CN110129571A - A method of extracting valuable metal from waste and old lithium ion battery material - Google Patents
A method of extracting valuable metal from waste and old lithium ion battery material Download PDFInfo
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- CN110129571A CN110129571A CN201910501368.9A CN201910501368A CN110129571A CN 110129571 A CN110129571 A CN 110129571A CN 201910501368 A CN201910501368 A CN 201910501368A CN 110129571 A CN110129571 A CN 110129571A
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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
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0069—Leaching or slurrying with acids or salts thereof containing halogen
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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
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
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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
- C22B23/0423—Halogenated 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 method that the present invention relates to a kind of to extract valuable metal from waste and old lithium ion battery material.Described method includes following steps: (1) mixing waste and old lithium ion battery material with leaching agent, obtain mixing material, the mixing material is heated pressurized treatments, after separation of solid and liquid, obtains leachate and a solid slag；(2) pH value of regulating step (1) described leachate, obtains secondary solid slag and scavenging solution containing lithium.The method of the invention can make the solution that enters of the selectivity of the lithium in waste and old lithium ion battery, and other metal components etc. are mainly present in the liquid after reaction in the form of solid slag.For leachate by deep impurity-removing and after being separated by solid-liquid separation, obtained rich lithium filtrate is used to prepare lithium product, and two step obtained solid slags further recycle valuable metal therein by other methods.The present invention is very good for the selective extraction effect of lithium.Meanwhile this method acid consumption is low, environmental-friendly without other additives, high financial profit.
Description
Technical field
The invention belongs to waste lithium cell recycling fields, and in particular to one kind is extracted from waste and old lithium ion battery material to be had
The method of valence metal.
Background technique
Lithium ion battery relies on the advantages such as its excellent charge-discharge performance, cycle performance and memory-less effect in recent years
It is paid close attention to, is grown rapidly both at home and abroad.In recent years, as environmental problem is increasingly severe, new-energy automobile by favor,
The yield of lithium ion battery as its major impetus source also increases year by year, becomes occupation rate of market and is only second to lead-acid battery
Secondary cell.However, there is also certain service life can generate after these lithium ion batteries reach the date of retirement for lithium ion battery
A large amount of solid waste.These discarded lithium ion batteries because containing Ni, the heavy metals such as Co, Mn, undegradable electrolyte and
There are huge hidden danger for other poisonous and harmful substances.Thus, from the point of view of environmental protection angle, recycling waste and old lithium ion battery is very
It is necessary.
The method recycled at present to waste and old lithium ion battery is broadly divided into pyrometallurgy and two kinds of hydrometallurgy.Pyrogenic process
Metallurgy has that high energy consumption, high pollution, the lithium rate of recovery are low.Hydrometallurgy then has low pollution, metal recovery rate height etc. excellent
Gesture.Hydrometallurgical general flow includes that pretreatment early period, leaching, purifying and product preparation four are carried out to waste and old lithium ion battery
A step.Wherein, it for the leaching of valuable metal in waste lithium ion cell anode waste, industrially mostly uses inorganic acid or has
Machine acid is as leaching agent, and using hydrogen peroxide or sodium sulfite as reducing agent, the consumption of process acid and reducing agent all compares
Greatly.Simultaneously as leaching process non-selectivity, valuable metal lithium therein can only be extracted in technique end, and loss is serious.
CN106878471A proposes a kind of leach by nitration mixture and recycles valuable gold in waste lithium ion cell anode material
The method of category.The method is to carry out restoring pre- leaching in mixed acid after crushing drying by lithium cobaltate cathode waste material, so
It is further continued for carrying out once leaching and secondary leaching after leached mud is carried out ball milling afterwards.The leachate of acquisition needs in advance through toning acid
The methods of it is rear recycling obtain product containing cobalt and lithium-containing solution.Saturated sodium carbonate is then added in lithium-containing solution and carries out lithium carbonate system
It is standby.The process flow is long, and each step can all cause the loss of lithium, causes the rate of recovery of final entire technique lithium low.
CN103326088A discloses a kind of comprehensive recovering process of waste and old lithium ion battery.The method to cobalt and nickel into
Effective recycling is gone.But it is not directed to the recycling of lithium, and lithium is important strategic resource, the wasting of resources resulting from is
It is huge.
CN107326181A discloses a kind of recovery method that waste and old lithium ion battery removing one step of leaching is completed.This method
Propose an a kind of method step processing waste and old lithium ion battery waste material and efficiently leach nickel cobalt manganese lithium therein, but gained
Iron in filtrate, aluminium, copper and other impurities ion concentration can make subsequent dedoping step become cumbersome close to 1g/L, increase process
The loss of middle lithium.
CN103035977A discloses a kind of method that lithium is separated and recovered from waste and old lithium ion battery.The method passes through
After traditional sulfuric acid adds hydrogen peroxide to leach, select ion exchange resin first by Li adsorbing and extracting in leachate, thus lithium during reducing
Loss.But ion exchange resin used in this method extracts Li and needs by absorption, desorption, so that technique becomes cumbersome.Together
When, the introducing of resin increases reagent dispensing and process costs.
Therefore, this field needs a kind of method that valuable metal is extracted from waste and old lithium ion battery material, the method
Simple process, valuable metal element extraction rate are higher.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide one kind extracts from waste and old lithium ion battery material
The method of valuable metal, the process flow that the method is able to solve existing recycling waste lithium ion cell anode material is long, returns
Easily there is secondary pollution in receipts process, and lithium loses serious problem, effectively improves the recovery rate of valuable metal element.
To reach this purpose, the invention provides the following technical scheme:
The method that one of the objects of the present invention is to provide a kind of to extract valuable metal from waste and old lithium ion battery material,
Described method includes following steps:
(1) waste and old lithium ion battery material is mixed with leaching agent, obtains mixing material, mixing material heating is added
Pressure processing obtains leachate and a solid slag after being separated by solid-liquid separation；
(2) pH value of regulating step (1) described leachate, obtains secondary solid slag and scavenging solution containing lithium.
The present invention regulates and controls the object phase composition in reaction solution by regulation reaction temperature and pressure, makes reaction system
In the suitable Predominance Area E-pH, and then realize the highly selective extraction of elemental lithium in waste and old lithium ion battery, and preferably press down
Make the leaching of other valuable metals.
The entrance solution that the method for the invention can make the lithium in waste and old lithium ion battery selective, and other metal groups
Divide in the liquid waited after being present in reaction in the form of solid slag, after being separated by solid-liquid separation, obtained rich lithium filtrate is used to prepare
Lithium product, solid slag further recycle valuable metal therein by other methods.The present invention imitates the selective extraction of lithium
Fruit is very good.Meanwhile this method acid consumption is low, environmental-friendly without other additives, high financial profit.
Heretofore described waste and old lithium ion battery material covering scope is wider, shows that adaptability of the present invention is extremely strong.It is described useless
Old lithium ion battery can be waste and old lithium ion battery and obtain powder through overdischarge and after being crushed；After waste and old lithium ion battery dismantling
Obtained anode waste, anode waste or positive and negative anodes mixture；It can also be the positive and negative anodes generated in lithium ion battery production process
Leftover pieces or defect ware waste material.
Preferably, the temperature of step (1) the heating pressurized treatments is 150~250 DEG C, such as 160 DEG C, 170 DEG C, 180
DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C or 240 DEG C etc..
The temperature that pressurized treatments are heated in the present invention is 150~250 DEG C, when the temperature is less than 150 DEG C, in reaction mass
Ni, the valuable metals such as Co, Mn can largely enter in solution, cause the selectivity of leaching process lithium to reduce, can also depth be made to remove
Miscellaneous process becomes complicated, so that lithium loss be caused to increase；When the temperature is greater than 250 DEG C, reaction pressure is big, to equipment requirement
Height causes process costs to rise, and operational risk increases.
Preferably, step (1) it is described heating pressurization pressure be 0.5~3Mpa, such as 0.6Mpa, 0.8Mpa, 1Mpa,
1.2Mpa, 1.5Mpa, 1.8Mpa, 2Mpa, 2.2Mpa, 2.5Mpa or 2.8Mpa etc..
Preferably, step (1) it is described heating pressurization time be 0.5~10h, such as 1h, 2h, 3h, 4h, 5h, 6h, 7h,
8h or 9h etc..
Preferably, step (1) the heating pressurized treatments are heating pressurization under agitation.
Preferably, the speed of the stirring be 100~2500rpm, such as 200rpm, 500rpm, 800rpm, 1000rpm,
1200rpm, 1500rpm, 1800rpm, 2000rpm or 2200rpm etc., preferably 400~1000rpm.
Preferably, the reactor of step (1) the heating pressurization is autoclave or water heating kettle.
Preferably, step (1) leaching agent is acid, preferably organic and or inorganic acids.
Preferably, the organic acid include in citric acid, acetic acid and aspartic acid any one or at least two group
It closes.
Preferably, the inorganic acid include in hydrochloric acid, sulfuric acid and nitric acid any one or at least two combination.
Preferably, H in step (1) described leaching agent+Molar ratio with active material in waste and old lithium ion battery material is
0.3~2:1, such as 0.5:1,0.6:1,0.8:1,1:1,1.2:1,1.4:1,1.5:1,1.6:1 or 1.8:1 etc..
H in leaching agent of the present invention+It is less than 0.3:1 with the molar ratio of active material in waste and old lithium ion battery material
When, due to H in leaching agent+The leaching rate of deficiency, lithium is low；H in the leaching agent+With active matter in waste and old lithium ion battery material
When the molar ratio of matter is greater than 2:1, due to H in leaching agent+Other excessive, in reaction mass valuable metals, with Ni2+, Co2+, Mn2 +Plasma form largely enters solution, and the selectivity of lithium reduces.
Preferably, the solid-to-liquid ratio of step (1) the waste and old lithium ion battery material and leaching agent is 10~600g/L, such as
20g/L, 50g/L, 100g/L, 150g/L, 200g/L, 250g/L, 300g/L, 350g/L, 400g/L, 450g/L, 500g/L or
550g/L etc., preferably 200~300g/L.
When the solid-to-liquid ratio of waste and old lithium ion battery material and leaching agent of the present invention is less than 10g/L, Li in leachate+It is dense
It spends low, is unfavorable for preparing lithium product；When the solid-to-liquid ratio of the waste and old lithium ion battery material and leaching agent is greater than 600g/L, reaction
It is insufficient, leaching agent H+Excessive concentration, the high requirements on the equipment, operating condition are harsh.
" solid-to-liquid ratio of waste and old lithium ion battery and leaching agent " of the present invention refers to: the quality of the waste and old lithium ion battery
The ratio between with the volume of leaching agent.
Preferably, active material includes positive active material in the waste and old lithium ion battery material.
Preferably, step (1) the waste and old lithium ion battery material include waste and old positive electrode or waste and old positive electrode and
The mixture of waste and old negative electrode material.
Preferably, the waste and old positive electrode includes any in cobalt acid lithium, nickle cobalt lithium manganate, LiMn2O4 and LiFePO4
It is a kind of or at least two combination.
Preferably, the waste and old negative electrode material include in graphite cathode, silicium cathode and silicon-carbon cathode any one or extremely
Few two kinds of combination.
Preferably, step (1) it is described be separated by solid-liquid separation include sedimentation separation, be separated by filtration and be centrifugated in any one
Or at least two combination.
Preferably, the adjusting method of step (2) described pH of leaching solution is to be adjusted using basic matterial.
Preferably, the pH value is 8~11, such as 8,9,10 or 11 etc..
It is that the rich lithium solution in order to purify leachate, after being purified is used to prepare lithium product that the present invention, which regulates and controls pH value,.Cause
Although in leaching stage there is very high lithium to leach selectivity for the present invention, still having part in leachate, other have
Valence metal or Ca, Mg and other impurities.These impurity can interfere the preparation process of lithium product.
Preferably, the basic matterial includes any one in sodium hydroxide, sodium carbonate and potassium hydroxide or at least two
The combination of kind.
It preferably, further include the process being separated by solid-liquid separation after step (2) the adjusting pH of leaching solution.
Preferably, it is described be separated by solid-liquid separation include sedimentation separation, be separated by filtration and be centrifugated in any one or at least
Two kinds of combination.
The present invention for separation of solid and liquid mode without limitation, as long as can achieve the purpose that separate liquid and solid i.e.
Can, typical but non-limiting separate mode are as follows: sedimentation separation is separated by filtration or is centrifugated.
Preferably, scavenging solution containing lithium described in step (2) can be used for extracting elemental lithium.
Preferably, the extraction process of the elemental lithium, which is included in the scavenging solution containing lithium, is added sodium carbonate.
In method of the invention, how lithium is mentioned to rich lithium filtrate and how filter residue is dried without limitation, those skilled in the art
Member can be selected according to actual needs, as long as product containing lithium can be extracted from rich lithium filtrate.For drying means,
It can be realized the purpose of filter residue and drying.
Preferably, the solid slag is for extracting other valuable metal elements in addition to lithium.
As optimal technical scheme, a kind of side extracting valuable metal from waste and old lithium ion battery material of the present invention
Method includes the following steps:
(1) waste and old lithium ion battery material is mixed with leaching agent, H in the leaching agent+With waste and old lithium ion battery material
The molar ratio of active material is 0.3~2:1 in material, the solid-to-liquid ratio of the waste and old lithium ion battery material and leaching agent is 200~
300g/L obtains mixing material, by the mixing material temperature be 150~250 DEG C, pressure be 0.5~10Mpa, stirring speed
Under conditions of degree is 400~1000rpm, 0.5~10h of pressurized treatments is heated in autoclave or water heating kettle, by being separated by solid-liquid separation
Afterwards, leachate and a solid slag are obtained；
(2) it uses the pH value of basic matterial regulating step (1) described leachate for 8~11, is separated by solid-liquid separation, obtains solid slag
With scavenging solution containing lithium；
(3) sodium carbonate is added in the scavenging solution containing lithium and extracts elemental lithium, the solid slag is for extracting in addition to lithium
Other valuable metal elements.
Compared with prior art, the present invention has following beneficial outcomes:
(1) present invention regulates and controls the object phase composition in reaction solution by regulation reaction temperature and pressure, makes to react
System is in the suitable Predominance Area E-pH, and then realizes the highly selective extraction of elemental lithium in waste and old lithium ion battery, and preferably
Ground inhibits the leaching of other valuable metals.
(2) lithium of the method property of the can choose of the invention ground in separating waste, worn lithium ion battery, obtains rich lithium solution, lithium
Separative efficiency is high, and up to 95% or more, reagent consumption is small, and process flow is simple, and does not generate secondary pollution.
(3) heretofore described waste and old lithium ion battery material covering scope is wider, shows that adaptability of the present invention is extremely strong.It is described
Waste and old lithium ion battery can be waste and old lithium ion battery and obtain powder through overdischarge and after being crushed；Waste and old lithium ion battery dismantling
Anode waste, anode waste or the positive and negative anodes mixture obtained afterwards；It can also be positive and negative to be generated in lithium ion battery production process
Pole leftover pieces or defect ware waste material, meanwhile, this method is very suitable for large scale processing waste and old lithium ion battery, either from warp
Ji angle, or be all of great significance from environmental angle.
Detailed description of the invention
Fig. 1 is the process flow chart that the specific embodiment of the invention 1 provides.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
It is a kind of from waste and old lithium ion battery material extract valuable metal method include the following steps:
(1) the 100 mesh battery powders that obtain after pretreatment will be mechanically pulverized (powder by old and useless battery positive and negative anodes, outside
The mixing such as shell are broken to be obtained, and the positive electrode is cobalt nickel lithium manganate ternary material, and negative electrode material is graphite, additionally containing just
The impurity such as the iron introduced in the aluminium and copper and shattering process that pole and negative current collector substitute into) it is added to the sulfuric acid solution of 5wt%
In, the solid-to-liquid ratio of the battery powder and sulfuric acid solution is 200g/L, obtains mixing material, is in temperature by the mixing material
180 DEG C, pressure 2Mpa, under conditions of mixing speed is 800rpm, pressurized treatments 1h is heated in autoclave, is leached
Liquid；
(2) it uses the pH value of NaOH regulating step (1) described leachate for 10, is separated by solid-liquid separation, obtain solid slag and containing lithium
Scavenging solution；
(3) sodium carbonate is added in the scavenging solution containing lithium and extracts elemental lithium, the solid slag is for extracting in addition to lithium
Other valuable metal elements.Fig. 1 is the concrete technology flow process figure of the present embodiment, and as seen in Figure 1, the present invention by locating in advance
Reason, the process for Selectively leaching (heating pressurized treatments), deep impurity-removing (adjusting pH value) and being separated by solid-liquid separation, finally obtain solid slag
With rich lithium leachate (scavenging solution containing lithium).
The leachate and lithium carbonate that the present embodiment is obtained, are tested for the property with the following method:
(1) lithium leaching rate: measuring elemental lithium content in leachate using Inductively coupled plasma optical emission spectrometer (ICP),
Elemental lithium molar content in elemental lithium molar content/waste and old lithium ion battery material in lithium leaching rate=leachate；
(2) in leachate in addition to lithium other valuable metal element total contents: use Inductively coupled plasma optical emission spectrometer
(ICP) measure leachate in addition to lithium other valuable metal constituent content (such as nickel, cobalt, manganese, aluminium, iron, the main valuable metals such as copper
Content)；
(3) lithium carbonate purity: obtained lithium carbonate product purity is tested according to GB/T 11064；
(4) lithium loss late:
Elemental lithium leaching rate obtained in the present embodiment is up to 98%, and the content of Ni, Co and Mn are respectively 0.5g/ in leachate
L, 0.05g/L and 0.01g/L, the content of Al, Fe and Cu are respectively 0.001g/L, 0.001g/L and 0.001g/L, gained carbonic acid
Lithium product purity is 99.56%, and lithium loss late is 3%.
Embodiment 2
The difference from embodiment 1 is that the concentration of step (1) described sulfuric acid solution is 7wt%.
The present embodiment is tested for the property using method same as Example 1, obtained elemental lithium leaching rate up to 98%,
The content of Ni, Co and Mn are respectively 0.7g/L, 0.3g/L and 0.01g/L in leachate, and the content of Al, Fe and Cu are respectively
0.001g/L, 0.001g/L and 0.001g/L, gained lithium carbonate product purity are 99.56%, and lithium loss late is 3%.
Embodiment 3
The difference from embodiment 1 is that step (1) are as follows: by the lithium cobaltate cathode pole piece obtained after overdischarge is disassembled in
After roasting 5h at 500 DEG C, the obtained waste and old powder separated with collector is added in the sulfuric acid solution of 5wt%, it is described useless
The solid-to-liquid ratio of old powder and sulfuric acid solution be 100g/L, obtain mixing material, by the mixing material temperature be 200 DEG C, pressure
Power is that 3Mpa heats pressurized treatments 1h in autoclave, obtain leachate under conditions of mixing speed is 600rpm.
The present embodiment is tested for the property using method same as Example 1, obtained elemental lithium leaching rate up to 98%,
Cobalt content is 0.2g/L in leachate, and gained lithium carbonate product purity is 99.56%, and lithium loss late is 3.2%.
Embodiment 4
The difference from embodiment 1 is that step (1) are as follows: the 100 mesh LiCoO that will be obtained after pretreatment and dismantling2With
LiFePO4Mixing pole piece is added in the sulfuric acid solution of 5wt%, and the solid-to-liquid ratio of the mixing pole piece and sulfuric acid solution is 100g/
L obtains mixing material, by the mixing material temperature be 200 DEG C, pressure 3Mpa, mixing speed be 500rpm condition
Under, pressurized treatments 1h is heated in autoclave, obtains leachate.
The present embodiment is tested for the property using method same as Example 1, obtained elemental lithium leaching rate up to 98%,
Cobalt, aluminium and iron content are respectively 0.2g/L, 0.01g/L and 0.01g/L in leachate, and gained lithium carbonate product purity is
99.56%, lithium loss late is 3.5%.
Embodiment 5
The difference from embodiment 1 is that step (1) are as follows: add the nickle cobalt lithium manganate pole piece obtained after pretreatment and dismantling
Enter into the sulfuric acid solution of 5wt%, the solid-to-liquid ratio of the mixing waste and sulfuric acid solution is 100g/L, obtains mixing material, will
The mixing material is 180 DEG C, pressure 2Mpa in temperature, under conditions of mixing speed is 900rpm, is heated in autoclave
Pressurized treatments 1h, obtains leachate.
The present embodiment is tested for the property using method same as Example 1, obtained elemental lithium leaching rate up to 98%,
Nickel, cobalt, aluminium and manganese element content are respectively 0.6g/L, 0.2g/L, 0.01g/L and 0.001g/L, gained lithium carbonate in leachate
Product purity is 99.56%, and lithium loss late is 3.2%.
Embodiment 6
The difference from embodiment 1 is that step (1) are as follows: will be by being separated from aluminum foil current collector after 450 DEG C of calcining 5h
The LiCoO to get off2It is added in the sulfuric acid solution of 5wt% with nickle cobalt lithium manganate anode material (production process leftover pieces), it is described mixed
The solid-to-liquid ratio for closing waste material and sulfuric acid solution is 100g/L, obtains mixing material, in temperature is 200 DEG C by the mixing material, pressure
Power is that 3Mpa heats pressurized treatments 1h in autoclave, obtain leachate under conditions of mixing speed is 800rpm.
The present embodiment is tested for the property using method same as Example 1, obtained elemental lithium leaching rate up to 98%,
Nickel, cobalt, aluminium and manganese element content are respectively 0.6g/L, 0.1g/L, 0.01g/L and 0.001g/L, gained lithium carbonate in leachate
Product purity is 99.56%, and lithium loss late is 2.6%.
Embodiment 7
The difference from embodiment 1 is that step (1) are as follows: by the battery powder obtained after pretreatment and dismantling (powder by
Old and useless battery positive and negative anodes, the mixing such as shell are broken to be obtained, and the positive electrode is cobalt nickel lithium manganate ternary material, and negative electrode material is
Graphite, additionally containing impurity such as the iron introduced in anode and the aluminium and copper and shattering process of negative current collector substitution) it is added
Into the sulfuric acid solution of 5wt%, the solid-to-liquid ratio of the mixing waste and sulfuric acid solution is 200g/L, mixing material is obtained, by institute
It is 160 DEG C, pressure 1.5Mpa that mixing material, which is stated, in temperature, under conditions of mixing speed is 600rpm, is heated in autoclave
Pressurized treatments 2h, obtains leachate.
The present embodiment is tested for the property using method same as Example 1, obtained elemental lithium leaching rate up to 97%,
The content of Ni, Co and Mn are respectively 1g/L, 0.5g/L and 0.5g/L in leachate, the content of Al, Fe and Cu be respectively 0.2g/L,
0.05g/L and 0.2g/L, gained lithium carbonate product purity are 99.56%, and lithium loss late is 4.1%.
Embodiment 8
The difference from embodiment 1 is that step (1) solid-to-liquid ratio is 400g/L.
The present embodiment is tested for the property using method same as Example 1, and obtained elemental lithium leaching rate is
50.12%, the content of Ni, Co and Mn are respectively 0.2g/L, 0.1g/L and 0.01g/L, the content point of Al, Fe and Cu in leachate
Not Wei 0.001g/L, 0.001g/L and 0.001g/L, gained lithium carbonate product purity be 99.26%, lithium loss late be 52.1%.
The present embodiment is lower relative to elemental lithium leaching rate in embodiment 1, because solid-to-liquid ratio greatly improves and leaching agent does not have
It is scaling up, thus causes to react insufficient, lithium leaching rate reduces, and lithium loss late is significantly increased.
Embodiment 9
The difference from embodiment 1 is that sulfuric acid amount be added is 9wt%, i.e., H in the described leaching agent in step (1)+With it is useless
The molar ratio of active material is 3:1 in old lithium ion battery material.
The present embodiment is tested for the property using method same as Example 1, and obtained elemental lithium leaching rate reaches
99.32%, the content of Ni, Co and Mn are respectively 5g/L, 10g/L and 3g/L in leachate, and the concentration of Al, Fe and Cu are respectively
1g/L, 0.5g/L and 2g/L；Acquired solution needs to consume a large amount of alkali tune since lithium metal ion concentration non-in leachate is excessively high
PH, final lithium loss late are up to 10%.
Embodiment 10
The difference from embodiment 1 is that the temperature of step (1) described mixing material is 100 DEG C.
The present embodiment is tested for the property using method same as Example 1, and obtained elemental lithium leaching rate is 70%,
The content of Ni, Co and Mn are respectively 3g/L, 5g/L and 1g/L in leachate, and the concentration of Al, Fe and Cu are respectively 1g/L, 0.5g/L
And 1.2g/L, lithium loss late are 50%.
The present embodiment is lower relative to elemental lithium leaching rate in embodiment 1, other valuable metals are first in addition to lithium in leachate
Plain total content is higher.Because reaction temperature is lower, causing to react insufficient, lithium leaching rate reduces, meanwhile, selectivity is pressed down
System, other non-lithium metal Elements Leaching rates increase, and need to consume a large amount of adjusting PH with base.Since generated precipitated product largely presss from both sides
Band, thus increase lithium loss late.
Embodiment 11
It is a kind of from waste and old lithium ion battery material extract valuable metal method include the following steps:
(1) the 100 mesh nickle cobalt lithium manganate battery powders obtained after pretreatment will be mechanically pulverized to be added in citric acid, it is described
H in citric acid+Molar ratio with active material in waste and old lithium ion battery material is 2:1, the waste and old lithium ion battery material
It is 300g/L with the solid-to-liquid ratio of citric acid, obtains mixing material, in temperature is 150 DEG C, pressure 1Mpa by the mixing material,
Under conditions of mixing speed is 1000rpm, pressurized treatments 10h is heated in water heating kettle, obtains leachate；
(2) it uses the pH value of NaOH regulating step (1) described leachate for 8, is separated by solid-liquid separation, obtain solid slag and net containing lithium
Change liquid；
(3) sodium carbonate is added in the scavenging solution containing lithium and extracts elemental lithium, the solid slag is for extracting in addition to lithium
Other valuable metal elements.
Elemental lithium leaching rate obtained in the present embodiment is up to 98%, and the content of Ni, Co and Mn are respectively 0.5g/ in leachate
L, 0.3g/L and 0.2g/L, gained lithium carbonate product purity are 99.56%, and lithium loss late is 3.2%.
Embodiment 12
It is a kind of from waste and old lithium ion battery material extract valuable metal method include the following steps:
(1) the 100 mesh nickle cobalt lithium manganate battery powders obtained after pretreatment will be mechanically pulverized to be added in nitric acid, the nitre
H in acid+Be 0.3:1 with the molar ratio of active material in waste and old lithium ion battery material, the waste and old lithium ion battery material with
The solid-to-liquid ratio of leaching agent be 200g/L, obtain mixing material, by the mixing material temperature be 250 DEG C, pressure 10Mpa,
Under conditions of mixing speed is 400rpm, pressurized treatments 0.5h is heated in autoclave or water heating kettle, obtains leachate；
(2) it uses the pH value of NaOH regulating step (1) described leachate for 11, is separated by solid-liquid separation, obtain solid slag and containing lithium
Scavenging solution；
(3) sodium carbonate is added in the scavenging solution containing lithium and extracts elemental lithium, the solid slag is for extracting in addition to lithium
Other valuable metal elements.
Elemental lithium leaching rate obtained in the present embodiment is up to 98%, and the content of Ni, Co and Mn are respectively 0.2g/ in leachate
L, 0.05g/L and 0.01g/L, gained lithium carbonate product purity are 99.56%, and lithium loss late is 2.4%.
Comparative example 1
The difference from embodiment 1 is that without step (2).
This comparative example is tested for the property using method same as Example 1, and obtained elemental lithium leaching rate is 98%,
The content of Ni, Co and Mn are respectively 0.5g/L, 0.05g/L and 0.01g/L in leachate, and the content of Al, Fe and Cu are respectively
0.001g/L, 0.001g/L and 0.001g/L, gained lithium carbonate product purity are 95.21%, and lithium loss late is 3%.
This comparative example is lower relative to lithium carbonate product purity in embodiment 1, because containing certain other miscellaneous in leachate
Matter ion.These ions carry out lithium carbonate preparation Shi Douhui prior to lithium precipitate, thus be mingled in lithium carbonate product it is a large amount of its
Its carbonate causes product purity lower.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of method for extracting valuable metal from waste and old lithium ion battery material, which is characterized in that the method includes such as
Lower step:
(1) waste and old lithium ion battery material is mixed with leaching agent, obtains mixing material, the mixing material is heated at pressurization
It manages, after separation of solid and liquid, obtains leachate and a solid slag；
(2) pH value of regulating step (1) described leachate, obtains secondary solid slag and scavenging solution containing lithium.
2. the method as described in claim 1, which is characterized in that the temperature of step (1) the heating pressurization is 150~250 DEG C；
Preferably, the pressure of step (1) the heating pressurization is 0.5~3Mpa；
Preferably, the time of step (1) the heating pressurization is 0.5~10h.
3. method according to claim 1 or 2, which is characterized in that step (1) the heating pressurized treatments are in stirring condition
Lower heating pressurization；
Preferably, the speed of the stirring is 100~2500rpm, preferably 400~1000rpm；
Preferably, the reactor of step (1) the heating pressurization is autoclave or water heating kettle.
4. the method as described in one of claim 1-3, which is characterized in that step (1) leaching agent is acid, preferably organic
Acid and/or inorganic acid；
Preferably, the organic acid include in citric acid, acetic acid and aspartic acid any one or at least two combination；
Preferably, the inorganic acid include in hydrochloric acid, sulfuric acid and nitric acid any one or at least two combination.
5. the method as described in one of claim 1-4, which is characterized in that H in step (1) described leaching agent+And applying waste lithium ionic
The molar ratio of active material is 0.3~2:1 in battery material；
Preferably, the solid-to-liquid ratio of step (1) the waste and old lithium ion battery material and leaching agent is 10~600g/L, preferably
200~300g/L；
Preferably, active material includes positive active material in the waste and old lithium ion battery material.
6. the method as described in one of claim 1-5, which is characterized in that step (1) the waste and old lithium ion battery material packet
Include the mixture of waste and old positive electrode or waste and old positive electrode and waste and old negative electrode material；
Preferably, the waste and old positive electrode includes any one in cobalt acid lithium, nickle cobalt lithium manganate, LiMn2O4 and LiFePO4
Or at least two combination；
Preferably, the waste and old negative electrode material includes any one in graphite cathode, silicium cathode and silicon-carbon cathode or at least two
The combination of kind；
Preferably, step (1) it is described be separated by solid-liquid separation include sedimentation separation, be separated by filtration and be centrifugated in any one or extremely
Few two kinds of combination.
7. the method as described in one of claim 1-6, which is characterized in that the adjusting method of step (2) described pH of leaching solution
To be adjusted using basic matterial；
Preferably, the pH value is 8~11；
Preferably, the basic matterial includes any one in sodium hydroxide, sodium carbonate and potassium hydroxide or at least two
Combination.
8. the method as described in one of claim 1-7, which is characterized in that also wrapped after step (2) the adjusting pH of leaching solution
Include the process of separation of solid and liquid；
Preferably, it is described be separated by solid-liquid separation include sedimentation separation, be separated by filtration and be centrifugated in any one or at least two
Combination.
9. method as described in one of claim 1-8, which is characterized in that scavenging solution containing lithium described in step (2) can be used for extracting
Elemental lithium；
Preferably, the extraction process of the elemental lithium, which is included in the scavenging solution containing lithium, is added sodium carbonate；
Preferably, the solid slag is for extracting other valuable metal elements in addition to lithium.
10. method as claimed in one of claims 1 to 9, which is characterized in that described method includes following steps:
(1) waste and old lithium ion battery material is mixed with leaching agent, H in the leaching agent+It lives in waste and old lithium ion battery material
Property substance molar ratio be 0.3~2:1, the solid-to-liquid ratio of the waste and old lithium ion battery material and leaching agent is 200~300g/L,
Obtain mixing material, by the mixing material temperature be 150~250 DEG C, pressure be 0.5~10Mpa, mixing speed 400
Under conditions of~1000rpm, 0.5~10h of pressurized treatments is heated in autoclave or water heating kettle, after being separated by solid-liquid separation, is obtained
Leachate and a solid slag；
(2) it uses the pH value of basic matterial regulating step (1) described leachate for 8~11, is separated by solid-liquid separation, obtains solid slag and contain
Lithium scavenging solution；
(3) sodium carbonate is added in the scavenging solution containing lithium and extracts elemental lithium, the solid slag is used to extract other in addition to lithium
Valuable metal element.
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