CN106834703B - A kind of leaching method of positive electrode active material of waste lithium ion battery - Google Patents
A kind of leaching method of positive electrode active material of waste lithium ion battery Download PDFInfo
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- CN106834703B CN106834703B CN201710200216.6A CN201710200216A CN106834703B CN 106834703 B CN106834703 B CN 106834703B CN 201710200216 A CN201710200216 A CN 201710200216A CN 106834703 B CN106834703 B CN 106834703B
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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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- 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
- C22B1/10—Roasting processes in fluidised form
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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
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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
- C22B47/00—Obtaining manganese
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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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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Abstract
本发明公开了一种废旧锂离子电池正极活性材料的浸出方法，废旧锂离子电池经短路放电、拆解、粘结剂剥离、破碎筛分得电极材料粉末；将所述的电极材料粉末在二氧化硫载气氛围下焙烧得焙砂，其中，二氧化硫载气流量为30～50L/h；焙烧温度为300～450℃；将所述的焙砂分散在水中搅拌过滤得正极活性材料的水溶液。此浸出方法大大提高了反应的速率和效率，绿色无污染，工艺简单，同时大大降低了商业实际应用的成本，可大规模生产。The invention discloses a method for leaching positive electrode active materials of waste lithium ion batteries. The waste lithium ion batteries are subjected to short-circuit discharge, disassembly, binder peeling, crushing and screening to obtain electrode material powder; the electrode material powder is immersed in sulfur dioxide. The calcine is obtained by roasting in a carrier gas atmosphere, wherein the sulfur dioxide carrier gas flow is 30-50L/h; the roasting temperature is 300-450°C; the calcine is dispersed in water, stirred and filtered to obtain an aqueous solution of the positive active material. The leaching method greatly improves the reaction rate and efficiency, is green and pollution-free, has a simple process, and at the same time greatly reduces the cost of commercial practical applications, and can be produced on a large scale.
Description
Technical field
The present invention relates to a kind of leaching method of positive electrode active materials in waste and old lithium ion battery removal process, belong to lithium from
Sub- field of batteries.
Background technique
Lithium ion battery since the advent of the world, because voltage itself is high, specific capacity is high, cyclicity is good, memory-less effect, small in size
The advantages that, extensive reference has been obtained in fields such as electronic product, electric tool, energy storage device, electric vehicles, has been acknowledged as most
Promising secondary cell.Especially along with the rise in domestic electric vehicle market in recent years and increase rapidly, lithium ion battery
Monomer scale and whole dosage be all obviously improved.Meanwhile more and more performance degradations and reaching service life
Battery faces disposal difficulties.
There are also in the leaching method about active material, such as Publication No. CN103035977A in the prior art
State's patent document disclose it is a kind of from waste and old lithium ion battery recycle valuable metal method, mainly using salt water electric discharge →
Artificial dismantling → alkali leaching separation (or low-temperature bake) → reduction acidleach (sulfuric acid+hydrogen peroxide) → chemical precipitation, extracts positive electrode
In valuable metal.In this process flow, core is that the leaching process of active material, leaching process directly determine valuable
Metal recovery rate, effect also can largely influence subsequent dedoping step, and rate influences the rate of overall flow.
In addition, the Chinese patent literature of Publication No. CN103762393A discloses one kind based on waste lithium ion oxygen
The recovery technology for changing cobalt discloses a kind of technique of ammonia leaching, material and ammonium sulfate roasting after such as discharging, and crush, aoxidize, with
It sinks, filter through sour molten, filtering, fractional extraction, alkali again afterwards, calcination forms cobalt oxide.But heated easily decompose of ammonium sulfate produces when roasting
Ammonifying gas and nitrogen, make troubles to vent gas treatment；Leaching process uses dissolving with hydrochloric acid, high to equipment anticorrosion Capability Requirement, and
It is with high costs.
For another example, the Chinese patent literature of Publication No. CN104466292A discloses one kind and returns from waste and old lithium ion battery
The method for receiving cobalt lithium metal, specifically discloses and mixes the useless cobalt acid lithium powder of collection with sodium bisulfate, roasts, then again with water
The technique of leaching.But calcination set temperature is higher, brings higher energy consumption；And sodium bisulfate keeps stablizing, calcination
For the solid-solid reaction in resistance furnace, its rate is influenced.
In conclusion this field is badly in need of developing a kind of efficient, quick, inexpensive, free of contamination active material leaching method,
To establish a kind of process flow of adaptation waste and old lithium ion battery recycling heavy industrialization operation.
Summary of the invention
It is of the invention to provide in a kind of waste and old lithium ion battery removal process just to overcome the problems, such as that the prior art encounters
The leaching method of pole active material, it is intended to promote valuable metal leaching rate, and reduce production cost.
A kind of leaching method of waste lithium ion cell anode active material, waste and old lithium ion battery through short circuit dischange, tear open
Solution, binder removing, crushing and screening obtain electrode material powder；By the electrode material powder under sulfur dioxide carrier gas atmosphere
Roast to obtain calcining, wherein sulfur dioxide carrier gas flux is 30~50L/h；Maturing temperature is 300~450 DEG C；
The calcining is dispersed in water leaching, filter positive electrode active materials aqueous solution.
In the present invention, under the sulfur dioxide, electrode material powder can be made to suspend in fluidization, be dispersed in gas atmosphere
In enclosing, then gas-solid reaction is carried out under the collaboration of the carrier gas flux and maturing temperature, helps to be obviously improved electrode material
With sulfur dioxide reaction efficiency, and then it is obviously improved the leaching rate of the metallic element of electrode material.
Existing conventional method can be used in short circuit dischange process.During short circuit dischange of the present invention, it is preferable to use medium be
Carbon ground-slag end.
The carbon ground-slag end is the solid portion being separated by solid-liquid separation after calcining leaches in water.
Preferably, during short circuit dischange, by waste and old lithium ion battery in the carbon ground-slag end short circuit dischange, directly
It is lower than 1V to final voltage.
Dismantling process can be used existing conventional method, in the present invention, preferably carry out under closed subnormal ambient.
Preferably, roasting process temperature is between 350~450 DEG C.Under the preferred temperature range, be conducive into one
Step promotes leaching effect.
Still more preferably, the temperature of roasting process is 380~420 DEG C.
Under the collaboration of the flow and maturing temperature of the sulfur dioxide, preferred calcining time is 1~2h；Further
Preferably 1~1.5h.
It is roasted under the fluidising conditions, obtained calcining is placed in water leaching.
Preferably, the time leached in water is 20~60min；Preferably 20~35min.
By the Collaborative Control of the roasting condition, it can be obviously shortened extraction time, it is by the method for the invention, entire to roast
Can be controlled in burning-leaching total time 2h and within, leaching efficiency is high, and valuable element leaching rate is high.
In the present invention, existing conventional method, such as the methods of solvent, roasting is can be used in binder removing.The present invention is preferred
Using low-temperature bake method.
Further preferably, it removes in adhesive process, by the material after dismantling at air atmosphere, 350~450 DEG C of heat
Reason, removes binder.
In the present invention, a kind of leaching method of waste lithium ion cell anode active material, specifically includes the following steps:
Step a): waste and old lithium ion battery is discharged in the powder of the slag containing waste carbon, blanking voltage 1V；
Step b): battery (such as under closed subnormal ambient) is disassembled, separate housing, core, electrolyte；
Step c): by 350~450 DEG C of core roastings, crushing and screenings, electrode material powder is obtained；
Step d): electrode material powder roasts under the sulfur dioxide gas stream of 30~50L/h, and maturing temperature is 300~450
℃；Calcining time is 1~2h；
Step e): step d) product of roasting is dispersed in water, and is obtained turbid solution, filtering, is taken filtrate.
In step c), the electrode material powder includes positive electrode active materials, conductive agent and cathode graphite etc., substantially not
Containing collector, binder.
In step e), the filtrate is the sulfate liquor containing lithium ion and valuable metal ions after leaching；It can be to this
Filtrate is handled, and is separated, is purified into each valuable element；It can also recycled in its entirety directly after edulcoration purification.
The invention has the benefit that
(1) under the purging of sulfur dioxide gas, electrode material powder is made to suspend in fluidization, be dispersed in atmosphere
It is interior, cooperate the regulation of the maturing temperature, the gas/solid reaction efficiency can be promoted, shorten extraction time, improves and leach
Rate；Experiment shows that extraction time of the invention can foreshorten within 2h, and the leaching rate of metal is up to 98% or more；
(2) solid carbon slag powder discharge is used, recycles anode waste, and reduce the corrosion to battery case；
(3) using water as leaching agent, the corrosion of save the cost and reduction to equipment.
Detailed description of the invention
Fig. 1 is the process flow chart that positive electrode active materials leach in waste and old lithium ion battery removal process of the present invention.
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention, rather than protects to the claims in the present invention
The limitation of range.
Embodiment 1:
It takes waste mobile phone cobalt acid lithium battery several, puts it into the powder of the slag containing waste carbon and discharge, until voltage is lower than
It is picked up when 1V, takes remaining electrolyte away after cutting open shell, take out core.Core is tentatively broken, it is put into roaster and is heated to 400
DEG C, the binder on burning-off pole piece and most of carbon material used as anode, tail gas are absorbed with lime aqueous solution in air atmosphere.It takes out
Sintered solid mixture is sieved, and is copper foil and aluminium foil fragment, the lower predominantly positive electrode active materials containing cobalt acid lithium of sieve on sieve.
Embodiment 2:
1 gained undersized product of 20g embodiment is taken, fluidized roaster is packed into, sulfur dioxide gas is passed through with the rate of 30L/h
Body, tail gas NaHCO3Lye absorbs.After atmosphere is stablized, 300 DEG C are warming up to the rate of 10 DEG C/min, solid particle is in furnace
Interior is in suspended state, keeps the temperature 1.5h.It is taken out after being cooled to room temperature, appropriate amount of deionized water is added, persistently stirs 20min.It will stirring
Turbid solution filtering afterwards, obtains clear filtrate.After sampling is evaporated, detected through X-ray diffractometer and Atomic Emission Spectrometer AES, filtrate
Middle main component is cobaltous sulfate, lithium sulfate, and wherein cobalt element content accounts for about the 87% of former old and useless battery standard amount containing Co；In filter residue
Main component is carbon, cobalt acid lithium, and wherein cobalt element content accounts for about the 12% of former old and useless battery standard amount containing Co.
Embodiment 3:
1 gained undersized product of 20g embodiment is taken, fluidized roaster is packed into, sulfur dioxide gas is passed through with the rate of 30L/h
Body, tail gas NaHCO3Lye absorbs.After atmosphere is stablized, 350 DEG C are warming up to the rate of 10 DEG C/min, solid particle is in furnace
Interior is in suspended state, keeps the temperature 1.5h.It is taken out after being cooled to room temperature, appropriate amount of deionized water is added, persistently stirs 35min.It will stirring
Turbid solution filtering afterwards, obtains clear filtrate.After sampling is evaporated, detected through X-ray diffractometer and Atomic Emission Spectrometer AES, filtrate
Middle main component is cobaltous sulfate, lithium sulfate, and wherein cobalt element content accounts for the 98.3% of former old and useless battery standard amount containing Co；In filter residue
Main component is carbon.
Embodiment 4:
1 gained undersized product of 20g embodiment is taken, fluidized roaster is packed into, sulfur dioxide gas is passed through with the rate of 30L/h
Body, tail gas NaHCO3Lye absorbs.After atmosphere is stablized, 380 DEG C are warming up to the rate of 10 DEG C/min, solid particle is in furnace
Interior is in suspended state, keeps the temperature 2h.It is taken out after being cooled to room temperature, appropriate amount of deionized water is added, persistently stirs 60min.After stirring
Turbid solution filtering, obtain clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, in filtrate
Main component is cobaltous sulfate, lithium sulfate, and wherein cobalt element content accounts for the 98.8% of former old and useless battery standard amount containing Co；It is main in filter residue
Wanting ingredient is carbon.
Embodiment 5:
1 gained undersized product of 20g embodiment is taken, fluidized roaster is packed into, sulfur dioxide gas is passed through with the rate of 50L/h
Body, tail gas NaHCO3Lye absorbs.After atmosphere is stablized, 380 DEG C are warming up to the rate of 10 DEG C/min, solid particle is in furnace
Interior is in suspended state, keeps the temperature 1.5h.It is taken out after being cooled to room temperature, appropriate amount of deionized water is added, persistently stirs 35min.It will stirring
Turbid solution filtering afterwards, obtains clear filtrate.After sampling is evaporated, detected through X-ray diffractometer and Atomic Emission Spectrometer AES, filtrate
Middle main component is cobaltous sulfate, lithium sulfate, and wherein cobalt element content accounts for the 98.6% of former old and useless battery standard amount containing Co；In filter residue
Main component is carbon.
Embodiment 6:
1 gained undersized product of 20g embodiment is taken, fluidized roaster is packed into, sulfur dioxide gas is passed through with the rate of 50L/h
Body, tail gas NaHCO3Lye absorbs.After atmosphere is stablized, 420 DEG C are warming up to the rate of 10 DEG C/min, solid particle is in furnace
Interior is in suspended state, keeps the temperature 1h.It is taken out after being cooled to room temperature, appropriate amount of deionized water is added, persistently stirs 35min.After stirring
Turbid solution filtering, obtain clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, in filtrate
Main component is cobaltous sulfate, lithium sulfate, and wherein cobalt element content accounts for the 98.0% of former old and useless battery standard amount containing Co；It is main in filter residue
Wanting ingredient is carbon.
Embodiment 7:
1 gained undersized product of 20g embodiment is taken, fluidized roaster is packed into, sulfur dioxide gas is passed through with the rate of 50L/h
Body, tail gas NaHCO3Lye absorbs.After atmosphere is stablized, 450 DEG C are warming up to the rate of 10 DEG C/min, solid particle is in furnace
Interior is in suspended state, keeps the temperature 1h.It is taken out after being cooled to room temperature, appropriate amount of deionized water is added, persistently stirs 35min.After stirring
Turbid solution filtering, obtain clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, in filtrate
Main component is cobaltous sulfate, lithium sulfate, and wherein cobalt element content accounts for the 97.2% of former old and useless battery standard amount containing Co；It is main in filter residue
Wanting ingredient is carbon.
Embodiment 8:
It takes waste and old automobile-used ternary battery several, puts it into the powder of the slag containing waste carbon and discharge, until when voltage is lower than 1V
It picks up, takes remaining electrolyte away after cutting open shell, take out core.Core is tentatively broken, it is put into roaster and is heated to 400 DEG C,
The binder on burning-off pole piece and most of carbon material used as anode, tail gas are absorbed with lime aqueous solution in air atmosphere.It takes out and burns
Solid mixture after knot is sieved, and is copper foil and aluminium foil fragment, the lower predominantly positive electrode active materials containing valuable metal of sieve on sieve.
1 gained undersized product of 20g embodiment is taken, fluidized roaster is packed into, sulfur dioxide gas is passed through with the rate of 30L/h
Body, tail gas NaHCO3Lye absorbs.After atmosphere is stablized, 380 DEG C are warming up to the rate of 10 DEG C/min, solid particle is in furnace
Interior is in suspended state, keeps the temperature 2h.It is taken out after being cooled to room temperature, appropriate amount of deionized water is added, persistently stirs 35min.After stirring
Turbid solution filtering, obtain clear filtrate.It after sampling is evaporated, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, in filtrate
Main component is cobaltous sulfate, manganese sulfate, nickel sulfate, lithium sulfate, and wherein cobalt, manganese, nickel element total content account for former old and useless battery standard
The 98.6% of content.It is compared with embodiment 3 it is found that the method for the present invention is applicable to having for different types of waste and old lithium ion battery
Valence Elements Leaching.
Comparative example 1:
1 gained undersized product of 20g embodiment is taken, magnetic boat is packed into, sulfur dioxide gas, tail gas is slowly introducing in tube furnace
Use NaHCO3Lye absorbs.After atmosphere is stablized, 300 DEG C are warming up to the rate of 10 DEG C/min, keeps the temperature 1h.After being cooled to room temperature
It takes out, appropriate amount of deionized water is added, persistently stirs 30min.By the turbid solution filtering after stirring, clear filtrate is obtained.Sampling is steamed
It after dry, is detected through X-ray diffractometer and Atomic Emission Spectrometer AES, main component is water in filtrate；In filter residue main component be carbon,
Cobalt acid lithium.In this comparative example, though roasting under sulfur dioxide atmosphere, without the purging of sulfur dioxide atmosphere, leaching effect is very
Difference.
Comparative example 2:
1 gained undersized product of 20g embodiment is taken, fluidized roaster is packed into, sulfur dioxide gas is passed through with the rate of 20L/h
Body, tail gas NaHCO3Lye absorbs.After atmosphere is stablized, 300 DEG C are warming up to the rate of 10 DEG C/min, solid particle is in furnace
It inside slightly fluctuates, keeps the temperature 2h.It is taken out after being cooled to room temperature, appropriate amount of deionized water is added, persistently stirs 30min.After stirring
Turbid solution filtering, obtains clear filtrate.After sampling is evaporated, detected through X-ray diffractometer and Atomic Emission Spectrometer AES, it is main in filtrate
Wanting ingredient is cobaltous sulfate, lithium sulfate, and wherein cobalt element content accounts for about the 62% of former old and useless battery standard amount containing Co；It is main in filter residue
Ingredient is carbon, cobalt acid lithium, and wherein cobalt element content accounts for about the 38% of former old and useless battery standard amount containing Co.In this comparative example, dioxy
Change sulphur flow is lower, and leaching effect is undesirable.
In conclusion the present invention is using sulfating roasting and leaching method to positive electrode active materials in waste and old lithium ion battery
It is recycled, the valuable constituent rate of recovery is 98% or more, and when air quantity and temperature are under optimum condition, the rate of recovery more reaches
98.5% or more, while the rate and efficiency of reaction are substantially increased, green non-pollution, simple process reduces industrial application
Cost.
Claims (6)
1. a kind of leaching method of waste lithium ion cell anode active material, which is characterized in that waste and old lithium ion battery is through short
Road electric discharge, dismantling, binder removing, crushing and screening obtain electrode material powder；The electrode material powder is hanged in fluidization
It floats, be dispersed under sulfur dioxide carrier gas atmosphere and roast to obtain calcining, wherein sulfur dioxide carrier gas flux is 30 ~ 50L/h；Roasting temperature
Degree is 350 ~ 450 DEG C；The waste and old lithium ion battery is waste and old cobalt acid lithium battery or waste and old nickle cobalt lithium manganate battery；
The calcining is dispersed in water leaching, filter positive electrode active materials aqueous solution.
2. the leaching method of waste lithium ion cell anode active material according to claim 1, which is characterized in that roasting
Temperature is 380 ~ 420 DEG C.
3. the leaching method of waste lithium ion cell anode active material according to claim 1, which is characterized in that roasting
Time is 1 ~ 2h.
4. the leaching method of waste lithium ion cell anode active material according to claim 1, which is characterized in that water logging
The time is 20 ~ 60min out.
5. the leaching method of waste lithium ion cell anode active material according to claim 1, which is characterized in that short circuit
In discharge process, medium used is the carbon ground-slag end that calcining water-leach liquor separates admittedly.
6. the leaching method of waste lithium ion cell anode active material according to claim 5, which is characterized in that short circuit
In discharge process, by waste and old lithium ion battery in the described carbon ground-slag end short circuit dischange, until final voltage is lower than 1V.
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| CN107492691A (en) * | 2017-06-21 | 2017-12-19 | 南京万舟发机电科技有限公司 | A kind of battery anhydrous discharge method |
| CN108134154B (en) * | 2018-01-12 | 2019-12-17 | 深圳市比克电池有限公司 | Safe disassembly method for waste lithium ion battery |
| CN108220607A (en) * | 2018-02-23 | 2018-06-29 | 中国科学院过程工程研究所 | A kind of method that lithium is recycled from waste material containing lithium electrode |
| KR101897134B1 (en) * | 2018-04-09 | 2018-09-10 | 에스케이이노베이션 주식회사 | Method of regenerating lithium precursor from used lithium secondary battery |
| KR102020238B1 (en) * | 2018-04-09 | 2019-09-10 | 에스케이이노베이션 주식회사 | Method of recycling active metal of lithium secondary battery |
| CN108767354B (en) * | 2018-05-29 | 2021-02-26 | 中南大学 | Method for recovering valuable metals from waste lithium ion battery anode materials |
| CN109935922B (en) * | 2019-03-14 | 2020-11-27 | 北京矿冶科技集团有限公司 | Method for recovering valuable metals from waste lithium ion battery materials |
| CN109881013A (en) * | 2019-04-02 | 2019-06-14 | 中国恩菲工程技术有限公司 | The method of valuable metal element is recycled from waste lithium ion cell anode material |
| CN110408796B (en) * | 2019-08-05 | 2021-08-10 | 江西理工大学 | Method for efficiently and selectively extracting lithium from waste lithium batteries through flash reduction |
| KR102738346B1 (en) * | 2020-02-27 | 2024-12-03 | 에스케이이노베이션 주식회사 | Method of recycling active metal of lithium secondary battery |
| CN113540603B (en) * | 2021-06-30 | 2023-04-11 | 广东邦普循环科技有限公司 | Method for safely pyrolyzing and removing impurities from waste lithium batteries and application |
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