CN107978814A - A kind of method of Selective Separation lithium in material from waste lithium ion cell anode - Google Patents
A kind of method of Selective Separation lithium in material from waste lithium ion cell anode Download PDFInfo
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- CN107978814A CN107978814A CN201710537314.9A CN201710537314A CN107978814A CN 107978814 A CN107978814 A CN 107978814A CN 201710537314 A CN201710537314 A CN 201710537314A CN 107978814 A CN107978814 A CN 107978814A
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention discloses a kind of method of Selective Separation lithium in material from waste lithium ion cell anode.It the described method comprises the following steps：(1) lithium ion battery positive plate and separating liquid are reacted, and oxidisability additive is added in reaction system and/or is passed through oxidizing gas, destroy the Li O keys in waste lithium ion cell anode material, the crystal structure of other residual metallic elements is stablized, lithium is selectively entered solution, and other metal waste residues and aluminium foil in addition to lithium are stayed in solid slag；(2) pass through separation of solid and liquid, obtain rich lithium solution and solid slag.Wherein, separating liquid is acid solution or pH alkaline solutions less than 10 of the pH more than 3.The present invention provides a kind of short route, the method for Selective Separation lithium, separating Li is efficient in the material from waste lithium ion cell anode, and disengaging time is short, and cost is low, and recovery process is pollution-free, is easy to industrialized production.
Description
Technical field
The invention belongs to lithium ion battery recovery technology field, more particularly to a kind of waste lithium ion cell anode material
Selective separation method.
Background technology
As lithium ion battery is in mobile phone, laptop, digital equipment, electric automobile, extensively should in intelligent grid
With, in addition the lithium ion battery service life be generally 3 years or so, electronic product updates than very fast, is produced per annual meeting a large amount of waste and old
Lithium ion battery；In addition, production waste material can be also produced in production process.The scrap lithium ion battery of these substantial amounts, can make
Into sizable pollution pressure.If waste and old lithium ion battery is arbitrarily abandoned in the environment, harmful substance will be into burying
Earth and water body, pollute, and are eventually entered into by food chain in human body and animal body.In addition for circular economy angle,
Metals resources containing the preciousness such as cobalt, manganese, nickel, lithium, copper, aluminium, iron in lithium ion battery.
Therefore metal is recycled from waste lithium cell, not only can be with environmental protection, but also can be to avoid the waste of resource.
Waste and old lithium ion battery discharges, and after the pretreatment such as disassembling, obtains including active material and aluminum foil current collector
Anode waste.There are the technologies such as dry method burning, hydrometallurgical process, biological treatment for the processing procedure of anode waste.Dry method
Burn, energy consumption is big, produces harmful exhaust, easily causes secondary pollution.Biologic treating technique is immature.Hydrometallurgy is used for lithium ion
The recycling of metal in anode waste, energy consumption is low, and pollution is few, and metal recovery rate is high, has been to be concerned by more and more people.
At present, the recycling for lithium ion cell anode waste also has some reports, and CN 101818251A disclose one kind
From the method for used Li ion cell Call Provision and lithium, by battery discharge, disassemble, positive plate alkali cleaning removes aluminium foil and obtains positive powder
End, with sodium salt and sylvite high-temperature roasting, then water logging goes out, and leachate obtains cobalt oxalate lithium carbonate, above-mentioned side through heavy cobalt and sinker
Method shortcoming is：High-temperature roasting, high energy consumption, alkali metal salt corrosion refractory material, long flow path.CN 106129511A have invented one kind
From the method for waste and old lithium ion battery recycling valuable metal, by the positive material of battery and reducing agent high-temperature roasting, product of roasting
The water logging being carbonized with titanium dioxide goes out, and obtains lithia water, prepares lithium carbonate；Water logging is slagged tap using oxidation acid leaching or amine-oxides
Leaching valuable metal is soaked, last extracting and purifying obtains metal product.The method high-temperature roasting, high energy consumption, first reduces rear oxidation flow
It is long, be not suitable for extensive raw processing lithium ion old and useless battery.CN 105907989A disclose one kind and are recycled from waste lithium cell
The method of cobalt and lithium, the method remove aluminium foil using high-temperature roasting, are leached with sulfuric acid and sodium thiosulfate under ultrasound condition,
Extract cobalt with extractant, raffinate leads to carbon dioxide and prepares lithium carbonate.The method uses high-temperature roasting, high energy consumption, and preparation flow
It is cumbersome, it is not suitable for mass producing.
In anode material for lithium-ion batteries, lithium is relatively low relative to other tenors, and stable structure.Charge in battery
During, the lithium in positive electrode is deviate from, release electronics, and other metal ions in positive electrode occur oxidation reaction and lose electricity
Son, positive electrode at this time are also highly stable.Based on this, a kind of thinking is additive of the selection with oxidation, will be waste and old
Based lithium-ion battery positive plate is reacted with the acidity containing additive or alkaline solution, to reach more preferable recovering effect.
CN 105789724A disclose a kind of processing method of used Li ion cell, which passes through used Li ion cell
A series of processing obtain powder, and powder is put into lye and carries out alkali turn dissolving recycling aluminium, then sour sediment is obtained by filtration
Liquid+hydrogen peroxide dissolves to form mixed solution, then iron removaling and aluminium impurity is gone with adjusting PH with base, afterwards using countercurrent multistage synergic solvent extraction
Lithium salts raffinate, nickel cobalt lithium, nickel cobalt or nickel cobalt manganese salt-mixture are obtained, cobalt salt is obtained by acid back extraction, then by processing system
Standby novel anode material.The shortcomings that patent is long flow path, and lithium extracts poor selectivity.
In short, patent or achievement in research that up to the present disclosed many waste and old lithium ion batteries are handled both at home and abroad, also
Do not have a kind of to realize lithium ion cell anode waste short route, low cost, the technology of selective recovery metal.So ability
Lithium is extracted in domain from waste and old lithium ion battery with high selectivity there is an urgent need for a kind of short route is developed, to realize resources economy economized
Method.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide one kind from waste and old lithium ion battery
The method of Selective Separation lithium in positive electrode, can solve existing waste lithium ion cell anode material recovery long flow path,
Removal process produces secondary pollution, is unable to the problems such as Selective Separation.
To reach this purpose, the present invention adopts the following technical scheme that：
The present invention provides a kind of method from waste lithium ion cell anode material selectivity separating Li, and the method is：
(1) lithium ion battery positive plate and separating liquid are reacted, and oxidisability addition is added in reaction system
Agent and/or oxidizing gas is passed through, destroys the Li-O keys in waste lithium ion cell anode material, lithium is selectively entered molten
Liquid, and other metal waste residues and aluminium foil in addition to lithium are stayed in solid slag；
(2) separation of solid and liquid, obtains rich lithium solution and solid slag；
Wherein, separating liquid is acid solutions of the pH more than 3, or alkaline solutions of the pH below 10.
In the present invention, " add oxidisability additive and/or be passed through oxidizing gas " refers to：Oxidisability can only be added
Additive, can also only be passed through oxidizing gas, can also not only add oxidisability additive but also be passed through oxidizing gas.
In the present invention, acid solutions of the pH more than 3, pH such as 3,3.2,3.5,4,4.5,5,5.5,6 or 6.5
Deng.If pH value is less than 3, the dissolving of metallic aluminium can be caused, and then the selectivity of lithium is deteriorated.
In the present invention, alkaline solutions of the pH below 10, pH is such as 10,9.5,9,8.5,8 or 7.5.If pH value
More than 10, the dissolving of metallic aluminium can be caused, and then the selectivity of lithium is deteriorated.
What this method can make the lithium selectivity in waste and old lithium ion battery enters solution, and other metal components and aluminium foil
It is present in the form of solid slag in the liquid after reaction, by separation of solid and liquid, obtains being rich in the separating liquid of lithium and containing aluminium foil
Slag is separated, so as to fulfill the Selective Separation of the lithium from waste lithium ion cell anode material.Moreover, the method for the present invention also has
There is flow short, there is no the advantages of secondary pollution.
Currently preferred technical solution is used as below, but not as the limitation to technical solution provided by the invention, is led to
Following preferable technical solution is crossed, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
Preferably, the oxidisability additive is sodium peroxide, sodium hypochlorite, hypochlorous acid, sodium peroxydisulfate or hydrogen peroxide
In any a kind or at least two kinds of of combination, the combination typical case but non-limiting examples have：The group of sodium peroxide and sodium hypochlorite
Close, sodium peroxide and hypochlorous combination, the combination of sodium peroxide and sodium peroxydisulfate, the combination of sodium peroxide and hydrogen peroxide,
The combination of sodium hypochlorite, hypochlorous acid and sodium peroxydisulfate, the combination of hypochlorous acid, sodium perchlorate and hydrogen peroxide, sodium hypochlorite, secondary chlorine
The combination of acid, sodium peroxydisulfate and hydrogen peroxide, the combination of sodium peroxide, sodium hypochlorite, hypochlorous acid, sodium peroxydisulfate and hydrogen peroxide
Deng.
Preferably, the oxidizing gas includes any a kind or at least 2 in fluorine gas, chlorine, ozone, oxygen or air
The mixed gas of kind, but the above-mentioned oxidizing gas enumerated is not limited to, other can reach the oxidizing gas of same effect
Available for the present invention.
As the optimal technical scheme of the method for the invention, the separating liquid is acid solutions of the pH 3~6.
As the optimal technical scheme of the method for the invention, the separating liquid is alkaline solutions of the pH 7~9.
Preferably, the acid in acid solutions of the pH more than 3 is any a kind or 2 kinds in inorganic acid or organic acid
Combination.
Preferably, it is described to have inorganic acid for any a kind or at least two kinds of of combination in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, allusion quotation
Type but non-limiting combinations are the combination of sulfuric acid and hydrochloric acid, the combination of sulfuric acid and nitric acid, the combination of sulfuric acid and phosphoric acid, hydrochloric acid and phosphorus
The combination of acid, the combination of hydrochloric acid and nitric acid, the combination etc. of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
Preferably, the carbon number that the organic acid includes but not limited to contain or not contain substituent is the organic of 1-8
Acid.
Preferably, the organic acid be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, any 1 in enanthic acid or octanoic acid
Kind or at least two kinds of combinations, typical case but non-limiting combinations are formic acid and acetic acid combinations, and formic acid and propionic acid combine, propionic acid and fourth
Acid combination, formic acid and valeric acid combination, acetic acid and valeric acid combination, butyric acid and valeric acid combination, formic acid, acetic acid, propionic acid and butyric acid combination
Deng.
Preferably, the substituent be fluorine, chlorine, any a kind or at least two kinds of of combination in bromine or iodine, typical but non-limit
Property processed is combined as the combination of fluorine and chlorine, the combination of fluorine and bromine, the combination of fluorine and iodine, the combination of chlorine and bromine, the combination of chlorine and iodine, bromine
With the combination of iodine, the combination of fluorine, chlorine, bromine, the combination of chlorine, bromine, iodine, the combination etc. of fluorine, chlorine, bromine, iodine, is preferably fluorine and/or chlorine.
" fluorine and/or chlorine " of the present invention refers to：Can be fluorine, can also chlorine, can also be the combination of fluorine and chlorine.
Preferably, the number of the substituent 1~9, such as 2,3,4,5,6,7 or 8, preferably
For 3~6.
Preferably, the alkali in alkaline solutions of the pH below 10 is sodium hydroxide, calcium hydroxide, barium hydroxide, hydrogen
Any a kind or at least two kinds of of combination of potassium oxide, cesium hydroxide, ammonium hydroxide or sodium carbonate, typical case but non-limiting combinations are hydrogen-oxygen
Change the combination of sodium and calcium hydroxide, the combination of sodium hydroxide and barium hydroxide, the combination of sodium hydroxide and potassium hydroxide, hydroxide
The combination of the combination of sodium calcium and cesium hydroxide, barium hydroxide and ammonium hydroxide, the combination of sodium hydroxide, calcium hydroxide and barium hydroxide,
The combination of cesium hydroxide, ammonium hydroxide and sodium carbonate, the combination of sodium hydroxide, calcium hydroxide, barium hydroxide and potassium hydroxide, hydroxide
The combination of barium, potassium hydroxide, cesium hydroxide, ammonium hydroxide and sodium carbonate, sodium hydroxide, calcium hydroxide, barium hydroxide, potassium hydroxide,
Combination of cesium hydroxide, ammonium hydroxide and sodium carbonate etc..
As the optimal technical scheme of the method for the invention, using the separating liquid and the gross mass of oxidisability additive as
100% meter, the mass percentage of oxidisability additive are 0.01%~20%, such as 0.02%, 0.05%, 0.08%,
0.1%th, 0.2%, 0.4%, 0.6%, 0.9%, 1%, 2%, 4%, 7%, 8%, 12%, 14%, 15% or 18% etc., preferably
0.02~18%.
Preferably, the flow that oxidizing gas is passed through in the reaction system is 0.01~20L/min, such as 0.01L/
min、0.04L/min、0.08L/min、0.1L/min、0.3L/min、0.7L/min、0.9L/min、1L/min、2L/min、5L/
Min, 8L/min, 10L/min, 12L/min, 15L/min or 18L/min etc., preferably 0.02~18L/min.
The present invention is to lithium ion battery positive plate
Source is not construed as limiting, and can is positive plate manufacturing scrap material or is manually disassembled waste and old lithium ion battery and obtain
To positive plate in any a kind or at least two kinds of of combination.
Preferably, the active material of the lithium ion battery positive plate for cobalt-based positive electrode, manganese-based anode material,
Any a kind or at least two kinds of of combination in nickel-base anode material or LiFePO4.
Preferably, the active material of the lithium ion battery positive plate is cobalt acid lithium, lithium nickelate, LiMn2O4, nickel cobalt
Any a kind or at least two kinds of of combination in LiMn2O4, nickel cobalt lithium aluminate or LiFePO4, typical but non-limiting combinations are manganese
The combination of sour lithium and nickle cobalt lithium manganate, the combination of LiMn2O4 and LiFePO4, the combination of nickle cobalt lithium manganate and LiFePO4, cobalt acid
The combination of lithium and lithium nickelate, the combination of lithium nickelate, LiMn2O4 and LiFePO4, the combination of cobalt acid lithium, lithium nickelate and LiMn2O4, nickel
The combination of sour lithium, LiMn2O4, nickle cobalt lithium manganate and nickel cobalt lithium aluminate, cobalt acid lithium, lithium nickelate, LiMn2O4, nickle cobalt lithium manganate and nickel
Combination of cobalt lithium aluminate etc..
Preferably, the active material of the lithium ion battery positive plate is in manganese-based anode material or LiFePO4
The combination of any one or two kinds.Find particular application for manganese-based anode material or lithium iron phosphate positive material, because lithium selects
Selecting property is leached into after solution, and the crystal structure of other residual metallic elements is stablized, and is adapted to large-scale waste and old lithium ion battery
The processing of anode pole piece.
Preferably, the liquid-solid ratio of the lithium ion battery positive plate and separating liquid is 0.1mL/g~200mL/g, such as
0.5mL/g, 2mL/g, 3mL/g, 4mL/g, 5mL/g, 8mL/g, 10mL/g, 20mL/g, 40mL/g, 50mL/g, 70mL/g or
160mL/g etc., is preferably 0.5mL/g~150mL/g.
In the present invention, " liquid-solid ratio of lithium ion battery positive plate and separating liquid " refers to：The body of the separating liquid
The mass ratio of product and the lithium ion battery positive plate.
Preferably, the temperature of the reaction be 10 DEG C~180 DEG C, such as 20 DEG C, 30 DEG C, 40 DEG C, 60 DEG C, 70 DEG C, 90 DEG C,
110 DEG C, 120 DEG C, 40 DEG C or 150 DEG C etc., be preferably 25 DEG C~150 DEG C.
Preferably, the time of the reaction is 10min~300min, as 20min, 30min, 40min, 50min, 60min,
80min, 100min, 120min, 140min, 170min, 200min or 250min etc., are preferably 30min~250min.
Preferably, the reaction carries out under agitation, and the speed of the stirring is preferably 100rpm~2500rpm,
As 150rpm, 200rpm, 300rpm, 400rpm, 500rpm, 600rpm, 700rpm, 900rpm, 1100rpm, 1400rpm,
1500rpm, 1800rpm or 2000rpm etc., more preferably 200rpm~2000rpm.
In the method for the present invention, the mode of separation of solid and liquid do not limited, as long as separation liquid and solid can be reached
Mesh ground, typical but non-limiting separate mode are：Sedimentation separation, is separated by filtration or centrifuges.
Preferably, the method further includes the step of solid slag that separation of solid and liquid obtains is dried and is sieved, so that
Obtain aluminium foil and the waste material (other metal waste residues i.e. in addition to lithium) without lithium.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) separating liquid is mixed with lithium ion battery positive plate by the liquid-solid ratio of 0.5mL/g~150mL/g, in 25
DEG C~150 DEG C react 30min~250min under agitation, lithium is entered solution, and other in addition to lithium
Metal waste residue and aluminium foil are stayed in solid slag；
(2) separation of solid and liquid, obtains rich lithium solution and solid slag；
Wherein, separating liquid is acid solution containing oxidizing additive of the pH value more than 3, or pH value containing below 10
The lye of oxidisability additive.
This optimal technical scheme is by using the liquid-solid ratio to lithium ion battery positive plate and separating liquid, reaction temperature
The control of degree, reaction time and pH, conformability have reached more preferable lithium separating effect, lithium separating effect more than 93%,
Up to 98%.
Compared with the prior art, the present invention has the advantages that：
(1) method of the invention can be optionally sequestered the lithium in lithium ion battery positive plate, and it is molten to obtain rich lithium
Liquid, the separative efficiency of lithium is high, and more than 93%, disengaging time is short, and technological process is simple, and does not produce secondary pollution.
(2) method provided by the invention based on Selective Separation lithium in lithium ion battery positive plate, the scope of application
Width, can be suitable for cobalt-based, manganese base, LiFePO4, the Selective Separation lithium of nickel-base anode waste material and its mixture, be adapted to big rule
The processing of the waste lithium ion cell anode pole piece of mould.
(3) method provided by the invention based on Selective Separation lithium in lithium ion battery positive plate, without passing through
Pre-treatment step separates lithium ion anode material and aluminum foil current collector, reduces processing cost, while avoid the prior art from using
Organic solvent or strong alkaline solution remove separation positive electrode and aluminium foil, damage to environment and human body.
(4) method provided by the invention based on Selective Separation lithium in lithium ion battery positive plate, was separating
Cheng Zhong, by regulating and controlling response parameter, reduces content of other foreign metal ions in separating liquid, selective to be separated to lithium
In separating liquid, other metals enter separation slag, have achieveed the purpose that short route separating Li.
Brief description of the drawings
Fig. 1 is that the technological process of Selective Separation lithium in the slave waste lithium ion cell anode material that embodiment 1 provides is shown
It is intended to.
Embodiment
Further illustrate technical scheme below with reference to the accompanying drawings and specific embodiments.But following reality
The simple example that example is only the present invention is applied, does not represent or limit the scope of the present invention, the scope of the present invention
It is subject to claims.
Embodiment 1
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) lithium ion battery lithium cobaltate cathode sheet waste material is taken, the mass percentage for measuring metal in anode waste is：
Co：45.28%, Li：1.13%, Al：2.06%.
(2) take the dry later waste and old lithium cobaltate cathode piece of step (1) a, the liquid-solid ratio of 0.6mL/g is pressed with separating liquid
Weigh the quality of positive plate solid and measure separating liquid (pH value be 4 acetic acid solution) liquid volume, be put into reactor, while to
Oxidisability additive sodium peroxydisulfate is added in reaction system (using the separating liquid and the gross mass of oxidisability additive as 100%
Meter, the mass percentage of oxidisability additive control mixing speed 800rpm, in 60 DEG C of reactions 3%), to be reacted
60min, the separation of making choice property；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 1.
Fig. 1 is that the technological process of Selective Separation lithium in the material provided in this embodiment from waste lithium ion cell anode is shown
It is intended to.
Embodiment 2
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is with reference to embodiment 1, and difference lies in the liquid-solid ratio of the waste and old lithium cobaltate cathode piece and separating liquid is 2mL/g.It the results are shown in Table 1.
Embodiment 3
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is with reference to embodiment 1, and difference lies in the liquid-solid ratio of the waste and old lithium cobaltate cathode piece and separating liquid is 10mL/g.It the results are shown in Table
1。
Embodiment 4
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) lithium ion battery lithium cobaltate cathode sheet waste material is taken, the mass percentage for measuring metal in anode waste is：
Co：45.28%, Li：1.13%, Al：2.06%.
(2) take the dry later waste and old lithium cobaltate cathode piece of step (1) a, the liquid-solid ratio of 0.6mL/g is pressed with separating liquid
Weigh the quality of positive plate solid and measure separating liquid (pH value is 9 sodium hydroxide solution) liquid volume, be put into reactor, together
When ozone is passed through into reaction system, flow 2L/min, is reacted, control mixing speed 800rpm, in 60 DEG C reaction
60min, the separation of making choice property；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 1.
Embodiment 5
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is with reference to embodiment 4, and difference lies in the liquid-solid ratio of the waste and old lithium cobaltate cathode piece and separating liquid is 2mL/g.It the results are shown in Table 1.
Embodiment 6
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is with reference to embodiment 4, and difference lies in the liquid-solid ratio of the waste and old lithium cobaltate cathode piece and separating liquid is 10mL/g.It the results are shown in Table
1。
Embodiment 7
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) lithium-ion battery lithium iron phosphate cathode sheet waste material is taken, and measures the mass percentage of metal in anode waste：
Fe：26.05%, Li：3.60%, Al：16.72%.
(2) take the dry later waste lithium iron phosphate positive plate of step (1) a, consolidate with separating liquid by the liquid of 0.6mL/g
Than weighing the quality of positive plate solid and measuring separating liquid (pH value is 3 phosphoric acid solution) liquid volume, reactor is put into, at the same time
Added into reaction system oxidisability additive hydrogen peroxide (using the separating liquid and the gross mass of oxidisability additive as
100% meter, the mass percentage of oxidisability additive control mixing speed 800rpm, in 60 DEG C instead 3%), to be reacted
60min is answered, the separation of making choice property；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 2.
Embodiment 8
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method reference implementation example 7, difference lies in the liquid-solid ratio of the waste lithium iron phosphate positive plate and separating liquid is 2mL/g.It the results are shown in Table
2。
Embodiment 9
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method reference implementation example 7, difference lies in the liquid-solid ratio of the waste lithium iron phosphate positive plate and separating liquid is 10mL/g.The result is shown in
Table 2.
Embodiment 10
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) lithium-ion battery lithium iron phosphate cathode sheet waste material is taken, and measures the mass percentage of metal in anode waste：
Fe：26.05%, Li：3.60%, Al：16.72%.
(2) take the dry later waste lithium iron phosphate positive plate of step (1) a, consolidate with separating liquid by the liquid of 0.6mL/g
Than weighing the quality of positive plate solid and measuring separating liquid (pH value is 9 ammonia spirit) liquid volume, reactor is put into, at the same time
Added into reaction system oxidisability additive sodium hypochlorite (using the separating liquid and the gross mass of oxidisability additive as
100% meter, 3%) mass percentage of oxidisability additive is.Reacted, control mixing speed 800rpm, it is anti-in 60 DEG C
60min is answered, the separation of making choice property；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 2.
Embodiment 11
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is with reference to embodiment 10, and difference lies in the liquid-solid ratio of the waste lithium iron phosphate positive plate and separating liquid is 2mL/g.Knot
Fruit is shown in Table 2.
Embodiment 12
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is with reference to embodiment 10, and difference lies in the liquid-solid ratio of the waste lithium iron phosphate positive plate and separating liquid is 10mL/g.The result is shown in
Table 2.
Embodiment 13
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) lithium ionic cell nickel acid lithium is taken, LiMn2O4 and iron phosphate lithium positive pole sheet waste material are uniformly mixed and measure cathode and give up
The mass percentage of metal in material：Fe:19.13%, Li：4.76%, Al:10.52%, Ni：16.43%, Mn：17.31%.
(2) take the dry later waste and old lithium ion battery mixing pole piece of step (1) a, with separating liquid by 0.6mL/g's
Liquid-solid ratio weighs the quality of positive plate solid and measures separating liquid (pH value is 4 2- neoprenes acid solution) liquid volume, is put into anti-
Answer device, while add into reaction system oxidisability additive sodium hypochlorite (with the total of the separating liquid and oxidisability additive
Quality is 100% meter, and 3%) mass percentage of oxidisability additive is, is reacted, control mixing speed 800rpm, in
60 DEG C of reaction 60min, the separation of making choice property；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 3.
Embodiment 14
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is with reference to embodiment 13, and difference lies in the liquid-solid ratio of the waste and old lithium ion battery mixing pole piece and separating liquid is 2mL/g.Knot
Fruit is shown in Table 3.
Embodiment 15
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is with reference to embodiment 13, and difference lies in the liquid-solid ratio of the waste and old lithium ion battery mixing pole piece and separating liquid is 10mL/g.Knot
Fruit is shown in Table 3.
Embodiment 16
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) lithium ionic cell nickel acid lithium is taken, LiMn2O4 and iron phosphate lithium positive pole sheet waste material are uniformly mixed and measure cathode and give up
The mass percentage of metal in material：Fe:19.13%, Li：4.76%, Al:10.52%, Ni：16.43%, Mn：17.31%.
(2) take the dry later waste and old lithium ion battery mixing pole piece of step (1) a, with separating liquid by 0.6mL/g's
Liquid-solid ratio weighs the quality of positive plate solid and measures separating liquid (pH value is 8 sodium carbonate liquor) liquid volume, is put into reaction
Device, while chlorine is passed through into reaction system, flow 1L/min, is reacted, and controls mixing speed 800rpm, anti-in 60 DEG C
60min is answered, the separation of making choice property；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 3.
Embodiment 17
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is with reference to embodiment 16, and difference lies in the liquid-solid ratio of the waste and old lithium ion battery mixing pole piece and separating liquid is 2mL/g.Knot
Fruit is shown in Table 3.
Embodiment 18
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is with reference to embodiment 16, and difference lies in the liquid-solid ratio of the waste and old lithium ion battery mixing pole piece and separating liquid is 10mL/g.Knot
Fruit is shown in Table 3.
Embodiment 19
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) lithium ion battery mangaic acid lithium cathode sheet waste material is taken, the mass percentage for measuring metal in anode waste is：
Li：3.89%, Al:13.21%, Mn：43.37%.
(2) take the dry later waste lithium manganese oxide positive plate of step (1) a, the liquid-solid ratio of 150mL/g is pressed with separating liquid
Weigh the quality of positive plate solid and measure separating liquid (pH value be 6 acetic acid solution) liquid volume, be put into reactor, while to
Oxidisability additive sodium peroxydisulfate is added in reaction system (using the separating liquid and the gross mass of oxidisability additive as 100%
Meter, the mass percentage of oxidisability additive control mixing speed 2000rpm, in 25 DEG C instead 0.02%), to be reacted
250min between seasonable, the separation of making choice property；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 4.
Embodiment 20
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) lithium ion battery mangaic acid lithium cathode sheet waste material is taken, the mass percentage for measuring metal in anode waste is：
Li：3.89%, Al:13.21%, Mn：43.37%.
(2) take the dry later waste lithium manganese oxide positive plate of step (1) a, the liquid-solid ratio of 0.5mL/g is pressed with separating liquid
Weigh the quality of positive plate solid and measure separating liquid (pH value be 5 acetic acid solution) liquid volume, be put into reactor, while to
Ozone is passed through in reaction system, flow 5L/min, controls mixing speed 200rpm, in 150 DEG C of reaction time 60min, carries out
Selective Separation；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 4.
Embodiment 21
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) lithium ion battery mangaic acid lithium cathode sheet waste material is taken, and measures the mass percentage of metal in anode waste：
Li：3.89%, Al:13.21%, Mn：43.37%.
(2) take the dry later waste lithium manganese oxide positive plate of step (1) a, the liquid-solid ratio of 0.1mL/g is pressed with separating liquid
Weigh the quality of positive plate solid and measure separating liquid (pH value is 10 sodium hydroxide solution) liquid volume, be put into reactor,
Ozone is passed through into reaction system at the same time, flow 5L/min, is reacted, and controls mixing speed 2500rpm, anti-in 100 DEG C
45min is answered, the separation of making choice property；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 4.
Embodiment 22
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) lithium ion battery mangaic acid lithium cathode sheet waste material is taken, and measures the mass percentage of metal in anode waste：
Li：3.89%, Al:13.21%, Mn：43.37%.
(2) take the dry later waste lithium manganese oxide positive plate of step (1) a, the liquid-solid ratio of 200mL/g is pressed with separating liquid
Weigh the quality of positive plate solid and measure separating liquid (pH value is 10 sodium hydroxide solution) liquid volume, be put into reactor,
Added at the same time into reaction system oxidisability additive sodium hypochlorite (using the separating liquid and the gross mass of oxidisability additive as
100% meter, the mass percentage of oxidisability additive control mixing speed 1000rpm, in 10 DEG C 18%) to be reacted
React 10min, the separation of making choice property；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 4.
Embodiment 23
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) take lithium ion battery mangaic acid lithium and iron phosphate lithium positive pole sheet waste material to be uniformly mixed, and measure golden in anode waste
The mass percentage of category：Fe:20.13%, Li：4.36%, Al:12.52%, Mn：18.96%.
(2) take the dry later waste lithium manganese oxide of step (1) and LiFePO4 blended anode piece a, pressed with separating liquid
The liquid-solid ratio of 2mL/g weighs the quality of positive plate solid and measures separating liquid (pH value is 3 2- neoprenes acid solution) liquid volume,
Reactor is put into, while adds oxidisability additive hydrogen peroxide into reaction system and (is added with the separating liquid and oxidisability
The gross mass of agent is 100% meter, and the mass percentage of oxidisability additive controls mixing speed 20%), to be reacted
1000rpm, 120min, the separation of making choice property are reacted in 80 DEG C；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 5.
Embodiment 24
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) take lithium ion battery mangaic acid lithium and iron phosphate lithium positive pole sheet waste material to be uniformly mixed, and measure golden in anode waste
The mass percentage of category：Fe:20.13%, Li：4.36%, Al:12.52%, Mn：18.96%.
(2) take the dry later waste lithium manganese oxide of step (1) and LiFePO4 blended anode piece a, pressed with separating liquid
The liquid-solid ratio of 2mL/g weighs the quality of positive plate solid and measures separating liquid (pH value is 3 2- neoprenes acid solution) liquid volume,
Reactor is put into, while adds oxidisability additive hydrogen peroxide into reaction system and (is added with the separating liquid and oxidisability
The gross mass of agent is 100% meter, and the mass percentage of oxidisability additive controls mixing speed 0.01%), to be reacted
100rpm, 30min, the separation of making choice property are reacted in 180 DEG C；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 5.
Embodiment 25
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) take lithium ion battery mangaic acid lithium and iron phosphate lithium positive pole sheet waste material to be uniformly mixed, and measure golden in anode waste
The mass percentage of category：Fe:20.13%, Li：4.36%, Al:12.52%, Mn：18.96%.
(2) take the dry later waste lithium manganese oxide of step (1) and LiFePO4 blended anode piece a, pressed with separating liquid
The liquid-solid ratio of 0.6mL/g weighs the quality of positive plate solid and measures separating liquid (pH value is 8 sodium carbonate liquor) liquid volume,
Reactor is put into, while chlorine is passed through into reaction system, flow 4L/min, is reacted, and controls mixing speed 800rpm, in
45 DEG C of reaction 300min, the separation of making choice property；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 5.
Embodiment 26
A kind of method of the Selective Separation lithium from lithium ion battery positive plate is present embodiments provided, its specific side
Method is：
(1) take lithium ion battery mangaic acid lithium and iron phosphate lithium positive pole sheet waste material to be uniformly mixed, and measure golden in anode waste
The mass percentage of category：Fe:20.13%, Li：4.36%, Al:12.52%, Mn：18.96%.
(2) take the dry later waste lithium manganese oxide of step (1) and LiFePO4 blended anode piece a, pressed with separating liquid
The liquid-solid ratio of 5mL/g weighs the quality of positive plate solid and measures separating liquid (pH value is 9 sodium carbonate liquor) liquid volume, puts
Enter reactor, while chlorine is passed through into reaction system, flow 4L/min, is reacted, and mixing speed 800rpm is controlled, in 60
DEG C reaction 120min, making choice property separation；
(3) after the completion of reacting, separation of solid and liquid is carried out, filter residue is washed with deionized three times, collect filtrate, measured in filtrate
Metal ion content, calculate above-mentioned metal leaching rate (Wherein XcFor leaching rate %, m is separating liquid
Middle tenor g, mrTo separate metal in the dreg content g).It the results are shown in Table 5.
Comparative example 1
Specific method, difference lies in ozone is not passed through in reaction system, the results are shown in Table 1 with reference to embodiment 6.
Comparative example 2
Specific method reference embodiment 12, difference lies in oxidisability additive sodium hypochlorite is free of in reaction system, as a result
It is shown in Table 2.
Comparative example 3
Specific method, difference lies in chlorine is not passed through in reaction system, the results are shown in Table 3 with reference to embodiment 18.
Comparative example 4
Specific method, difference lies in ozone is not passed through in reaction system, the results are shown in Table 4 with reference to embodiment 20.
Comparative example 5
Specific method is with reference to embodiment 22, difference lies in being free of oxidisability additive sodium hypochlorite in separating liquid, the result is shown in
Table 4.
Comparative example 6
Specific method is referring to embodiment 24, difference lies in being free of oxidisability additive hydrogen peroxide in separating liquid, the result is shown in
Table 5.
The leaching rate result of 1 lithium cobaltate cathode waste material of table
The leaching rate result of 2 iron phosphate lithium positive pole waste material of table
The leaching rate result of 3 lithium nickelate of table, LiMn2O4 and LiFePO4 blended anode waste material
The leaching rate result of 4 lithium manganate cathode waste material of table
The leaching rate result of 5 LiMn2O4 of table and LiFePO4 blended anode waste material
It is provided by the invention to be selected from lithium ion battery positive plate from embodiment 1-26 and comparative example 1-6
Property separating Li method, pass through and select separating liquid and waste and old lithium ion battery specifically containing oxidizing additive and acid or alkali
Positive plate is reacted, and lithium is entered solution, and other metal waste residues and aluminium foil in addition to lithium are stayed in solid
Body slag, achievees the purpose that lithium efficiently separates, and the separative efficiency of lithium is high, and more than 93%, disengaging time is short, and the scope of application is wide, into
This is low, and recovery process is pollution-free, is easy to industrialized production.
Oxidizing additive is free of in the separating liquid of comparative example or is not passed through oxidizing gas.Test result shows, institute
There is the high efficiency Selective Separation that comparative example can not realize lithium.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all fall within protection scope of the present invention and the open scope.
Claims (10)
- A kind of 1. method of the Selective Separation lithium from lithium ion battery positive plate, it is characterised in that the described method includes Following steps：(1) lithium ion battery positive plate and separating liquid are reacted, and in reaction system add oxidisability additive and/ Or oxidizing gas is passed through, destroy the Li-O keys in waste lithium ion cell anode material, the crystalline substance of other residual metallic elements Body stable structure, lithium is selectively entered solution, and other metal waste residues and aluminium foil in addition to lithium are stayed in solid slag；(2) separation of solid and liquid, obtains rich lithium solution and solid slag；Wherein, separating liquid is acid solutions of the pH more than 3, or alkaline solutions of the pH below 10.
- 2. according to the method described in claim 1, it is characterized in that, the oxidisability additive for sodium peroxide, sodium hypochlorite, Any a kind or at least two kinds of of combination in hypochlorous acid, sodium peroxydisulfate or hydrogen peroxide；Preferably, the oxidizing gas includes any a kind or at least two kinds of in fluorine gas, chlorine, ozone, oxygen or air Mixed gas；Preferably, the separating liquid is acid solutions of the pH 3~6；Preferably, the separating liquid is alkaline solutions of the pH 7~9.
- 3. method according to claim 1 or 2, it is characterised in that the acid in acid solutions of the pH more than 3 is nothing Any a kind or at least two kinds of of combination in machine acid or organic acid；Preferably, the inorganic acid is any a kind or at least two kinds of of combination in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid；Preferably, the organic acid that the carbon number that the organic acid includes containing or not contain substituent is 1-8；Preferably, the substituent is any a kind or at least two kinds of of combination in fluorine, chlorine, bromine or iodine, preferably fluorine and/or chlorine；Preferably, the number of the substituent is 1~9, preferably 3~6；Preferably, the organic acid be formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, any a kind in enanthic acid or octanoic acid or At least two kinds of combinations.
- 4. according to claim 1-3 any one of them methods, it is characterised in that in alkaline solutions of the pH below 10 Alkali is sodium hydroxide, calcium hydroxide, barium hydroxide, potassium hydroxide, cesium hydroxide, ammonium hydroxide or any a kind of sodium carbonate or at least 2 The combination of kind.
- 5. according to claim 1-4 any one of them methods, it is characterised in that with the separating liquid and oxidisability additive Gross mass is 100% meter, and the mass percentage of oxidisability additive is 0.01%~20%, preferably 0.02%~18%；Preferably, the flow that oxidizing gas is passed through in the reaction system is 0.01~20L/min, preferably 0.02~18L/ min。
- 6. according to claim 1-5 any one of them methods, it is characterised in that the lithium ion battery positive plate is just Pole piece manufacturing scrap material or artificial any a kind or at least two kinds of of the combination disassembled in the positive plate that waste and old lithium ion battery obtains；Preferably, the active material of the lithium ion battery positive plate be cobalt-based positive electrode, it is manganese-based anode material, Ni-based Any a kind or at least two kinds of of combination in positive electrode or LiFePO4, is preferably cobalt acid lithium, lithium nickelate, LiMn2O4, nickel cobalt Any a kind or at least two kinds of of combination in LiMn2O4, nickel cobalt lithium aluminate or LiFePO4；Preferably, the active material of the lithium ion battery positive plate is any in manganese-based anode material or LiFePO4 One or two kinds of combinations.
- 7. according to claim 1-6 any one of them methods, it is characterised in that the lithium ion battery positive plate is with dividing The liquid-solid ratio of chaotropic is 0.1mL/g~200mL/g, preferably 0.5mL/g~150mL/g；Preferably, the temperature of the reaction is 10 DEG C~180 DEG C, is preferably 25 DEG C~150 DEG C；Preferably, the time of the reaction is 10min~300min, is preferably 30min~250min；Preferably, the reaction carries out under agitation, and the speed of the stirring is preferably 100rpm~2500rpm, into one Step is preferably 200rpm~2000rpm.
- 8. according to claim 1-7 any one of them methods, it is characterised in that the mode of the separation of solid and liquid includes sedimentation point From, be separated by filtration or centrifuge in any a kind or at least two kinds of of combination；Preferably, the method further includes the step of solid slag that separation of solid and liquid obtains is dried and is sieved.
- 9. according to claim 1-8 any one of them methods, it is characterised in that the described method comprises the following steps：(1) separating liquid is mixed with lithium ion battery positive plate by the liquid-solid ratio of 0.5mL/g~150mL/g, and reactant Oxidisability additive is added in system and/or is passed through oxidizing gas, reacted under agitation in 25 DEG C~150 DEG C 30min~ 250min, optionally makes lithium enter solution, and other metal waste residues and aluminium foil in addition to lithium are stayed in solid slag；(2) separation of solid and liquid, obtains rich lithium solution and solid slag；Wherein, separating liquid is acid solutions of the pH more than 3, or alkaline solutions of the pH below 10.
- 10. according to claim 1-9 any one of them methods, it is characterised in that the separative efficiency of lithium is more than 93%, preferably More than 98%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109234546A (en) * | 2018-09-17 | 2019-01-18 | 合肥国轩高科动力能源有限公司 | A kind of waste lithium cell positive mix subsequent leaching system and leaching technology |
| CN109852801A (en) * | 2018-12-29 | 2019-06-07 | 桑德集团有限公司 | The recovery method of cobalt and lithium in anode material for lithium-ion batteries |
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| CN111924892A (en) * | 2020-07-24 | 2020-11-13 | 中国科学院过程工程研究所 | Method for selectively recovering lithium ion battery electrode powder |
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| CN112342405A (en) * | 2019-08-09 | 2021-02-09 | 浙江新化化工股份有限公司 | Method for extracting lithium from lithium-containing solution |
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| WO2022116691A1 (en) * | 2020-12-03 | 2022-06-09 | 广东邦普循环科技有限公司 | Preparation method for isophosphorite iron-type iron phosphate and application thereof |
| CN114804049A (en) * | 2022-06-13 | 2022-07-29 | 中南大学 | Method for recovering and obtaining high-purity iron phosphate from waste lithium iron phosphate batteries |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106848473A (en) * | 2017-04-18 | 2017-06-13 | 中科过程（北京）科技有限公司 | A kind of selective recovery method of lithium in waste lithium iron phosphate battery |
| CN106910959A (en) * | 2017-05-04 | 2017-06-30 | 北京科技大学 | A kind of method of selective recovery lithium in waste material from LiFePO4 |
-
2017
- 2017-07-04 CN CN201710537314.9A patent/CN107978814A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106848473A (en) * | 2017-04-18 | 2017-06-13 | 中科过程（北京）科技有限公司 | A kind of selective recovery method of lithium in waste lithium iron phosphate battery |
| CN106910959A (en) * | 2017-05-04 | 2017-06-30 | 北京科技大学 | A kind of method of selective recovery lithium in waste material from LiFePO4 |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109082522B (en) * | 2018-08-15 | 2019-12-13 | 合肥国轩高科动力能源有限公司 | Method for recovering anode powder of waste ternary lithium battery |
| CN109082522A (en) * | 2018-08-15 | 2018-12-25 | 合肥国轩高科动力能源有限公司 | A kind of recovery method of waste and old ternary lithium battery anode powder |
| CN109234546A (en) * | 2018-09-17 | 2019-01-18 | 合肥国轩高科动力能源有限公司 | A kind of waste lithium cell positive mix subsequent leaching system and leaching technology |
| CN109852801A (en) * | 2018-12-29 | 2019-06-07 | 桑德集团有限公司 | The recovery method of cobalt and lithium in anode material for lithium-ion batteries |
| CN109852807A (en) * | 2019-03-18 | 2019-06-07 | 中国科学院过程工程研究所 | A kind of oxidation treatment method of waste and old lithium ion battery |
| CN109921126B (en) * | 2019-04-16 | 2020-07-10 | 常熟理工学院 | Method for recovering active material from waste cobalt-containing lithium ion battery positive electrode material |
| CN109921126A (en) * | 2019-04-16 | 2019-06-21 | 常熟理工学院 | A method of active material is recycled from waste and old anode material for lithium-ion batteries containing cobalt |
| CN110129571A (en) * | 2019-06-11 | 2019-08-16 | 中国科学院过程工程研究所 | A method of extracting valuable metal from waste and old lithium ion battery material |
| CN110474121A (en) * | 2019-07-05 | 2019-11-19 | 常熟理工学院 | A method of dissolving waste and old cobalt acid lithium battery positive electrode |
| CN112342405A (en) * | 2019-08-09 | 2021-02-09 | 浙江新化化工股份有限公司 | Method for extracting lithium from lithium-containing solution |
| CN110615486A (en) * | 2019-09-18 | 2019-12-27 | 陕西科技大学 | Process for selectively extracting valuable metals from waste power lithium batteries and preparing ternary cathode material |
| CN110697673A (en) * | 2019-10-15 | 2020-01-17 | 俞杰 | Method for recycling regenerated lithium iron phosphate from waste power lithium ion battery |
| CN110747340A (en) * | 2019-10-30 | 2020-02-04 | 中国科学院过程工程研究所 | Method for extracting lithium from lithium-containing secondary battery waste |
| US11713494B2 (en) | 2019-11-04 | 2023-08-01 | Basf Corporation | Methods for extracting Li and Ni from a solution |
| CN114630915A (en) * | 2019-11-04 | 2022-06-14 | 巴斯夫公司 | Method for extracting Li and Ni from solution |
| WO2021091929A1 (en) * | 2019-11-04 | 2021-05-14 | Basf Corporation | Methods for extracting li and ni from a solution |
| CN111129636A (en) * | 2019-12-31 | 2020-05-08 | 深圳清华大学研究院 | Regeneration method of waste lithium iron phosphate battery positive electrode material |
| CN111170376A (en) * | 2020-01-15 | 2020-05-19 | 南开大学 | Positive electrode material precursor and preparation method thereof |
| CN111924892A (en) * | 2020-07-24 | 2020-11-13 | 中国科学院过程工程研究所 | Method for selectively recovering lithium ion battery electrode powder |
| CN112038722A (en) * | 2020-08-12 | 2020-12-04 | 中南大学 | Method for efficiently treating waste lithium iron phosphate positive plate |
| CN112207119A (en) * | 2020-10-10 | 2021-01-12 | 荆门市格林美新材料有限公司 | Method for treating battery black powder |
| WO2022116691A1 (en) * | 2020-12-03 | 2022-06-09 | 广东邦普循环科技有限公司 | Preparation method for isophosphorite iron-type iron phosphate and application thereof |
| CN113501510A (en) * | 2021-07-13 | 2021-10-15 | 郑州中科新兴产业技术研究院 | Method for recycling and regenerating anode material of waste lithium iron phosphate battery |
| WO2023029898A1 (en) * | 2021-09-01 | 2023-03-09 | 格林美股份有限公司 | Method for recovering valuable metals from spent lithium-ion batteries |
| CN113800488A (en) * | 2021-10-13 | 2021-12-17 | 中南大学 | Resource recovery method of lithium iron phosphate waste |
| CN113800488B (en) * | 2021-10-13 | 2023-02-21 | 中南大学 | Resource recovery method of lithium iron phosphate waste |
| CN114024054A (en) * | 2021-11-04 | 2022-02-08 | 中国科学院生态环境研究中心 | Green stripping of waste lithium iron phosphate battery positive electrode material by utilizing free radical system |
| CN114024054B (en) * | 2021-11-04 | 2024-02-27 | 中国科学院生态环境研究中心 | Green stripping waste lithium iron phosphate battery anode material by utilizing free radical system |
| CN114214519A (en) * | 2021-11-29 | 2022-03-22 | 上海交通大学 | Method for selectively extracting lithium from lithium ion battery anode material |
| CN114804049A (en) * | 2022-06-13 | 2022-07-29 | 中南大学 | Method for recovering and obtaining high-purity iron phosphate from waste lithium iron phosphate batteries |
| CN114804049B (en) * | 2022-06-13 | 2023-12-12 | 中南大学 | Method for recovering high-purity ferric phosphate from lithium iron phosphate waste batteries |
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