CN109868364A - A kind of waste lithium cell wet process line recovery method - Google Patents
A kind of waste lithium cell wet process line recovery method Download PDFInfo
- Publication number
- CN109868364A CN109868364A CN201910182214.8A CN201910182214A CN109868364A CN 109868364 A CN109868364 A CN 109868364A CN 201910182214 A CN201910182214 A CN 201910182214A CN 109868364 A CN109868364 A CN 109868364A
- Authority
- CN
- China
- Prior art keywords
- lithium
- citric acid
- added
- waste
- glucose
- 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.)
- Pending
Links
Classifications
-
- 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
-
- 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 a kind of waste lithium cell wet process line recovery methods, comprising the following steps: Step 1: useless lithium battery carries out discharge treatment, abolishes the negative copper foil piece and positive electrode of acquisition graphitiferous negative electrode material after li battery shell；Step 2: taking the graphite composite powder material after heat treatment that citric acid-D glucose leaching agent is added, the leaching of lithium ion, after process to be leached, isolated lithium-containing solution and graphite material are carried out in the cryogenic thermostat reactor with agitating device；Step 3: being activated to positive mix；Step 4: carrying out Leach reaction after the positive mix after activation is mixed with citric acid-D glucose leaching agent, nickel, cobalt, manganese, the elemental lithium being dissolved in filtrate are precipitated out, and level-one waste liquid is obtained after precipitating；The present invention effectively recycles lithium battery anode and negative electrode material simultaneously, improves recovery efficiency, environmentally friendly and at low cost using citric acid-D glucose Leaching Systems.
Description
Technical field
The present invention relates to waste lithium cell hydrometallurgic recovery production line technology field, specifically a kind of waste lithium cell wet process lines
Recovery method.
Background technique
The energy and environment are the 21 century necessary for human two great problems to be faced, and the exploitation of new energy and resource are comprehensive
Close the basis and direction that recycling is human kind sustainable development.In recent years, lithium ion battery due to light weight, it is small in size, from
The advantages such as small, memory-less effect, operating temperature range are wide, can be quickly charged and discharged, long service life, environmental protection of discharging and obtain
It is widely applied.First lithium battery is made using Li-TiS system in earliest Whittingham, realizes and is commercialized to nineteen ninety, until
The present developed for more than 40 years, had made significant headway.According to statistics, 1~October in 2017, China's lithium ion battery cumulative production was
89.9 hundred million, accumulated growth rate is up to 34.6%.In the world, application of the lithium ion battery in space power field has entered engineering
Change the application stage, some companies in the whole world and military service research and develop lithium ion battery applications in space flight, such as the U.S.
" state aviation and spaceflight management office " (NASA), Eagle-Picher Battery Company, Saft Groupe Sa of France, Japanese JAXA
Company etc..
With the extensive use of lithium ion battery, the quantity for causing old and useless battery is more and more.It is contemplated that before the year two thousand twenty
Afterwards, only pure electric vehicle (contains plug-in) the accumulative learies of passenger car and hybrid power passenger car power battery 12~17 in China
Ten thousand t.Though lithium battery is referred to as " green battery ", without containing the harmful elements such as Hg, Pb, its positive electrode, electrolyte solution
Etc. very big pollution can be caused to environment, while causing the waste of resource.Therefore, it summarizes at domestic and international waste lithium cell recycling
The state of art of reason, and the developing direction of waste and old lithium ion battery recovery process is summarized on this basis, have highly important
Realistic meaning.
The main component of lithium ion battery
Lithium ion battery main component includes shell, electrolyte, anode material, cathode material, adhesive, copper foil and aluminium foil
Deng.Wherein, Co, Li, Ni mass fraction are respectively 5%~15%, 2%~7%, 0.5%~2%, and there are also the gold such as Al, Cu, Fe
Belong to element；From the point of view of main component is worth accounting, anode material and cathode material account for about 33% and 10%, electrolyte and diaphragm
Account for about 12% and 30% respectively.The metal mainly recycled in waste and old lithium ion battery is Co and Li, is concentrated mainly on anode material
On cobalt-lithium membrane on.Especially China's cobalt resource is relatively poor, and development and utilization are more difficult, and the cobalt in lithium ion battery
Mass fraction accounts for about 15%, is 850 times of association cobalt ore or so.Currently, being answered by the lithium ion battery of positive electrode of LiCoO2
With relatively broad, wherein containing chemical substances such as cobalt acid lithium, lithium hexafluoro phosphate, organic carbonate, carbon materials, copper, aluminium, it is main
Want tenor as shown in table 1.
Waste and old lithium ion battery recovery process
It is to study more and more mature technique at present using wet processing processing waste and old lithium ion battery, it is main to undergo
3 stages: 1) waste and old lithium ion battery of recycling thoroughly discharged, simply split the pretreatment such as broken, obtained after screening
Electrode material is obtained after roasting removes organic matter after obtaining main electrode material or being crushed；2) electrode that will be obtained after pretreatment
Material dissolution is leached, and enters various metals and its compound in leachate in the form of ion；3) valuable metal in leachate
Separation and recycling, this stage is the key that waste lithium cell treatment process, and for many years researchers research emphasis
With difficult point.Currently, the method for separation and recovery mainly has solvent extraction, the precipitation method, electrolysis method, ion-exchange, salting out method
Deng.
1, it pre-processes
1.1, pre-arcing
Mostly nubbin electricity in waste and old lithium ion battery, needs thoroughly to be discharged before treatment, otherwise rear
In continuous processing, remaining energy can focus on the release of a large amount of heat, be likely to result in the adverse effect such as security risk.It is waste and old
The discharge mode of lithium battery can be divided into 2 kinds, be physics electric discharge and chemistry electric discharge respectively.Wherein, physics electric discharge is put for short circuit
Electricity usually first carries out cryogenic freezing to it using freezing liquids such as liquid nitrogen, forced electric discharge of perforating afterwards.In early days, U.S. Umicore,
Toxco company carries out (- 198 DEG C) of low temperature electric discharges to waste lithium cell using liquid nitrogen, but this method is to the more demanding of equipment,
Be not suitable for large-scale industrial application；Chemistry electric discharge is discharged by way of electrolysis in conducting solution (mostly NaCl solution)
Residual amount of energy.In early days, monomer waste lithium cell is placed in the steel vessel of water and electronic conductor by pretty people in south etc. discharges,
But it can be reacted due to containing LiPF6 in the electrolyte of lithium ion battery, after being contacted with water and generate the very strong HF of toxicity, give environment
Harm is brought with operator, therefore needs to carry out alkali leaching to it immediately after discharge.In recent years, Song Xiuling etc. utilizes Vitamin C
Acidity, reproducibility and the stability of acid construct the relatively mild sulfate liquor electric discharge system of chemical property, it is determined that best
Discharging condition are as follows: concentration 2g/L, the discharge time 8h of electrolyte MnSO4 concentration 0.8mol/L, pH=2.78, ascorbic acid, most
Whole electric eliminating voltage drop meets the electric discharge requirement of green high-efficient as low as 0.54V.In contrast, chemistry electric discharge cost is lower, operation
Simply, the application of industrial-scale electric discharge, but corrosion of the electrolyte to metal shell and equipment can be met, it can be in discharge flow path
In bring adverse effect.
1.2, broken apart
Broken apart process is primarily to electrode material and other materials (organic matter etc.) are led under mechanical action
The combination of the isolation technics such as multiple stage crushing, screening is crossed, the separation and concentration of electrode material is realized, in order to later use pyrogenic process, wet process
Etc. techniques therefrom recycle valuable metal and compound.Mechanical phonograph recorder separation is currently widely used one of preprocess method, is easy to
Realize the recovery processing of waste and old lithium ion battery heavy industrialization.Shin etc. is by crushing, screening, magnetic separation, fine crushing and divides
The process of class is to reach the separation and concentration of LiCoO2.The result shows that the recycling of metal target can be improved under the conditions of preferable
Rate, but due to lithium battery structure complexity, it is difficult thoroughly to separate each component by this method；Li et al. uses a kind of novel
Mechanical separation method improves the recovery efficiency of Co while reducing energy consumption and pollution.For the electrode material split out,
10min is rinsed and stirred using ultrasonic wave in 55 DEG C of water-baths, as a result makes 92% electrode material and collector metal point
From.Meanwhile collector can be recycled in a metallic form.
1.3, it is heat-treated
The process of heat treatment is primarily to remove organic matter, the carbon dust etc. of indissoluble in waste lithium cell, and for electricity
The separation of pole material and collector.Currently used heat treatment mode is mostly high temperature normative heat treatment, but there is separation depth
It is the problems such as low, environmental pollution, in recent years, more and more to the research of high-temperature vacuum pyrolysismethod further to improve technique.Sun
Old and useless battery material is pyrolyzed in vacuum drying oven before crushing Deng the method using high-temperature vacuum pyrolysis, with 10 DEG C
Constant temperature 30min after the speed of min-1 is warming up to 600 DEG C, organic matter are decomposed in the form of small molecule liquid or gas, can be independent
Chemical raw material is used for after collection, meanwhile, after high temperature pyrolysis, LiCoO2 layers become loose and are easy to separate from aluminium foil, are conducive to
Final inorganic, metal oxide can efficiently separate enrichment；Sun Liang is electric using the method pretreatment applying waste lithium ionic of vacuum pyrolysis
Pond positive electrode.The result shows that when system pressure is lower than 1.0kPa, it is 600 DEG C of reaction temperature, organic when reaction time 30min
Binder can be substantially removed, and the most of separation that falls off from aluminium foil of positive active material, aluminium foil remains intact.Compared to
Normative heat treatment technology, high-temperature vacuum pyrolysismethod can individually recycle organic matter, improve comprehensive resource utilization rate, while can keep away
The toxic gas for exempting to generate after organic material decomposes pollutes the environment, but high, complicated for operation to its equipment requirement, industry
Change to promote and there is certain limitation.
1.4, dissolution method
Dissolution method is the principle according to " similar to mix ", miscellaneous using positive electrode and adhesive (mostly PVDF), aluminium foil etc.
The deliquescent difference of matter in organic solvent realizes separation and concentration.It often chooses in highly polar organic solvent lysis electrodes
PVDF makes positive electrode fall off from current collector aluminum foil.Liang Lijun chooses various polarity organic solvent to broken positive material
Material carries out separated and dissolved comparative experiments, and discovery optimum solvent is N-Methyl pyrrolidone (NMP), can make in optimal conditions
The mixture of active substances in cathode materials LiFePO4 and carbon is completely separated with aluminium foil；Hanisch etc. is using dissolution method to process
Electrode after heat treatment and mechanical pressure separation and screening process is thoroughly sorted.Electrode is placed in NMP at 90 DEG C
10~20min is handled, after being repeated 6 times, the binder in electrode material can be completely dissolved, and separating effect is more thorough.Dissolution
Method is easy to operate compared to other pre-treating methods, while can effectively improve separating effect and recovery rate, and industrialization is answered
It is preferable with prospect.Currently, adhesive mostly uses NMP separated and dissolved, effect is preferable, but because its price is higher, volatile, less toxic
The deficiencies of property, to limit its popularization and application industrially to a certain extent.
2, the dissolution of electrode material is leached
Dissolving leaching process is to carry out dissolution leaching to obtained electrode material after pretreatment, makes the metal in electrode material
Element is entered in solution in the form of ion, is then mainly had by the way that the recycling of various isolation technics Selective Separations is therein
Valence metal Co, Li et al..The method that dissolution is leached mainly includes Chemical Leaching and Bioleaching method.
2.1, Chemical Leaching
Traditional Chemical Leaching method is to realize that the dissolution of electrode material is leached by way of acidleach or alkali leaching, main to wrap
Include a step lixiviation process and two step lixiviation process.One step lixiviation process generallys use inorganic acid HCl, HNO3, H2SO4 etc. as leaching agent
Leaching is directly dissolved to electrode material.Two step lixiviation process are that waste lithium cell is first carried out to alkali leaching after simply pre-processing,
Enter Al in solution in the form of NaAlO2, later be added leach acid, and wherein be added reducing agent H2O2 or
As leachate, obtained leachate settles Al, Fe and is separately recovered, will be obtained Na2S2O3 by adjusting pH value, selectivity
The extraction and separation of mother liquor further progress Co, the Li element obtained.Deng carries out alkali leaching, Al using 10%NaOH solution towards brave wait
The H2SO4 and 30%H2O2 that leaching rate is 96.5%, 2mol/L carry out acidleach, and Co leaching rate is 98.8%.Leaching mechanism is such as
Under:
By leachate obtained, through techniques such as multitple extractions, the rate of recovery of final Co reaches 98% or more.This method stream
Journey is simple, easily operated, small to equipment corrosion, and pollution is few.
2.2, Bioleaching method
With the development of technology, biological metallurgy technology preferably develops because the advantages such as its high-efficiency environment friendly, at low cost have
Gesture and application prospect.Bioleaching method is the oxidation by bacterium, and metal is made to enter solution in the form of ion.Closely
Nian Lai, some researchers have studied the valuable metals leached in waste and old lithium ion battery using Bioleaching method.Mishra etc. is used
Inorganic acid and acidophil acid oxidase ferrous iron Thiobacillus leach waste lithium cell, using element S and Fe2+ as the energy,
The metabolites such as H2SO4 and Fe3+ are generated in leaching medium, utilize the gold in these metabolins dissolution waste and old lithium ion battery
Belong to.The study found that the biological dissolution speed ratio Li of Co is fast.Fe2+ can promote biological bacteria growth and breeding, in Fe3+ and residue
Metal co-precipitation.Higher liquid-solid ratio, the i.e. increase of metal concentration, can inhibit the growth of bacterium, be unfavorable for the molten of metal
Solution；Marcin á kov á etc. carries out Bioleaching to Li and Co using the consortium of acidophilic bacteria under two kinds of different mediums.It is rich in
The culture medium of nutrition all minerals needed for bacterial growth are constituted, and low nutrition culture medium is using H2SO4 and element S as energy
Source.The study found that the Bioleaching rate of Li and Co are respectively 80% and 67% in eutrophic environment；And in sub-nutrition environment
In, only dissolve the Co of 35% Li and 10.5%.Bioleaching method compared to traditional acid-reducing agent Leaching Systems, have at
Originally the advantages such as low, environmentally protective, but the leaching rate of major metal (Co, Li et al.) is relatively low, and industrialization large scale processing has
Certain limitation.
In conclusion on the one hand old and useless battery hydrometallurgic recovery technology in the prior art lacks for lithium cell cathode material
Effective recycling, on the other hand using inorganic acid pollution it is larger, using the higher cost of inorganic base.
Summary of the invention
The purpose of the present invention is to provide a kind of effectively recycling lithium cell cathode materials, are leached using citric acid systems useless
Old lithium pond wet process line recovery method, 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 waste lithium cell wet process line recovery method, comprising the following steps:
Step 1: useless lithium battery carries out discharge treatment, the cathode of acquisition graphitiferous negative electrode material after li battery shell is abolished
Copper foil and positive electrode；Removing obtains graphite composite powder material from negative copper foil piece, and positive electrode is ground into as positive powder
Material, and graphite composite powder material and positive mix are heat-treated respectively；Graphite composite powder material is placed in 500 DEG C~700 DEG C Muffles
1~2h of calcination in furnace；Positive mix is placed in calcination 0.5h in 500 DEG C~700 DEG C Muffle furnaces；
Step 2: taking the graphite composite powder material after heat treatment that citric acid-D glucose leaching agent is added, with stirring dress
The leaching that lithium ion is carried out in the cryogenic thermostat reactor set, after process to be leached, isolated lithium-containing solution and graphite
Material；Oxidant is added in batch-type while leaching lithium ion, and control mixing speed is 50-120r/min, the Portugal citric acid-D
Grape sugar leaching agent concentration is 2.5~4.0mol/L, solid-to-liquid ratio control in 1g:50ml~1g:70ml, the reaction time be 90min~
120min, temperature is 70 DEG C~90 DEG C, the volume ratio of citric acid-D glucose leaching agent and oxidant is 2:0~10:1；
Step 3: by after heat treatment positive mix and active additive agent mix in proportion after machine is carried out in ball grinder
Tool is levigate, to activate to positive mix；The active additive include ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate,
One of aminotriacetic acid is a variety of；The positive mix and the mass ratio of active additive agent are 3:1；When the activation
Between be 0.5-10h；The mechanical grinding carries out in planetary ball grinder, and the revolving speed of ball grinder is 500-3000rpm, ball material
Mass ratio is 2:10, and ball-milling medium is that zirconium oxide, agate, quartz are one such or a variety of；
Step 4: carrying out Leach reaction after the positive mix after activation is mixed with citric acid-D glucose leaching agent, make
Nickel, cobalt, manganese, the elemental lithium of anode are dissolved in citric acid-D glucose leaching agent, and after Leach reaction, filter is obtained by filtration
Liquid, the nickel being dissolved in filtrate, cobalt, manganese, elemental lithium are precipitated out, and level-one waste liquid is obtained after precipitating；The Leach reaction
Temperature, time are respectively 20-80 DEG C, 0.5-8h, it is preferred that the Leach reaction carries out under stiring, stirring rate 200-
1000rpm.After the positive mix is mixed with citric acid-D glucose leaching agent, solid-to-liquid ratio 10-50g/L；
Step 5: lithium precipitating reagent is added into lithium-containing solution, reaction obtains lithium sediment and secondary waste stream；Lithium precipitating reagent packet
Include sodium carbonate, sodium bicarbonate or sodium fluoride.
The method of the nickel, cobalt, manganese, elemental lithium that are dissolved in filtrate is precipitated in step 4 are as follows:
KMnO solution is first added to the metal oxide for obtaining manganese in filtrate, then sequentially adds dimethylglyoxime, oxalic acid
With H2PO4 solution, nickel, cobalt, lithium is precipitated successively with its precipitation form, be obtained by filtration precipitating to get；Preferably, described
KMnO, dimethylglyoxime, oxalic acid, H2PO4 solution concentration be 0.3-1mol/L.
Citric acid-D glucose the leaching agent is by citric acid and D glucose group at and the quality of citric acid, D glucose
Than for 0.05-0.5.
As a further solution of the present invention: graphite material obtained by the step 2 is used to prepare graphene film, specifically
Steps are as follows:
Step 1 takes graphite material obtained by 1g to be placed in a beaker, and acid 15mL~30mL is added, is fixed on agitating device
Cryogenic thermostat reactor in, it is lasting to stir under the conditions of 5 DEG C, oxidant 2g~3g is added in batches, the control reaction time is
30min~45min；Temperature of reaction system is risen to 35 DEG C, is diluted with deionized water, oxidant to no gas is added and generates；So
0.02mol/L lye is added afterwards, being neutralized to pH is 7, and filtering, 100-120 DEG C of drying 10-24h obtains graphite oxide；
Step 2 weighs 0.2g graphite oxide in beaker, and 1mol/L lye 5-50ml is added, and control pH is 11~13,
Processing solution 30-180min, obtains graphite oxide dispersion under 200W ultrasonic power conditions；Graphite oxide dispersion is existed
It is centrifugated 10min under the conditions of 10000rpm, obtains stablizing graphene oxide suspension, adds in graphene oxide suspension
Enter hydrazine hydrate, control hydrazine hydrate/graphene oxide suspension mass ratio is 3:4~1:2,90 DEG C of water-baths, and 50-100r/min is stirred
12h is mixed, gluey graphene suspension is obtained；Gluey graphene is obtained by filtration, 80-120 DEG C of drying obtains graphene film.
Compared with prior art, the beneficial effects of the present invention are:
One, the present invention effectively recycles lithium battery anode and negative electrode material simultaneously, improves recovery efficiency.
Two, by the way that active additive is added in positive pole powder, and using mechanical-chemical collaboration activation positive pole powder, carefully
Change particle, increases specific surface area, reduces the enhanced leaching that reaction activity is conducive to metal ion.
Three, the present invention prepares graphene using the graphite material that cathode recycles, and improves the value of recycling product.
Four, the present invention uses citric acid-D glucose Leaching Systems, and citric acid is not only environmentally friendly, but also the precipitating formed is easy to
Reduction, makes it possible to restore to utilize, avoids a large amount of consumption of leachate, improve leaching efficiency, reduce cost recovery.
Specific embodiment
The technical solution of the patent is explained in further detail With reference to embodiment.
Embodiment one
A kind of waste lithium cell wet process line recovery method, comprising the following steps:
Step 1: useless lithium battery carries out discharge treatment, the cathode of acquisition graphitiferous negative electrode material after li battery shell is abolished
Copper foil and positive electrode；Removing obtains graphite composite powder material from negative copper foil piece, and positive electrode is ground into as positive powder
Material, and graphite composite powder material and positive mix are heat-treated respectively；
Step 2: taking the graphite composite powder material after heat treatment that citric acid-D glucose leaching agent is added, with stirring dress
The leaching that lithium ion is carried out in the cryogenic thermostat reactor set, after process to be leached, isolated lithium-containing solution and graphite
Material；
Step 3: by after heat treatment positive mix and active additive agent mix in proportion after machine is carried out in ball grinder
Tool is levigate, to activate to positive mix；
Step 4: carrying out Leach reaction after the positive mix after activation is mixed with citric acid-D glucose leaching agent, make
Nickel, cobalt, manganese, the elemental lithium of anode are dissolved in citric acid-D glucose leaching agent, and after Leach reaction, filter is obtained by filtration
Liquid, the nickel being dissolved in filtrate, cobalt, manganese, elemental lithium are precipitated out, and level-one waste liquid is obtained after precipitating；
Step 5: lithium precipitating reagent is added into lithium-containing solution, reaction obtains lithium sediment and secondary waste stream；
Heat treatment in step 1 is the following steps are included: graphite composite powder material is placed in calcination in 500 DEG C~700 DEG C Muffle furnaces
1~2h；Positive mix is placed in calcination 0.5h in 500 DEG C~700 DEG C Muffle furnaces；
Oxidant is added in batch-type while leaching lithium ion in step 2, and control mixing speed is 50-120r/min,
Citric acid-D glucose leaching agent concentration is 2.5~4.0mol/L, and solid-to-liquid ratio is controlled in 1g:50ml~1g:70ml, reaction
Between be 90min~120min, temperature is 70 DEG C~90 DEG C, the volume ratio of citric acid-D glucose leaching agent and oxidant is 2:0
~10:1.
Active additive described in step 3 includes ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, in aminotriacetic acid
It is one or more；The positive mix and the mass ratio of active additive agent are 3:1；The activation time is 0.5-10h；
The mechanical grinding carries out in planetary ball grinder, and the revolving speed of ball grinder is 500-3000rpm, and ball material mass ratio is 2:10,
Ball-milling medium be zirconium oxide, agate, quartz it is one such or a variety of.
The method of the nickel, cobalt, manganese, elemental lithium that are dissolved in filtrate is precipitated in step 4 are as follows: be first added to KMnO solution
The metal oxide of manganese is obtained in filtrate, then sequentially adds dimethylglyoxime, oxalic acid and H2PO4Solution makes nickel, cobalt, lithium with it
Precipitation form is successively precipitated, be obtained by filtration precipitating to get；Preferably, the KMnO, dimethylglyoxime, oxalic acid, H2PO4Solution it is dense
Degree is 0.3-1mol/L.
The temperature of Leach reaction described in step 4, time are respectively 20-80 DEG C, 0.5-8h, it is preferred that described to leach instead
It should carry out under stiring, stirring rate 200-1000rpm.The positive mix is mixed with citric acid-D glucose leaching agent
Afterwards, solid-to-liquid ratio 10-50g/L.
Lithium precipitating reagent includes sodium carbonate, sodium bicarbonate or sodium fluoride in step 5.
The main chemical compositions and content (unit: mg/L) of each solution involved in embodiment one are as follows:
The main chemical compositions and content of each solution
| Element | Li | Mn | Co | Ni | Fe | Cu | Mg | Na |
| Lithium-containing solution | 3830 | 0 | 0 | 0 | 0 | 260 | 0 | 0 |
| Level-one waste liquid | 46 | 18 | 12 | 2 | 4 | 20 | 21 | 2 |
| Lithium-containing solution is concentrated | 4301 | 13 | 10 | 1 | 2 | 16 | 16 | 1 |
| Secondary waste stream | 11 | 13 | 10 | 1 | 2 | 16 | 16 | 1 |
As can be seen from the above table, the content of metal cation is less in the secondary waste stream obtained after final process, obtains
The higher rate of recovery, it is sufficiently effective to have recycled the valuable metals such as Li, Mn, Co, Ni.
Embodiment two
Citric acid-D glucose the leaching agent is by citric acid and D glucose group at and the quality of citric acid, D glucose
Than for 0.05-0.5.
The concentration of the citric acid-D glucose leaching agent is 0.1-10mol/L.
Embodiment three
Graphite material obtained by step 2 is used to prepare graphene film, the specific steps are as follows:
Step 1 takes graphite material obtained by 1g to be placed in a beaker, and acid 15mL~30mL is added, is fixed on agitating device
Cryogenic thermostat reactor in, it is lasting to stir under the conditions of 5 DEG C, oxidant 2g~3g is added in batches, the control reaction time is
30min~45min；Temperature of reaction system is risen to 35 DEG C, is diluted with deionized water, oxidant to no gas is added and generates；So
0.02mol/L lye is added afterwards, being neutralized to pH is 7, and filtering, 100-120 DEG C of drying 10-24h obtains graphite oxide；
Step 2 weighs 0.2g graphite oxide in beaker, and 1mol/L lye 5-50ml is added, and control pH is 11~13,
Processing solution 30-180min, obtains graphite oxide dispersion under 200W ultrasonic power conditions；Graphite oxide dispersion is existed
It is centrifugated 10min under the conditions of 10000rpm, obtains stablizing graphene oxide suspension, adds in graphene oxide suspension
Enter hydrazine hydrate, control hydrazine hydrate/graphene oxide suspension mass ratio is 3:4~1:2,90 DEG C of water-baths, and 50-100r/min is stirred
12h is mixed, gluey graphene suspension is obtained；Gluey graphene is obtained by filtration, 80-120 DEG C of drying obtains graphene film.
Example IV
A kind of waste lithium cell wet process line recovery method, comprising the following steps:
Step 1: useless lithium battery carries out discharge treatment, the cathode of acquisition graphitiferous negative electrode material after li battery shell is abolished
Copper foil and positive electrode；Removing obtains graphite composite powder material from negative copper foil piece, and positive electrode is ground into as positive powder
Material, and graphite composite powder material and positive mix are heat-treated respectively；
Step 2: taking the graphite composite powder material after heat treatment that citric acid-D glucose leaching agent is added, with stirring dress
The leaching that lithium ion is carried out in the cryogenic thermostat reactor set, after process to be leached, isolated lithium-containing solution and graphite
Material；
Step 3: by after heat treatment positive mix and active additive agent mix in proportion after machine is carried out in ball grinder
Tool is levigate, to activate to positive mix；
Step 4: carrying out Leach reaction after the positive mix after activation is mixed with citric acid-D glucose leaching agent, make
Nickel, cobalt, manganese, the elemental lithium of anode are dissolved in citric acid-D glucose leaching agent, and after Leach reaction, filter is obtained by filtration
Liquid, the nickel being dissolved in filtrate, cobalt, manganese, elemental lithium are precipitated out, and level-one waste liquid is obtained after precipitating；
Step 5: passing through respectively after lithium-containing solution obtained in level-one waste liquid obtained in step 4 and step 2 is mixed
Ultrafiltration membrane, nanofiltration membrane and reverse osmosis membrane obtain concentration lithium-containing solution (containing a small amount of other cations)；
Step 6: lithium precipitating reagent is added into lithium-containing solution, reaction obtains lithium sediment and secondary waste stream；
It is 0.1~1.5MPa that the aperture of ultrafiltration membrane, which is preferably operating pressure, in step 5, the work pressure of the nanofiltration membrane
Power is 0.1~6MPa, and monolithic membrane flow velocity is 0.1~5L/min, and working ph values are 2~10, molten containing lithium after being finally concentrated
Liquid and solution containing other cations；
The material of the nanofiltration membrane includes polyamide, polysulfones, polyvinyl alcohol, sulfonated polysulfone, sulfonated polyether sulfone, acetate fiber
Any two or more combination in element, especially preferably polyamide and polysulfone composite membrane, retaining molecular weight are 50~1000
Dalton；
The nanofiltration membrane includes board-like nanofiltration membrane or rolling nanofiltration membrane.
Embodiment five
Step 1: useless lithium battery carries out discharge treatment, the cathode of acquisition graphitiferous negative electrode material after li battery shell is abolished
Copper foil and positive electrode；Removing obtains graphite composite powder material from negative copper foil piece, and positive electrode is ground into as positive powder
Material, and graphite composite powder material and positive mix are heat-treated respectively；
Step 2: taking the graphite composite powder material after heat treatment that citric acid-D glucose leaching agent is added, with stirring dress
The leaching that lithium ion is carried out in the cryogenic thermostat reactor set, after process to be leached, isolated lithium-containing solution and graphite
Material；
Step 3: by after heat treatment positive mix and active additive agent mix in proportion after machine is carried out in ball grinder
Tool is levigate, to activate to positive mix；
Step 4: carrying out Leach reaction after the positive mix after activation is mixed with citric acid-D glucose leaching agent, make
Nickel, cobalt, manganese, the elemental lithium of anode are dissolved in citric acid-D glucose leaching agent, and after Leach reaction, filter is obtained by filtration
Liquid, the nickel being dissolved in filtrate, cobalt, manganese, elemental lithium are precipitated out, and level-one waste liquid is obtained after precipitating；
Step 5: sequentially add dimethylglyoxime, oxalic acid and H2PO4 solution into lithium-containing solution, make nickel, cobalt,
Lithium is successively precipitated with its precipitation form, and precipitating and secondary waste stream is obtained by filtration.
The preferred embodiment of the patent is described in detail above, but this patent is not limited to above-mentioned embodiment party
Formula within the knowledge of one of ordinary skill in the art can also be under the premise of not departing from this patent objective
Various changes can be made.
Claims (9)
1. a kind of waste lithium cell wet process line recovery method, which comprises the following steps:
Step 1: useless lithium battery carries out discharge treatment, the negative copper foil of acquisition graphitiferous negative electrode material after li battery shell is abolished
Piece and positive electrode；Removing obtains graphite composite powder material from negative copper foil piece, and positive electrode is ground into as positive mix, and point
It is other that graphite composite powder material and positive mix are heat-treated；
Step 2: taking the graphite composite powder material after heat treatment that citric acid-D glucose leaching agent is added, agitating device is being had
The leaching that lithium ion is carried out in cryogenic thermostat reactor, after process to be leached, isolated lithium-containing solution and graphite material；
Step 3: by after heat treatment positive mix and active additive agent mix in proportion after mechanical mill is carried out in ball grinder
Carefully, to be activated to positive mix；
Step 4: carrying out Leach reaction after the positive mix after activation is mixed with citric acid-D glucose leaching agent, make anode
Nickel, cobalt, manganese, elemental lithium be dissolved in citric acid-D glucose leaching agent, after Leach reaction, filtrate is obtained by filtration, will
Nickel, cobalt, manganese, the elemental lithium being dissolved in filtrate are precipitated out, and level-one waste liquid is obtained after precipitating；
Step 5: lithium precipitating reagent is added into lithium-containing solution, reaction obtains lithium sediment and secondary waste stream.
2. waste lithium cell wet process line recovery method according to claim 1, which is characterized in that the heat in the step 1
Processing is the following steps are included: graphite composite powder material is placed in 1~2h of calcination in 500 DEG C~700 DEG C Muffle furnaces；Positive mix is placed in
Calcination 0.5h in 500 DEG C~700 DEG C Muffle furnaces.
3. waste lithium cell wet process line recovery method according to claim 1, which is characterized in that soaked in the step 2
Oxidant is added in batch-type while lithium ion out, and control mixing speed is 50-120r/min, citric acid-D glucose leaching agent
Concentration is 2.5~4.0mol/L, and in 1g:50ml~1g:70ml, the reaction time is 90min~120min, temperature for solid-to-liquid ratio control
Volume ratio for 70 DEG C~90 DEG C, citric acid-D glucose leaching agent and oxidant is 2:0~10:1.
4. waste lithium cell wet process line recovery method according to claim 1, which is characterized in that described in the step 3
Active additive includes one of ethylenediamine tetra-acetic acid, disodium ethylene diamine tetraacetate, aminotriacetic acid or a variety of；The anode
Powder and the mass ratio of active additive agent are 3:1；The activation time is 0.5-10h；The mechanical grinding is in planetary ball
Carried out in grinding jar, the revolving speed of ball grinder is 500-3000rpm, and ball material mass ratio is 2:10, ball-milling medium be zirconium oxide, agate,
Quartz is one such or a variety of.
5. waste lithium cell wet process line recovery method according to claim 1, which is characterized in that precipitated in the step 4
The method for being dissolved in nickel in filtrate, cobalt, manganese, elemental lithium are as follows:
KMnO solution is first added to the metal oxide that manganese is obtained in filtrate, then sequentially add dimethylglyoxime, oxalic acid and
Nickel, cobalt, lithium is precipitated successively with its precipitation form in H2PO4 solution, be obtained by filtration precipitating to get.
6. waste lithium cell wet process line recovery method according to claim 1, which is characterized in that described in the step 4
The temperature of Leach reaction, time are respectively 20-80 DEG C, 0.5-8h, and the Leach reaction carries out under stiring, and stirring rate is
200-1000rpm。
7. waste lithium cell wet process line recovery method according to claim 1, which is characterized in that lithium is heavy in the step 5
Shallow lake agent includes sodium carbonate, sodium bicarbonate or sodium fluoride.
8. waste lithium cell wet process line recovery method described in -7 according to claim 1, which is characterized in that the Portugal the citric acid-D
Grape sugar leaching agent is by citric acid and D glucose group at and the mass ratio of citric acid, D glucose is 0.05-0.5.
9. waste lithium cell wet process line recovery method according to claim 1, which is characterized in that stone obtained by the step 2
Ink material is used to prepare graphene film, the specific steps are as follows:
Step 1 takes graphite material obtained by 1g to be placed in a beaker, and acid 15mL~30mL is added, is fixed on the low of agitating device
It is lasting to stir under the conditions of 5 DEG C in warm isothermal reactor, oxidant 2g~3g is added in batches, the control reaction time is 30min
~45min；Temperature of reaction system is risen to 35 DEG C, is diluted with deionized water, oxidant to no gas is added and generates；Then it is added
0.02mol/L lye, being neutralized to pH is 7, and filtering, 100-120 DEG C of drying 10-24h obtains graphite oxide；
Step 2 weighs 0.2g graphite oxide in beaker, and 1mol/L lye 5-50ml is added, and it is super for 11~13,200W to control pH
Processing solution 30-180min under the conditions of acoustical power, obtains graphite oxide dispersion；By graphite oxide dispersion in 10000rpm item
It is centrifugated 10min under part, obtains stablizing graphene oxide suspension, hydrazine hydrate is added in graphene oxide suspension, is controlled
Hydrazine hydrate processed/graphene oxide suspension mass ratio is 3:4~1:2,90 DEG C of water-baths, 50-100r/min stirring 12h, acquisition glue
Shape graphene suspension；Gluey graphene is obtained by filtration, 80-120 DEG C of drying obtains graphene film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910182214.8A CN109868364A (en) | 2019-03-12 | 2019-03-12 | A kind of waste lithium cell wet process line recovery method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910182214.8A CN109868364A (en) | 2019-03-12 | 2019-03-12 | A kind of waste lithium cell wet process line recovery method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109868364A true CN109868364A (en) | 2019-06-11 |
Family
ID=66920204
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910182214.8A Pending CN109868364A (en) | 2019-03-12 | 2019-03-12 | A kind of waste lithium cell wet process line recovery method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109868364A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110828926A (en) * | 2019-09-26 | 2020-02-21 | 北京矿冶科技集团有限公司 | Method for cooperatively recovering metal and graphite from anode and cathode materials of waste lithium ion battery |
| CN111302408A (en) * | 2020-02-21 | 2020-06-19 | 北京蒙京石墨新材料科技研究院有限公司 | Method for recycling nickel, cobalt and manganese from scrapped lithium ion battery |
| CN111484044A (en) * | 2020-04-26 | 2020-08-04 | 北京矿冶科技集团有限公司 | Method for extracting lithium in lithium battery waste at front end |
| CN111778401A (en) * | 2020-05-26 | 2020-10-16 | 常州大学 | Waste ternary power lithium ion battery green recovery method based on electrolytic sodium sulfate |
| CN111945006A (en) * | 2020-08-21 | 2020-11-17 | 昆明理工大学 | Method for separating and recovering valuable metals in lithium ion battery roasting product |
| CN112310499A (en) * | 2019-07-31 | 2021-02-02 | 中国科学院过程工程研究所 | Recovery method of waste lithium iron phosphate material and obtained recovery liquid |
| CN113054233A (en) * | 2021-03-13 | 2021-06-29 | 靖江市创力智能制造有限公司 | Configuration method of lithium battery recovery agent and lithium battery pack maintenance and matching method |
| WO2021161240A1 (en) * | 2020-02-12 | 2021-08-19 | Lohum Cleantech Private Limited | System for extracting electrode material from batteries |
| CN113517484A (en) * | 2021-03-08 | 2021-10-19 | 清华大学 | Method for treating waste lithium cobalt oxide battery and product thereof |
| CN113913612A (en) * | 2020-07-09 | 2022-01-11 | 瀜矿环保科技(上海)有限公司 | Method and system for recovering cobalt lithium battery material by gas acidification method |
| CN115109925A (en) * | 2022-06-20 | 2022-09-27 | 东北大学 | Method for treating transition metal oxide ore by citric acid system |
| CN115181866A (en) * | 2022-07-25 | 2022-10-14 | 中南大学 | Combined leaching agent and application thereof in anode leaching |
| CN115466842A (en) * | 2021-11-12 | 2022-12-13 | 金为环保科技(常州)有限公司 | Treatment method and application of waste lithium battery waste liquid |
| CN115109925B (en) * | 2022-06-20 | 2024-05-17 | 东北大学 | Method for treating transition metal oxide ore by using citric acid system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0150081A2 (en) * | 1984-01-24 | 1985-07-31 | Metallgesellschaft Ag | Process for recycling miniature batteries |
| CN102208706A (en) * | 2011-05-04 | 2011-10-05 | 合肥国轩高科动力能源有限公司 | Recycling treatment method of waste and old lithium iron phosphate battery anode materials |
| CN105355996A (en) * | 2015-10-09 | 2016-02-24 | 同济大学 | Method for separating lithium and graphite from negative electrode material of waste lithium battery and resource utilization |
| CN108913873A (en) * | 2018-07-05 | 2018-11-30 | 山东省科学院能源研究所 | A method of recycling high added value metal from waste and old nickel cobalt manganese lithium ion battery |
| CN109207725A (en) * | 2018-09-19 | 2019-01-15 | 中国科学院青海盐湖研究所 | A kind of method and system recycling lithium and manganese from waste lithium manganese oxide battery |
-
2019
- 2019-03-12 CN CN201910182214.8A patent/CN109868364A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0150081A2 (en) * | 1984-01-24 | 1985-07-31 | Metallgesellschaft Ag | Process for recycling miniature batteries |
| CN102208706A (en) * | 2011-05-04 | 2011-10-05 | 合肥国轩高科动力能源有限公司 | Recycling treatment method of waste and old lithium iron phosphate battery anode materials |
| CN105355996A (en) * | 2015-10-09 | 2016-02-24 | 同济大学 | Method for separating lithium and graphite from negative electrode material of waste lithium battery and resource utilization |
| CN108913873A (en) * | 2018-07-05 | 2018-11-30 | 山东省科学院能源研究所 | A method of recycling high added value metal from waste and old nickel cobalt manganese lithium ion battery |
| CN109207725A (en) * | 2018-09-19 | 2019-01-15 | 中国科学院青海盐湖研究所 | A kind of method and system recycling lithium and manganese from waste lithium manganese oxide battery |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112310499A (en) * | 2019-07-31 | 2021-02-02 | 中国科学院过程工程研究所 | Recovery method of waste lithium iron phosphate material and obtained recovery liquid |
| CN112310499B (en) * | 2019-07-31 | 2022-05-13 | 中国科学院过程工程研究所 | Recovery method of waste lithium iron phosphate material and obtained recovery liquid |
| CN110828926A (en) * | 2019-09-26 | 2020-02-21 | 北京矿冶科技集团有限公司 | Method for cooperatively recovering metal and graphite from anode and cathode materials of waste lithium ion battery |
| WO2021161240A1 (en) * | 2020-02-12 | 2021-08-19 | Lohum Cleantech Private Limited | System for extracting electrode material from batteries |
| CN111302408A (en) * | 2020-02-21 | 2020-06-19 | 北京蒙京石墨新材料科技研究院有限公司 | Method for recycling nickel, cobalt and manganese from scrapped lithium ion battery |
| CN111484044A (en) * | 2020-04-26 | 2020-08-04 | 北京矿冶科技集团有限公司 | Method for extracting lithium in lithium battery waste at front end |
| CN111778401B (en) * | 2020-05-26 | 2022-03-29 | 常州大学 | Waste ternary power lithium ion battery green recovery method based on electrolytic sodium sulfate |
| CN111778401A (en) * | 2020-05-26 | 2020-10-16 | 常州大学 | Waste ternary power lithium ion battery green recovery method based on electrolytic sodium sulfate |
| CN113913612A (en) * | 2020-07-09 | 2022-01-11 | 瀜矿环保科技(上海)有限公司 | Method and system for recovering cobalt lithium battery material by gas acidification method |
| CN111945006A (en) * | 2020-08-21 | 2020-11-17 | 昆明理工大学 | Method for separating and recovering valuable metals in lithium ion battery roasting product |
| CN113517484A (en) * | 2021-03-08 | 2021-10-19 | 清华大学 | Method for treating waste lithium cobalt oxide battery and product thereof |
| CN113517484B (en) * | 2021-03-08 | 2022-08-05 | 清华大学 | Method for treating waste lithium cobalt oxide battery and product thereof |
| CN113054233A (en) * | 2021-03-13 | 2021-06-29 | 靖江市创力智能制造有限公司 | Configuration method of lithium battery recovery agent and lithium battery pack maintenance and matching method |
| CN113054233B (en) * | 2021-03-13 | 2023-10-10 | 上海烯海新能源科技有限公司 | Configuration method of lithium battery restorative and maintenance and repair method of lithium battery pack |
| CN115466842A (en) * | 2021-11-12 | 2022-12-13 | 金为环保科技(常州)有限公司 | Treatment method and application of waste lithium battery waste liquid |
| CN115109925A (en) * | 2022-06-20 | 2022-09-27 | 东北大学 | Method for treating transition metal oxide ore by citric acid system |
| CN115109925B (en) * | 2022-06-20 | 2024-05-17 | 东北大学 | Method for treating transition metal oxide ore by using citric acid system |
| CN115181866A (en) * | 2022-07-25 | 2022-10-14 | 中南大学 | Combined leaching agent and application thereof in anode leaching |
| CN115181866B (en) * | 2022-07-25 | 2023-05-30 | 中南大学 | Combined leaching agent and application thereof in positive electrode leaching |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109868364A (en) | A kind of waste lithium cell wet process line recovery method | |
| CN109207730B (en) | Method and system for recovering lithium from waste lithium iron phosphate batteries | |
| CN109256597B (en) | Method and system for recovering lithium and cobalt from waste lithium cobalt oxide battery | |
| Wu et al. | Progress, Key Issues, and Future Prospects for Li‐Ion Battery Recycling | |
| CN107196004B (en) | A method of recycling valuable metal from applying waste lithium ionic power battery | |
| CN110783658B (en) | Ex-service power ternary lithium battery recovery demonstration process method | |
| CN109207725B (en) | Method and system for recovering lithium and manganese from waste lithium manganate battery | |
| CN107275700B (en) | A kind of waste and old lithium ion battery recovery and treatment method being crushed based on wet type | |
| CN111082043A (en) | Recycling method of waste nickel cobalt lithium manganate ternary battery positive electrode material | |
| CN112680598A (en) | Method for low-cost clean treatment of waste lithium ion battery anode material | |
| CN108365290A (en) | A kind of full component recycle and reuse method of waste and old new-energy automobile lithium-ion-power cell | |
| CN110724820B (en) | Method for recycling decommissioned lithium ion battery anode material by using hydrothermal method | |
| CN113415793B (en) | Method for preparing high-purity iron phosphate from lithium iron phosphate battery waste | |
| CN111455177B (en) | Method for recovering valuable metals of lithium battery positive electrode material by using saccharides and hydrogen peroxide | |
| CN110620277A (en) | Method for separating and recovering valuable metal from waste lithium ion battery anode material | |
| CN112877548B (en) | Method for recovering valuable metals from waste lithium ion battery anode powder | |
| CN109921125B (en) | Lithium battery recovery pretreatment method | |
| CN107611514B (en) | Lithium ion battery positive plate regeneration system and method thereof | |
| GB2623222A (en) | Method for extracting lithium from waste lithium battery | |
| CN114927788A (en) | Method for recovering lithium from lithium iron phosphate cathode material in mechanical acid-free high selectivity manner | |
| CN113206227B (en) | Method for preparing carbon-based metal sulfide negative electrode material by simultaneously recycling positive and negative electrode materials of waste nickel-cobalt-manganese lithium ion battery | |
| CN108251648A (en) | Nanofiltering membrane efficiently separates recovery method to metallic element in waste and old lithium ion battery | |
| CN114381601A (en) | Method for gradient separation of valuable metals in waste ternary lithium ion battery anode material | |
| CN114583303B (en) | Crushing method and system for waste lithium ion batteries | |
| CN115181866B (en) | Combined leaching agent and application thereof in positive electrode leaching |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190611 |