CN110343864A - The method that microwave calcining auxiliary recycles lithium and cobalt in waste and old electrode material - Google Patents
The method that microwave calcining auxiliary recycles lithium and cobalt in waste and old electrode material Download PDFInfo
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- CN110343864A CN110343864A CN201910673101.8A CN201910673101A CN110343864A CN 110343864 A CN110343864 A CN 110343864A CN 201910673101 A CN201910673101 A CN 201910673101A CN 110343864 A CN110343864 A CN 110343864A
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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
- C22B1/02—Roasting processes
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
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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
- C22B7/007—Wet processes by acid leaching
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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
Abstract
The invention discloses the methods that a kind of microwave calcining auxiliary recycles lithium and cobalt in waste and old electrode material, comprising: positive plate is obtained electrode material powdery after broken, screening by step (1)；Obtained positive electrode active materials are put into the microwave tube type oven filled with inert protective gas and roast by step (2), the solid product after collecting roasting；Step (3) mixes solid product with excessive organic acid, prepares Acid leaching liquid, recycles cobalt salt sediment；Any one of phosphoric acid, phosphate or carbonate are added into leaching liquid for step (4), recycle the sediment of lithium.The present invention restores electrode material using the form of microwave calcining in advance, binder PVDF plays the role of reducing agent wherein, optimize the acidleach characteristic of lithium and cobalt in positive electrode, reduce the energy consumption and reagent consumption of removal process, pretreating process is simplified, there are the advantages such as efficient, low energy consumption, environmental protection.
Description
Technical field
The invention belongs to waste and old lithium ion battery recycling fields, and in particular to a kind of waste and old electrode of microwave calcining auxiliary recycling
The method of lithium and cobalt in material.
Background technique
Lithium ion battery is as a kind of electric energy carrier efficiently, environmentally friendly, because its energy density is big, has extended cycle life, without note
It is widely applied in fields such as energy storage device, consumer electronics and power batteries in many advantages, such as recalling effect.As China consumes
Electronic product and new-energy automobile industry flourish, and the demand and yield of lithium ion battery are constantly soaring therewith.According to statistics,
National lithium battery yield reaches 12,100,000,000 within 2018, increases by 22.86% on a year-on-year basis.Usual lithium ion battery is after using 1-3
It is easy to appear the expansion of electric grade and the date of retirement of entering the problems such as capacitor declines, it is contemplated that before and after the year two thousand twenty, China's old and useless battery total amount
Will be up to 25,000,000,000, weight is up to 500,000 tons.So a large amount of waste and old lithium ion battery cannot such as rationalize disposition, contained by
Electrolyte and heavy metal can cause seriously to pollute to soil, atmosphere and water body.In addition, if institute in waste and old lithium ion battery can be recycled
The precious metal elements such as the lithium, the cobalt that are rich in will alleviate the pressure of China's metal resource shortage significantly.Therefore, waste and old lithium ion battery
Recycling be of great significance to Environmental Protection in China and sustainable development.
It is wet method combined that the method for current industrial recycling waste and old lithium ion battery can substantially be divided into pyrogenic process, wet process and pyrogenic process-
Technique.The application of these processes achieves preferable recovering effect, but there are still some technical problems.Firstly, electric
The elements such as cobalt, manganese in the material of pole due to valence state is high and indissoluble solution in the solution, cause wet-leaching inefficient.In addition, by
The external heated type leaching method used by conventional wet recovery process makes chemical reaction occur over just solid particles surface, causes
So that leaching reaction is obstructed, rate it is slack-off, and heat transfer difficult.And organic binder PVDF the cover table contained in electrode material
Face influences its acidleach behavior.It needs to develop a kind of waste and old lithium ion battery resource optimization recovery method efficiently, environmentally friendly.It is based on
This, proposes that the present invention is above-mentioned to solve the problems, such as.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the present invention provides a kind of microwave calcining auxiliary recycling
The method of lithium and cobalt in waste and old electrode material, compared with the preprocessing means such as traditional organic solvent dissolution and high-temperature roasting,
With advantages such as efficient, low energy consumption, environmental protection.
Technical solution: to achieve the above object, the present invention adopts the following technical scheme:
A kind of method that microwave calcining auxiliary recycles lithium and cobalt in waste and old electrode material, which is characterized in that including following step
It is rapid:
Step (1) prepares active electrode material: disassembling out anode from the waste lithium cell through overdischarge and air-dried processing
Piece is crushed, screening, obtains the positive electrode active materials of powdery；
Step (2), microwave calcining: positive electrode active materials obtained in step (1) are put into filled with inert protective gas
It is roasted in microwave tube type oven, the solid product after collecting roasting；
Step (3), prepare Acid leaching liquid, recycling cobalt salt sediment: by step (2) solid product with it is excessive organic
Acid-mixed is closed, and the Acid leaching liquid of waste and old electrode material is prepared, and cobalt element is separated in the form of complex-precipitation under excess acid effect, directly
Take back the precipitated product for receiving cobalt salt；
Step (4), the sediment for recycling lithium: it is added in the leaching liquid after taking out the precipitated product of cobalt salt into step (3)
Any one of phosphoric acid, phosphate or carbonate, lithium ion are precipitated from solution in the form precipitated, recycle sediment phosphoric acid
Lithium.Using salt, such as sodium phosphate, potassium phosphate, sodium carbonate, ammonium carbonate, solution is neutrality, environmental protection；According to phosphoric acid, after leaching
The main body of acid solution is recycled again into initial organic acid soln, recyclable to continue to use as leaching agent；.
Preferably, positive plate material is cobalt acid lithium, the positive electrode active materials of obtained powdery in the step (1)
Particle is less than 74 microns.
Preferably, the microwave reducing roasting is by organic binder in positive electrode in the step (2)
Transition metal is reduced into lower valency by PVDF, and the power of the microwave is 200W-800W, and the microwave constent temperature time is 10~
30min。
Preferably, the solid product of waste and old electrode and the solid-to-liquid ratio of organic acid are 30g/L, stirring in the step (3)
Speed is 500rpm.
Preferably, it is the benzene sulfonic acid solution of 1~2.2mol/L that the organic acid in the step (3), which takes concentration, 60
DEG C water bath with thermostatic control under stir 60min, obtain cobalt complex compound sediment and the solution containing lithium.C6H5SO3H
Preferably, the organic acid in the step (3) uses hydroxycarboxylic acid or amino carboxylic acid, hydroxycarboxylic acid such as lemon
Acid, tartaric acid or gluconic acid, aminocarboxylic acids such as ethylenediamine tetra-acetic acid (EDTA), aminotriacetic acid (NTA) or diethylidene
Pentaacetic acid.With the cobalt in solution complex reaction can occur for these types of acid, make cobalt in a manner of precipitating directly from solution
Middle precipitation.Organic acid preferred concentration is the solution of 0.4~6mol/L.
Preferably, the concentration of phosphoric acid is 1.5mol/L in the step (4).
Preferably, waste and old lithium ion battery is placed in salting liquid and discharges in the step (1), natural air drying
It carries out dismantling by hand afterwards for 24 hours and isolates positive plate and negative electrode tab, and electrode slice is crushed using Universalpulverizer.
Preferably, the inert gas in the step (2) is argon gas.
The utility model has the advantages that compared with prior art, beneficial effects of the present invention are as follows:
(1), difference of the invention is to restore electrode material in advance using the form of microwave calcining, utilizes microwave
The effect of substance is heated, provides hot conditions for reduction reaction, and will wherein using PVDF binder contained in electrode material
High valence transition metal element reduction improves its solubility in the solution to lower valency, and then optimizes the acidleach of lithium and cobalt
Characteristic simplifies pretreating process, reduces the energy consumption and reagent consumption of removal process, with traditional organic solvent dissolution and height
The preprocessing means such as temperature roasting are compared, and Microwave Pretreatment has efficient, low energy consumption, without advantages such as waste liquid generations；
(2), using the PVDF binder reducing material in positive electrode material in the present invention, one is a simplified pretreatment work
The pretreatment link of PVDF binder removing is omitted without removing binder in advance in skill；Second is that it is not necessarily to additional carbonaceous reducing agent,
The organic binder PVDF as contained by material itself is under microwave oxygen free condition to transition metal Ni, Co, Mn in electrode material
Element is restored；
(3), the present invention keeps the cobalt ions of dissolution straight by the way that excessive acid solution is added in the leaching process of waste and old electrode material
Connect the precipitation and separation in the form of complex compound, the method effectively simplifies lithium in waste and old electrode material, cobalt element separating-purifying
Process, and separative efficiency is improved, toxic gas is not generated, the main body of the acid solution after leaching is recycled again into initial organic acid
Solution can be added, continue to use as leaching agent.
Detailed description of the invention
Fig. 1 is the flow chart that a kind of microwave calcining auxiliary of the present invention recycles the method for lithium and cobalt in waste and old electrode material；
Fig. 2 is X-ray diffraction (XRD) figure of microwave reducing roasting product in the embodiment of the present invention 5.
Specific embodiment
The present invention will be further explained with reference to the accompanying drawing.
As shown in Figure 1, the present invention provides the method that a kind of microwave calcining auxiliary recycles lithium and cobalt in waste and old electrode material,
The following steps are included: positive and negative electrode electricity is isolated in dismantling by hand by waste and old lithium ion battery after overdischarge, natural air drying processing
Pole piece, metal shell and diaphragm, extracting screen underflow material after electrode slice is crushed and is sieved；By positive pole powder merging argon gas protection
In microwave tube type oven, by controlling microwave parameters, makes material reduction roasting at a certain temperature, collect product of roasting；With organic
Acid is leaching agent, is leached to the material after above-mentioned reduction treatment, and the metallic element in leaching liquid is extracted, wherein cobalt, lithium
Rate of recovery calculation formula are as follows:
In formula, maFor lithium/cobalt quality, m in purified product0For the quality of metal in electrode material original sample.
Specific embodiment is illustrated by taking following 7 embodiments as an example:
Embodiment one
By waste and old cobalt acid lithium ion battery after overdischarge, air-drying processing, positive and negative electrode electrode slice is disassembled out, by positive plate
Less than 74 microns materials are taken after broken and sieve, and are placed in the microwave tube type oven of argon gas protection, are roasted under 200W microwave power
20min is burnt, roasting solid product is collected.Reduction roasting product is mixed with 1.5mol/L benzene sulfonic acid, solid-to-liquid ratio 30g/L, constant temperature
60min is stirred under 500rpm revolving speed in water-bath, prepares the Acid leaching liquid of waste and old electrode material, cobalt element is straight in the form precipitated
Take back receipts.Phosphoric acid is added into filtered leaching liquid, lithium ion is precipitated from solution in the form precipitated, recycles the precipitating of lithium
Product.The rate of recovery of the present embodiment cobalt and lithium is respectively 90.5% and 92.8%.
Embodiment two
By waste and old cobalt acid lithium ion battery after overdischarge, air-drying processing, positive and negative electrode electrode slice is disassembled out, by positive plate
- 74 microns of materials are taken after broken and sieve, and are placed in the microwave tube type oven of argon gas protection, are roasted under 500W microwave power
20min collects roasting solid product.Reduction roasting product is mixed with 1.5mol/L benzene sulfonic acid, solid-to-liquid ratio 30g/L, thermostatted water
60min is stirred under 500rpm revolving speed in bath, prepares the Acid leaching liquid of waste and old electrode material, cobalt element is direct in the form precipitated
Recycling.Phosphoric acid is added into filtered leaching liquid, lithium ion is precipitated from solution in the form precipitated, and the precipitating for recycling lithium produces
Object.The present embodiment is that microwave power is different from the difference of the implementation condition of embodiment one, the rate of recovery difference of obtained cobalt and lithium
For 95.3% and 96.8%.
Embodiment three
By waste and old cobalt acid lithium ion battery after overdischarge, air-drying processing, positive and negative electrode electrode slice is disassembled out, by positive plate
- 74 microns of materials are taken after broken and sieve, and are placed in the microwave tube type oven of argon gas protection, are roasted under 800W microwave power
20min collects roasting solid product.Reduction roasting product is mixed with 1.5mol/L benzene sulfonic acid, solid-to-liquid ratio 30g/L, thermostatted water
60min is stirred under 500rpm revolving speed in bath, prepares the Acid leaching liquid of waste and old electrode material, cobalt element is direct in the form precipitated
Recycling.Phosphoric acid is added into filtered leaching liquid, lithium ion is precipitated from solution in the form precipitated, and the precipitating for recycling lithium produces
Object.The present embodiment is that microwave power is different from embodiment one, the difference of the implementation condition of embodiment two, time of obtained cobalt and lithium
Yield is respectively 96.4% and 97.5%.
Example IV
It is different that the present embodiment and the difference that example applies three essentially consist in the microwave constent temperature time, specific as follows:
By waste and old cobalt acid lithium ion battery after overdischarge, air-drying processing, positive and negative electrode electrode slice is disassembled out, by positive plate
In the microwave tube type oven for taking -74 microns of material merging argon gas protections after broken and sieve, roasted under 800W microwave power
10min collects roasting solid product.Reduction roasting product is mixed with 1.5mol/L benzene sulfonic acid, solid-to-liquid ratio 30g/L, thermostatted water
60min is stirred under 500rpm revolving speed in bath, prepares the Acid leaching liquid of waste and old electrode material, cobalt element is direct in the form precipitated
Recycling.Phosphoric acid is added into filtered leaching liquid, lithium ion is precipitated from solution in the form precipitated, and the precipitating for recycling lithium produces
Object.The rate of recovery of obtained cobalt and lithium is respectively 90.4% and 90.6%.
Embodiment five
It is different that this example and the difference of example three, example IV essentially consist in the additive amount of negative electrode material, specific as follows:
By waste and old cobalt acid lithium ion battery after overdischarge, air-drying processing, positive and negative electrode electrode slice is disassembled out, by positive plate
- 74 microns of materials are taken after broken and sieve, and are placed in the microwave tube type oven of argon gas protection, are roasted under 800W microwave power
30min, collects roasting solid product, and the XRD diagram of product of roasting is shown in Fig. 2.As seen from Figure 2, product of roasting is by cobalt acid lithium
It is converted into lithium carbonate, simple substance cobalt and a small amount of MnO, this part low-valent metal simple substance and oxide of generation have better than raw material
Acidleach effect.Reduction roasting product is mixed with 1.5mol/L benzene sulfonic acid, solid-to-liquid ratio 30g/L, 500rpm turns in thermostat water bath
Speed is lower to stir 60min, prepares the Acid leaching liquid of waste and old electrode material, cobalt element is directly recycled in the form precipitated.To after filtering
Leaching liquid in phosphoric acid is added, lithium ion is precipitated from solution in the form precipitated, recycles the precipitated product of lithium.Obtained cobalt and
The rate of recovery of lithium is respectively 96.8% and 98.5%.
Embodiment six
It is different that the present embodiment and the difference of example IV essentially consist in benzene sulfonic acid concentration, specific as follows:
By waste and old cobalt acid lithium ion battery after overdischarge, air-drying processing, positive and negative electrode electrode slice is disassembled out, by positive plate
- 74 microns of materials are taken after broken and sieve, and are placed in the microwave tube type oven of argon gas protection, are roasted under 800W microwave power
20min collects roasting solid product.Reduction roasting product is mixed with 2.2mol/L benzene sulfonic acid, solid-to-liquid ratio 30g/L, thermostatted water
60min is stirred under 500rpm revolving speed in bath, prepares the Acid leaching liquid of waste and old electrode material, cobalt element is direct in the form precipitated
Recycling.Phosphoric acid is added into filtered leaching liquid, lithium ion is precipitated from solution in the form precipitated, and the precipitating for recycling lithium produces
Object.The rate of recovery of obtained cobalt and lithium is respectively 93.5% and 97.7%.
Embodiment seven
It is different that the present embodiment and the difference of embodiment two essentially consist in benzene sulfonic acid concentration, specific as follows:
By waste and old cobalt acid lithium ion battery after overdischarge, air-drying processing, positive and negative electrode electrode slice is disassembled out, by positive plate
- 74 microns of materials are taken after broken and sieve, and are placed in the microwave tube type oven of argon gas protection, are roasted under 500W microwave power
10min collects roasting solid product.Reduction roasting product is mixed with 1mol/L organic acid, solid-to-liquid ratio 30g/L, water bath with thermostatic control
60min is stirred under 500rpm revolving speed in pot, prepares the Acid leaching liquid of waste and old electrode material, cobalt element is directly returned in the form precipitated
It receives.Phosphoric acid is added into filtered leaching liquid, lithium ion is precipitated from solution in the form precipitated, and the precipitating for recycling lithium produces
Object.The rate of recovery of obtained cobalt and lithium is respectively 94.3% and 95.9%.
The rate of recovery of main distinction implementation condition, obtained cobalt and lithium compares in embodiment one to seven, such as 1 institute of table
Show:
Table 1
As it can be seen from table 1 the rate of recovery of cobalt, lithium and constant temperature time, microwave power, the concentration of organic acid (benzene sulfonic acid) are equal
There are proportional relationship, signified constant temperature time refers to that system reaches the soaking time under final temperature, and temperature-rise period is actually also wanted
It is time consuming.The long purpose of calcining time is sufficiently to react PVDF with electrode material at a set temperature, makes transition metal also
It is former.By microwave calcining, product of roasting is converted into lithium carbonate, simple substance cobalt and a small amount of MnO by cobalt acid lithium, this part of generation is low
Valence metal simple-substance and oxide have better acidleach effect than raw material, therefore can obtain higher cobalt, the lithium rate of recovery.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of method that microwave calcining auxiliary recycles lithium and cobalt in waste and old electrode material, which comprises the following steps:
Step (1) prepares active electrode material: positive plate is disassembled out from the waste lithium cell through overdischarge and air-dried processing,
After broken, screening, the positive electrode active materials of powdery are obtained；
Step (2), microwave calcining: positive electrode active materials obtained in step (1) are put into the microwave filled with inert protective gas
It is roasted in tube furnace, the solid product after collecting roasting；
Step (3), prepare Acid leaching liquid, recycling cobalt salt sediment: by step (2) solid product and excessive organic acid-mixed
It closes, prepares the Acid leaching liquid of waste and old electrode material, cobalt element is separated in the form of complex-precipitation under excess acid effect, directly returned
Receive the precipitated product of cobalt salt；
Step (4), the sediment for recycling lithium: be added into the leaching liquid after the precipitated product for taking out cobalt salt in step (3) phosphoric acid,
Any one of phosphate or carbonate, lithium ion are precipitated from solution in the form precipitated, recycle sediment lithium phosphate.
2. the method that microwave calcining auxiliary according to claim 1 recycles lithium and cobalt in waste and old electrode material, feature exist
In: in the step (1), positive plate material is cobalt acid lithium, and the particle of the positive electrode active materials of obtained powdery is less than 74 microns.
3. the method that microwave calcining auxiliary according to claim 1 recycles lithium and cobalt in waste and old electrode material, feature exist
In: in the step (2), the microwave reducing roasting be by organic binder PVDF in positive electrode by transition metal also
For original at lower valency, the power of the microwave is 200W-800W, and the microwave constent temperature time is 10~30min.
4. the method that microwave calcining auxiliary according to claim 1 recycles lithium and cobalt in waste and old electrode material, feature exist
In: in the step (3), the solid product of waste and old electrode and the solid-to-liquid ratio of organic acid are 30g/L, mixing speed 500rpm.
5. the method that microwave calcining auxiliary according to claim 1 recycles lithium and cobalt in waste and old electrode material, feature exist
In: it is the benzene sulfonic acid solution of 1~2.2mol/L that the organic acid in the step (3), which takes concentration, under 60 DEG C of water bath with thermostatic control
60min is stirred, the complex compound sediment for obtaining cobalt and the solution containing lithium.
6. the method that microwave calcining auxiliary according to claim 1 recycles lithium and cobalt in waste and old electrode material, feature exist
In: the organic acid in the step (3) uses hydroxycarboxylic acid or amino carboxylic acid.
7. the method that microwave calcining auxiliary according to claim 1 recycles lithium and cobalt in waste and old electrode material, feature exist
In: the concentration of phosphoric acid is 1.5mol/L in the step (4).
8. the method that microwave calcining auxiliary according to claim 1 recycles lithium and cobalt in waste and old electrode material, feature exist
In: waste and old lithium ion battery, which is placed in salting liquid, in the step (1) discharges, and natural air drying carries out tearing open by hand for 24 hours afterwards
Solution isolates positive plate and negative electrode tab, and is crushed using Universalpulverizer to electrode slice.
9. the method that microwave calcining auxiliary according to claim 1 recycles lithium and cobalt in waste and old electrode material, feature exist
In: the inert gas in the step (2) is argon gas.
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| CN110817905A (en) * | 2019-12-11 | 2020-02-21 | 赣州有色冶金研究所 | Method for recovering lithium in ternary cathode material by microwave roasting |
| CN111430829A (en) * | 2020-03-11 | 2020-07-17 | 中南大学 | Method for recycling and regenerating waste lithium battery anode material under assistance of biomass waste |
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| CN111961860A (en) * | 2020-08-21 | 2020-11-20 | 昆明理工大学 | Method for recovering lithium ion battery by ultrasonic-microwave assistance |
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| CN112662881A (en) * | 2020-12-14 | 2021-04-16 | 徐州宇帆机电科技有限公司 | Method for preparing industrial cobalt powder by microwave reduction pyrolysis of cobalt acid lithium battery |
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