducing oxygen at normal temperature for 25min, starting to heat the tubular furnace to 750 ℃, reacting for 50min, cooling, stopping introducing the oxygen when the temperature in the furnace is reduced to the normal temperature, and opening the tubular furnace to obtain 98.79g of a roasted product, wherein the main components are marked as (%): li 5.38, Ni 29.19, Co 11.49, Mn 14.86, Fe 0.13, Al 0.52, Cu 0.04, C0.004. The carbon volatilization rate was 98.67%.
Taking 15g of the obtained roasting product, adding the roasting product into a mixed solution of ammonia-ammonium sulfate and hydrazine hydrate according to a liquid-solid ratio (the ratio of liquid volume mL to solid weight g) of 6:1, wherein the concentration of the ammonium sulfate in the mixed solution is 4mol/L, the concentration of ammonia water in the mixed solution is 1.44mol/L, the volume ratio of the hydrazine hydrate in the mixed solution is 3.2%, controlling the reaction temperature to be 150 ℃, and filtering and washing after reacting for 90min to obtain a leaching solution and leaching residues. The obtained leaching residue is dried and then weighed to be 1.45g, and the main components of the leaching residue are calculated by weight percent (%): li 0.48, Ni 26.21, Co 10.66, Mn 12.93, Fe 1.33, Al 0.28, Cu 0.41. The leaching rates of lithium, nickel, cobalt, manganese, iron, aluminum and copper are respectively 99.14%, 91.32%, 91.03%, 91.59%, 1.34%, 94.88% and 2.39%.
Claims (3)
1. A method for recovering valuable metals from a waste ternary lithium ion battery anode material is characterized by comprising the following steps:
(1) oxidizing roasting
Carrying out oxidizing roasting on the anode material of the waste ternary lithium ion battery in an oxygen atmosphere to realize decarburization: putting the waste ternary lithium ion battery anode material into a tubular furnace, continuously introducing oxygen into the tubular furnace at the normal temperature at the speed of 60-300 mL/min for 10-30 min, then raising the temperature in the furnace to 400-800 ℃, roasting for 15-75 min, allowing carbon in the waste ternary lithium ion battery anode material to enter a subsequent absorption bottle in the form of carbon dioxide, and after the reaction is finished, closing the oxygen after the temperature in the furnace is reduced to the normal temperature to obtain a roasted product;
(2) pressure reduction leaching
Adding the obtained roasting product into a mixed solution of ammonia-ammonium sulfate and hydrazine hydrate according to a liquid-solid ratio, namely a ratio of a liquid volume mL to a solid weight g, which is 5-10: 1, wherein the concentration of the ammonium sulfate in the mixed solution is 1-6 mol/L, the concentration of ammonia water in the mixed solution is 0.36-1.80 mol/L, the volume ratio of the hydrazine hydrate in the mixed solution is 1.6-6.4%, controlling the reaction temperature to be 100-160 ℃, reacting for 30-150 min, and then filtering and washing to obtain leaching residues and a leaching solution containing lithium, nickel, cobalt, manganese, iron, aluminum and copper.
2. The method for recovering valuable metals from the anode materials of the waste ternary lithium ion batteries according to claim 1, wherein the oxygen, the ammonium sulfate, the ammonia water and the hydrazine hydrate are all industrial-grade reagents.
3. The method for recovering valuable metals from the anode materials of the waste ternary lithium ion batteries according to claim 1, characterized in that: the anode material of the waste ternary lithium ion battery comprises the following valuable metals in mass content range: li 5.0-10.0, Ni 25.0-35.0, Co 10.0-20.0, Mn 10.0-20.0, Fe 0.1-1.0, Al 0.1-1.0, Cu 0.01-1.0, C1.0-5.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910367297.8A CN110029225B (en) | 2019-05-05 | 2019-05-05 | Method for recycling valuable metal from waste ternary lithium ion battery anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910367297.8A CN110029225B (en) | 2019-05-05 | 2019-05-05 | Method for recycling valuable metal from waste ternary lithium ion battery anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110029225A CN110029225A (en) | 2019-07-19 |
| CN110029225B true CN110029225B (en) | 2021-01-19 |
Family
ID=67241223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910367297.8A Active CN110029225B (en) | 2019-05-05 | 2019-05-05 | Method for recycling valuable metal from waste ternary lithium ion battery anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110029225B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110396607A (en) * | 2019-09-03 | 2019-11-01 | 中南大学 | A kind of processing method of waste and old ternary lithium ion battery powder |
| CN110643816A (en) * | 2019-09-16 | 2020-01-03 | 浙江省冶金研究院有限公司 | Method for recovering lithium from waste ternary lithium battery |
| CN112758963A (en) * | 2020-12-30 | 2021-05-07 | 重庆大学 | Method for preparing cathode active material by recovering waste lithium battery through step-by-step roasting |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105331819A (en) * | 2015-11-09 | 2016-02-17 | 湖北大学 | Method for recycling Co3O4 from positive electrode material of waste lithium cobalt oxide battery |
| CN107230811B (en) * | 2016-03-25 | 2019-03-05 | 中国科学院过程工程研究所 | The Selectively leaching agent of metal component and recovery method in a kind of positive electrode |
| CN108011150A (en) * | 2017-12-28 | 2018-05-08 | 许昌学院 | A kind of method that lithium carbonate is produced from waste and old ternary lithium ion cell electrode powder |
-
2019
- 2019-05-05 CN CN201910367297.8A patent/CN110029225B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110029225A (en) | 2019-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11459636B2 (en) | Method and system for comprehensive recovery and utilization of copper-nickel sulfide ore | |
| CN110029225B (en) | Method for recycling valuable metal from waste ternary lithium ion battery anode material | |
| CN111118294A (en) | Method for recycling valuable metals from waste lithium ion battery materials step by step | |
| CN110828927A (en) | Method for comprehensively recovering waste lithium ion batteries | |
| CN104831065B (en) | Manganese cobalt high is than method that nickel cobalt in nickel cobalt manganese raw material with manganese separate | |
| CN113258158B (en) | Treatment method for recycling waste lithium ion batteries | |
| CN106129511A (en) | A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material | |
| CN107863583A (en) | Valuable metal Leaching Systems and leaching method in a kind of waste lithium cell | |
| CN109022793B (en) | Method for selectively leaching lithium from waste powder of cathode material containing at least one of cobalt, nickel and manganese | |
| CN112779421B (en) | Method for recycling anode material of waste lithium ion battery | |
| US20230335818A1 (en) | Method for separating and recovering valuable metals from waste ternary lithium batteries | |
| CN113415813A (en) | Method for recovering lithium nickel cobalt manganese from waste ternary battery material | |
| CN110396607A (en) | A kind of processing method of waste and old ternary lithium ion battery powder | |
| CN106048251A (en) | Technological method for cleaning and efficiently treating arsenic matte | |
| CN105567974B (en) | The metal recovery and comprehensive utilization process of heavy metal-containing waste water slag | |
| CN110029226B (en) | Method for recycling valuable metal from waste ternary lithium ion positive electrode material | |
| CN111187927A (en) | Method for selectively sulfating and recovering rare earth in neodymium iron boron waste | |
| CN113511664A (en) | Method for preparing battery-grade lithium carbonate by selectively extracting lithium from battery waste | |
| CN113430395A (en) | Method for extracting lithium from waste lithium ion battery material by using lithium ion sieve | |
| CN112322901B (en) | Method for selectively leaching rhenium from molybdenum concentrate roasting soot | |
| CN117210687A (en) | Alkaline leaching recovery method for waste oxide battery anode material | |
| CN110872648B (en) | Method for recovering valuable metals from waste ternary lithium ion battery positive electrode material | |
| CN105755283A (en) | Method for selectively leaching valuable metals in laterite-nickel ore by aid of chloride | |
| CN113793995A (en) | Method for recovering nickel, cobalt and manganese in anode material of waste ternary lithium ion battery | |
| CN112652807A (en) | Method for selectively recovering lithium in anode material of waste lithium ion battery by using Lewis acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: 1418-22 Moganshan Road, Hangzhou, Zhejiang 310011 Patentee after: ZHEJIANG METALLURGICAL RESEARCH INSTITUTE Co.,Ltd. Address before: No.18, Mushan Road, Hangzhou, Zhejiang 310011 Patentee before: ZHEJIANG METALLURGICAL RESEARCH INSTITUTE Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220111 Address after: 323300 long ban Shan District, Suichang Industrial Park, Lishui City, Zhejiang Province Patentee after: Zhejiang Weitong catalytic new materials Co.,Ltd. Address before: 1418-22 Moganshan Road, Hangzhou, Zhejiang 310011 Patentee before: Zhejiang Metallurgical Research Institute Co.,Ltd. |
|
| TR01 | Transfer of patent right |