CN109439904A - A method of the leaching valuable metal from waste lithium cell positive electrode - Google Patents
A method of the leaching valuable metal from waste lithium cell positive electrode Download PDFInfo
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- CN109439904A CN109439904A CN201811102039.9A CN201811102039A CN109439904A CN 109439904 A CN109439904 A CN 109439904A CN 201811102039 A CN201811102039 A CN 201811102039A CN 109439904 A CN109439904 A CN 109439904A
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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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- 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
- C22B23/043—Sulfurated acids or salts thereof
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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
- 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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Abstract
The invention discloses a kind of methods of leaching valuable metal from waste lithium cell positive electrode comprising the steps of: first dries waste lithium ion cell anode material, places into and be crushed and mix in crusher, mixture crosses 200 meshes；Secondly the inorganic acid prepared and reducing agent 1 are poured into resulting material at a lower temperature；Then the reaction a period of time of reducing agent 2 is added in the system after above-mentioned steps react a period of time；To above-mentioned gained leached mud filtration washing, the valuable metal in leached mud is measured.The present invention uses inorganic acid for leaching agent, non-metallic ion compound is reducing agent, by being leached under low temperature to waste material, then reducing agent 2 is added at relatively high temperatures, has many advantages, such as simple process, at low cost to the leaching of valuable metal in lithium ion battery waste material using this method, and other metal ions are not introduced in leachate, subsequent workshop section is reduced to leachate separating-purifying operation, and industrial application metaplasia is suitble to produce.
Description
Technical field
The present invention relates to a kind of recovery method from waste lithium cell positive electrode, specially one kind from waste lithium cell just
The method of leaching valuable metal in the material of pole.
Background technique
Lithium ion battery is high and wide because having many advantages, such as big energy density, safety and good cycle, efficiency for charge-discharge
It is general apply all kinds of portable power tools, laptop, mobile phone and in terms of, especially with New energy electric vapour
The development of vehicle, power-type lithium ion battery are even more to have welcome to develop on an unprecedented scale.Positive electrode is as lithium ion battery important composition portion
Point, performance superiority and inferiority is also one of the most critical factor of decision performance of lithium ion battery superiority and inferiority, and anode material for lithium-ion batteries
Presoma performance superiority and inferiority is to determine the key factor of anode material for lithium-ion batteries performance superiority and inferiority, therefore high-performance lithium ion again
Battery presoma has been prepared into current research hot spot.
Precursor of lithium ionic cell positive material is because of the difference of raw material and preparation method, and the impurity content contained is not yet
Together, but the type that contains is almost the same, mainly has: the impurity such as Cu, Fe, Ca, Mg, Zn, Si, Na, S and all kinds of magnetisable materials,
Wherein especially based on Fe, Na, S and magnetisable material, the performance of anode material for lithium-ion batteries is even more seriously affected.Such as impurity
Fe element in Fe and magnetisable material is easy enrichment in charging and discharging lithium battery process, and fever is caused to influence the circulating battery longevity for a long time
Life.And Na+ is easy to occupy the position of Li element in positive electrode in charge and discharge process, so that capacity of lithium ion battery was decayed
Fastly.And SO4 2-It is easy to influence the main grade of positive electrode, reduces active material, eventually leading to electrification tankage reduces, simultaneously
SO4 2-Also environment can be influenced in calcination process.
With the development of lithium ion battery technology, anode material for lithium-ion batteries from cobalt acid lithium, LiMn2O4, LiFePO4,
Binary positive material develops to third generation positive electrode-ternary NCM/NCA positive electrode epoch.Especially NCM111,
The positive electrode of NCM523 mass production has the advantages such as have extended cycle life, stability is high, electric conductivity is strong.As portable storage
Can product and New-energy electric vehicle power core component and be widely applied, but be also a kind of consumables.It is expected that 2018 dynamic
Power lithium battery yield will reach 11GWh, account for 1/3 or so of entire lithium battery recovery total.And as country is to new-energy automobile
Propulsion, it is contemplated that the year two thousand twenty power lithium battery yield will reach 32.2GWh, nearly 500,000 tons, with lithium battery development scale
Rapid development, the valuable metal recovery in waste lithium cell are worth huger, the especially recycling of metallic cobalt and lithium.Positive material
The valuable metals such as nickel, cobalt, manganese and lithium in material belong to secondary resource, if waste lithium cell is mishandling, not only result in resource
Waste, serious pollution but will be generated to environment, finally be gathered in human body by prolonged biological chain enrichment, to people
Body health causes to seriously endanger.
Currently, lot of domestic and foreign researcher has carried out a large amount of research to waste lithium cell recycling, after pretreatment
To the recovery method of waste lithium cell positive electrode powder mainly have the methods of pyrogenic process, wet process and Bioleaching.But pyrogenic process
Energy consumption is high, and the Bioleaching period is too long, it is difficult to meet industrial application.Wet-leaching is not only high-efficient, and treating capacity is big, and resource is returned
High income.Wet-leaching is mainly based on inorganic acid+reducing agent and ammono-system+reducing agent at present.But ammono-system leaching will cause
Ammonia and nitrogen pollution increases subsequent treatment cost.
Number of patent application CN107959080A discloses a kind of pretreatment that valuable metal is recycled from waste and old lithium electric material
Waste lithium cell material and metal oxide roasting a period of time are obtained fired slags under certain atmosphere, then again by method
Acidleach nickel, cobalt, manganese, aluminium and lithium, but the impurity that metal oxide introduces increases subsequent removal of impurities cost；CN107475538A is announced
A kind of method leached using citric acid and sodium thiosulfate to valuable metal in waste and old cobalt acid lithium, citric acid is compared to common
Inorganic acid is expensive, and reaction process is easy release SO2, the S in slag is not readily separated out, and carries out heavy cobalt with ammonium oxalate and be easy to cause
Pollution；CN106848474A discloses one kind and recycles positive electrode material precursor and carbonic acid from lithium ion battery anode material waste material
The method of lithium, but contain volatile acid in the mixed acid of method use, it be easy to cause volatile organic acids to lose；
CN106129511A discloses a kind of method that valuable metal is recycled from the waste and old lithium electric material of lithium electricity, but the method uses oxidation
The valuable metal in water logging slag is leached in ammonia leaching, be easy to cause ammonia and nitrogen pollution.
To sum up, waste lithium ion cell anode material recovery is mainly first pre-processed at present, then with acid-reduction
Two methods of agent Leaching Systems and ammonia-reducing agent Leaching Systems leach the valuable metal in waste material.Ammonia leaching and oxalic acid
Ammonia-sinking shallow lake be easy to cause ammonia and nitrogen pollution, later regulation higher cost, therefore is not suitable for contemporary industry production.And leaching process adds
Other metal ion reducing agents increase separating-purifying cost.And it is preferable to do reducing agent leaching effect using sulfide, but in slag
S (sulphur) be not readily separated out, and be possible to production SO2(sulfur dioxide) causes environmental pollution.Though therefore above a few class methods
Right leaching effect may preferably, but there are certain defects in terms of cost and environment, therefore is not suitable for industrial production.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of leaching valuable metal from waste lithium cell positive electrode, have
Simple process, it is at low cost the advantages that, and other metal ions are not introduced in leachate, reduce subsequent workshop section and leachate is separated
Operation is purified, is suitble to industrial application metaplasia to produce, to solve the problems mentioned in the above background technology.
To achieve the above object, the invention provides the following technical scheme: a kind of leach from waste lithium cell positive electrode
The method of valuable metal, comprising the following steps:
S1: waste lithium ion cell anode material is dried, and is placed into and is crushed and mixes in crusher, and mixture mistake
200 meshes；
The inorganic acid prepared and reducing agent 1: being added in the resulting material of S1 by S2 under 40-60 DEG C of lower temperature,
Reaction time is 45-90min；
S3: after S2 system reacts a period of time, addition reducing agent 2, reaction time are under 60-85 DEG C of higher temperature
30-75min filters to obtain leachate and leached mud afterwards；
S4: gained leached mud in S3 is washed with hot water, is filtered, the valuable metal content in leached mud is measured.
Wherein, waste lithium ion cell anode material described in S1 is cobalt acid lithium, LiMn2O4, lithium nickelate and nickel cobalt mangaic acid
Two or more in lithium anode material, and the waste and old positive electrode of 20-70% extracts lithium metal in advance.
Inorganic acid described in S2 is one or both of sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.Reducing agent described in S2 and S3
1 and reducing agent 2 be oxydol H2O2, vitamin C6H8O6, glucose C6H12O6, maltose C12H22O11·H2O, sulfur dioxide
SO2In any two kinds.Reducing agent 1 described in S2 and waste and old lithium ion battery amount ratio are 0.8-1.2, reducing agent 2 described in S3
It is 0.1-0.4 with waste lithium cell total mass ratio.Inorganic acid concentration described in S2 is 1.5-3.5mol/L.It is stirred described in S2 and S3
Mixing rate is 200r/min-500r/min.
Compared with prior art, the beneficial effects of the present invention are:
The present invention provides a kind of method of leaching valuable metal from waste lithium cell positive electrode, uses inorganic acid for leaching
Agent out, non-metallic ion compound are reducing agent, by using 1 system of inorganic acid-reducing agent to carry out waste material under low temperature
A period of time is leached, a certain amount of reducing agent 2 is then added into leachate at relatively high temperatures the reaction was continued a period of time, make
Has many advantages, such as simple process, at low cost to the leaching of valuable metal in lithium ion battery waste material with this method, and in leachate
Other metal ions are not introduced, reduce subsequent workshop section to leachate separating-purifying operation, industrial application metaplasia is suitble to produce.
Specific embodiment
It will be detailed below the embodiment of the present invention, however, the embodiment of the present invention is not limited thereto.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts,
It shall fall within the protection scope of the present invention.
In the embodiment of the present invention: a kind of method of leaching valuable metal from waste lithium cell positive electrode is provided, including
Following steps:
Step 1: waste lithium ion cell anode material is dried, and is placed into and is crushed and mixes in crusher, and mixture
Cross 200 meshes；Wherein, waste lithium ion cell anode material is cobalt acid lithium, LiMn2O4, lithium nickelate and nickle cobalt lithium manganate anode material
Two or more in material, and the waste and old positive electrode of 20-70% extracts lithium metal in advance；
Step 2: the inorganic acid prepared and reducing agent 1 are added in the resulting material of step 1 at a lower temperature；Its
Lower temperature is 40-60 DEG C, and inorganic acid is one or both of sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid, inorganic acid concentration 1.5-
3.5mol/L；Reducing agent 1 and waste and old lithium ion battery amount ratio are 0.8-1.2；Reaction time is 45-90min；Stirring rate is
200r/min-500r/min；
Step 3: after step 2 system reacts a period of time, reducing agent 2 is added at relatively high temperatures, when reacting one section
Between after filter to obtain leachate and leached mud；Above-mentioned reducing agent 1 and reducing agent 2 are oxydol H2O2, vitamin C6H8O6, glucose
C6H12O6, maltose C12H22O11·H2O, sulfur dioxide SO2In any two kinds；Reducing agent 2 and waste lithium cell total mass ratio
For 0.1-0.4；Higher temperature is 60-85 DEG C；Reaction time is 30-75min；Stirring rate is 200r/min-500r/min；
Step 4: gained leached mud in step 3 being washed with hot water, is filtered, to the valuable metal content in leached mud into
Row measurement.
It is preferably explained in order to further above-mentioned, following specific embodiment is also provided:
Embodiment 1:
Material composition (w/%)
Step 1: by diluting concentrated sulfuric acid to required concentration, waste material 50g after mixing is taken；
Step 2: by the H of 500ml 2.04mol/L2SO4With 70ml H2O2It is added in step 1, at 55 ± 2 DEG C,
Stirring rate 330r/min reacts 1.5h；
Step 3: adding glucose 7.0g after step 2 system reacts 1.5h, and temperature rises to 80 ± 2 DEG C, reacts 1.5h
Filtering, hot water washing afterwards；
Step 4: gained leached mud is filtered to step 3 and dries the 7.2g that weighs to obtain, and to Ni, Co, Mn and Li in leached mud
Assay obtains leaching rate, is as follows:
Leaching rate (%)
Embodiment 2:
Material composition (w/%)
Step 1: by diluting concentrated sulfuric acid to required concentration, waste material 50g after mixing is taken；
Step 2: by the H of 500ml 2.51mol/L2SO4With 60ml H2O2It is added in step 1, at 55 ± 2 DEG C,
Stirring rate 330r/min reacts 1.5h；
Step 3: adding glucose 10.0g after step 2 system reacts 1.5h, and temperature rises to 80 ± 2 DEG C, reacts 1.5h
Filtering, hot water washing afterwards；
Step 4: gained leached mud is filtered to step 3 and dries the 8.6g that weighs to obtain, and to Ni, Co, Mn and Li in leached mud
Assay content obtains leaching rate, is as follows:
Leaching rate (%)
Embodiment 3:
Material composition (w/%)
Step 1: by diluting concentrated sulfuric acid to required concentration, waste material 50g after mixing is taken；
Step 2: by the H of 500ml 3.24mol/L2SO4With 40ml H2O2It is added in step 1, at 55 ± 2 DEG C,
Stirring rate 330r/min reacts 1.5h；
Step 3: adding glucose 20.0g after step 2 system reacts 1.5h, and temperature rises to 80 ± 2 DEG C, reacts 1.5h
Filtering, hot water washing afterwards；
Step 4: gained leached mud is filtered to step 3 and dries the 5.8g that weighs to obtain, and to Ni, Co, Mn and Li in leached mud
Assay obtains leaching rate, is as follows:
Leaching rate (%)
Embodiment 4:
Material composition (w/%)
Step 1: by diluting concentrated sulfuric acid to required concentration, waste material 50g after mixing is taken；
Step 2: by the H of 500ml 2.59mol/L2SO4With 80ml H2O2It is added in step 1, at 55 ± 2 DEG C,
Stirring rate 330r/min reacts 1.5h；
Step 3: adding glucose 15.0g after step 2 system reacts 1.5h, and temperature rises to 80 ± 2 DEG C, reacts 1.5h
Filtering, hot water washing afterwards；
Step 4: gained leached mud is filtered to step 3 and dries the 6.7g that weighs to obtain, and to Ni, Co, Mn and Li in leached mud
Assay obtains leaching rate: being as follows:
Leaching rate (%)
Embodiment 5:
Material composition (w/%)
Step 1: by diluting concentrated sulfuric acid to required concentration, waste material 50g after mixing is taken；
Step 2: by the H of 500ml 1.80mol/L2SO4With 50ml H2O2It is added in step 1, at 55 ± 2 DEG C,
Stirring rate 330r/min reacts 1.5h；
Step 3: adding glucose 5.0g after step 2 system reacts 1.5h, and temperature rises to 80 ± 2 DEG C, reacts 1.5h
Filtering, hot water washing afterwards；
Step 4: gained leached mud is filtered to step 3 and dries the 5.9g that weighs to obtain, and to Ni, Co, Mn and Li in leached mud
Assay obtains leaching rate, is as follows:
Leaching rate (%)
Two sections of lixiviation process that the present invention uses it can be seen from above-described embodiment 1-5, leaching effect is good, and leaches
Journey does not introduce other impurity metal ions, and reducing agent is fully used；Secondly, with conventional acid-reducing agent system leaching side
Method is compared, and present invention process process is simple and easy, and treating capacity is flexible, low in cost, thus be more suitable for it is industrial extensive right
The leaching of waste lithium cell positive electrode；In addition, the present invention is subsequent to be not present compared with conventional ammono-system-reducing agent leaches
Ammonia nitrogen is administered, and production cost is low.
In order to further protrude innovative effect of the invention, also provide as follows with the present invention the most close to it is existing
Technical characteristic does further comparative illustration:
Documents 1: application number 201510372381.0 disclose in ferric phosphate lithium cell recycle battery-grade iron phosphate and
The method for preparing lithium iron phosphate positive material using waste lithium iron phosphate battery, it solves recycling LiFePO4 lithium-ion electric at present
The element or material purity that the method for pond anode obtains are low, can not prepare again LiFePO4 lithium ion cell positive using it
Problem.Step method: one, crushing positive plate, heat treatment；Two, acid solution dissolves；Three, add surfactant；Four, add lye, obtain
Battery-grade iron phosphate；Five, add sodium carbonate, obtain lithium carbonate；Six, ferric phosphate, lithium carbonate and the mixing of carbon source reducing agent；Seven, it calcines.Its
Secondary pollution is not caused in preparation process, realizes synthesis, high added value recycling and the utilization of waste lithium iron phosphate battery, it is real
Existing is to waste lithium iron phosphate synthetical recovery.
Compared with the invention patent, raw material of the present invention is one of cobalt acid lithium, LiMn2O4, lithium nickelate and nickle cobalt lithium manganate
Or more than one, and part waste lithium cell waste material has removed lithium, therefore there are larger differences on raw material；Secondly, documents 1
Be using a step acidleach, after surfactant is added, then adjust pH etc., removal of impurities and etc. obtain lithium carbonate and ferric phosphate, calcine
After obtain LiFePO4, technique differs larger with the invention patent；In addition, this patent raw material is part compared with documents 1
It is processed by mentioning lithium, it does not need the pre-treatment steps such as to be again heat-treated it, disassemble, be crushed, being burnt, and the present invention is special
Benefit pertains only to leach tetra- kinds of elements of Ni, Co, Mn and Li in waste material, and not subsequent to leachate how to handle is made specifically
Answer, and documents 1 be related to leach and utilize two processes, emphasis all to leachate prepare presoma and positive electrode into
Row narration.
Documents 2: application number 201310104022.8 discloses the method for nickel-cobalt-manganternary ternary anode material recycling,
It includes that removal binder step is heat-treated from cobalt nickel lithium manganate ternary material positive plate, removes cobalt nickel lithium manganate ternary material
Agent method is bonded in positive plate are as follows: by cobalt nickel lithium manganate ternary material positive plate in 400-1000 DEG C of heat treatment 0.5-5h.The hair
Bright patent is adjusted pH and removes aluminium using first being leached to waste material roasting, then using acid-reducing agent, then is carried out to leachate
Proportion obtains metal ion mixed liquor, and finally co-precipitation obtains presoma, and sintering prepares positive electrode.
Compared with the patent of invention, the innovation of the invention patent, which is in, is leached in one section of acidleach with Sulfuric-acid-hydrogen-peroxide, and two
Section acidleach is leached with sulfuric acid-starch, using hydrogen peroxide and starch reducing agent, whole process be all not introduced into other metals from
Son saves all multi-steps for subsequent impurity removal process.
Documents 3: application number 201710144074.6 discloses a kind of from waste and old nickel-cobalt-manganese ternary lithium ion battery time
It receives, the method for preparation nickel cobalt manganese aluminium quaternary positive electrode；
Documents 4: application number 201710135011.4 discloses one kind from waste and old nickel-cobalt-manganese ternary lithium ion battery
The method for recycling, preparing tertiary cathode material；
Compared with documents 3 and documents 4, present invention focuses on the leaching of valuable metal in waste material, and it is above-mentioned
Patent is that valuable metal recovery prepares positive electrode.The rarely seen report that industry at present is leached using hydrogen peroxide and starch joint
Road, and the technique hardly introduces impurity.
To sum up: present invention focuses on the leachings of nickel cobalt manganese lithium, compared with above-mentioned documents 1-4, neither before preparation
Body is driven, nor preparing positive electrode, final purpose is different.Next is not directed to white picking and precipitates, but secondary reduction
Acidleach, and two-stage leaching temperature is different, reducing agent used also do not occur in related patents simultaneously again.
In summary: the present invention provides a kind of method of leaching valuable metal from waste lithium cell positive electrode, uses
Inorganic acid is leaching agent, and non-metallic ion compound is reducing agent, by using 1 system of inorganic acid-reducing agent under low temperature
Waste material is carried out to leach a period of time, then adding a certain amount of reducing agent 2 into leachate at relatively high temperatures, the reaction was continued
For a period of time, have many advantages, such as simple process, at low cost to the leaching of valuable metal in lithium ion battery waste material using this method,
And other metal ions are not introduced in leachate, subsequent workshop section is reduced to leachate separating-purifying operation, is suitble to industrial application
Metaplasia produces.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (7)
1. a kind of method of the leaching valuable metal from waste lithium cell positive electrode, comprising the following steps:
S1: waste lithium ion cell anode material is dried, and is placed into and is crushed and mixes in crusher, and mixture crosses 200 mesh
Sieve；
The inorganic acid prepared and reducing agent 1: being added in the resulting material of S1 by S2 at a temperature of 40-60 DEG C, and the reaction time is
45-90min；
S3: after the reaction of S2 system, reducing agent 2 is added at a temperature of 60-85 DEG C, reaction time 30-75min is filtered afterwards
Leachate and leached mud；
S4: gained leached mud in S3 is washed with hot water, is filtered, the valuable metal content in leached mud is measured.
2. according to claim 1 from waste lithium cell positive electrode leaching valuable metal method, which is characterized in that S1
Described in waste lithium ion cell anode material be cobalt acid lithium, LiMn2O4, lithium nickelate and nickel-cobalt lithium manganate cathode material in two
Kind is two or more, and the waste and old positive electrode of 20-70% extracts lithium metal in advance.
3. according to claim 1 from waste lithium cell positive electrode leaching valuable metal method, which is characterized in that S2
Described in inorganic acid be one or both of sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid.
4. according to claim 1 from waste lithium cell positive electrode leaching valuable metal method, which is characterized in that S2
It is oxydol H with reducing agent 1 described in S3 and reducing agent 22O2, vitamin C6H8O6, glucose C6H12O6, maltose
C12H22O11·H2O, sulfur dioxide SO2In any two kinds.
5. according to claim 1 from waste lithium cell positive electrode leaching valuable metal method, which is characterized in that S2
Described in reducing agent 1 and waste and old lithium ion battery amount ratio be 0.8-1.2, reducing agent 2 described in S3 and waste lithium cell gross mass
Than for 0.1-0.4.
6. according to claim 1 from waste lithium cell positive electrode leaching valuable metal method, which is characterized in that S2
Described in inorganic acid concentration be 1.5-3.5mol/L.
7. according to claim 1 from waste lithium cell positive electrode leaching valuable metal method, which is characterized in that S2
It is 200r/min-500r/min with stirring rate described in S3.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110172592A (en) * | 2019-05-28 | 2019-08-27 | 上海第二工业大学 | A method of recycling β type cobalt oxalate from waste and old ternary lithium battery |
| CN110690429A (en) * | 2019-10-14 | 2020-01-14 | 王敏 | Treatment method of waste lithium iron phosphate |
| CN110791652A (en) * | 2019-10-31 | 2020-02-14 | 华中科技大学 | Method for recovering anode material of waste lithium ion battery based on mechanochemical method |
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| CN110791652A (en) * | 2019-10-31 | 2020-02-14 | 华中科技大学 | Method for recovering anode material of waste lithium ion battery based on mechanochemical method |
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| CN112310502A (en) * | 2020-11-11 | 2021-02-02 | 广西师范大学 | Method for recycling and reusing anode material of waste lithium manganate lithium ion battery |
| CN112812315A (en) * | 2020-12-01 | 2021-05-18 | 北京理工大学 | Method for preparing manganese-based MOF material based on waste lithium ion battery leachate |
| CN113025826A (en) * | 2021-03-05 | 2021-06-25 | 华东理工大学 | Method for leaching lithium, cobalt, nickel and manganese from lithium ion battery anode by using tribasic acid |
| CN113200574A (en) * | 2021-03-29 | 2021-08-03 | 中南大学 | Method for regenerating lithium-rich manganese-based positive electrode from mixed waste lithium battery |
| CN113104897A (en) * | 2021-04-12 | 2021-07-13 | 浙江天能新材料有限公司 | Method for preparing battery-grade manganese sulfate by separating nickel, cobalt, lithium and manganese from battery black powder |
| CN113224402A (en) * | 2021-05-10 | 2021-08-06 | 中南大学 | Method for efficiently and environmentally recycling waste power lithium battery cathode material based on antibiotic bacterium residues |
| CN113224402B (en) * | 2021-05-10 | 2022-07-15 | 中南大学 | Method for efficiently and environmentally recycling waste power lithium battery cathode material based on antibiotic bacterium residues |
| CN113943867A (en) * | 2021-10-22 | 2022-01-18 | 江门市恒创睿能环保科技有限公司 | Method for leaching cobalt and lithium from waste lithium cobalt oxide battery |
| CN114335781A (en) * | 2021-12-27 | 2022-04-12 | 上海电力大学 | Method for extracting precious metal from waste lithium battery |
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