CN109837392A - The recycling and regeneration method of lithium ion battery anode material waste material - Google Patents
The recycling and regeneration method of lithium ion battery anode material waste material Download PDFInfo
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- CN109837392A CN109837392A CN201910071856.0A CN201910071856A CN109837392A CN 109837392 A CN109837392 A CN 109837392A CN 201910071856 A CN201910071856 A CN 201910071856A CN 109837392 A CN109837392 A CN 109837392A
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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
Abstract
The invention discloses the recycling and regeneration method of a kind of lithium ion battery anode material waste material, recovery method is to react lithium ion battery anode material waste material with the acid solution containing reducing agent, it is separated by solid-liquid separation after reaction, obtain leachate and filter residue, realize the leaching of metallic element, the reducing agent contains at least two hydroxyls, and two hydroxyls therein must be located on adjacent carbon atom；Regeneration method includes the recycling of positive material waste, the preparation of precursor solution, the preparation of target positive electrode material precursor, the preparation of the elemental lithium in reclaim liquid phase and target positive electrode.The reducing agent reactivity that the present invention uses is big, environmentally protective, and the less soluble metal ion of high-valence state in useless positive electrode can be reduced into lower valency ion soluble easily in water, and leaching recovery process route is short and at low cost, and leaching rate is high, and extraction time is short；The present invention is based on metallic element closed loop cycles, applied widely convenient for recycling and regenerating.
Description
Technical field
The present invention relates to the recycling of battery recycling technical field more particularly to a kind of lithium ion battery anode material waste material and
Regeneration method.
Background technique
Since 2017, rise as the ownership of superseded power battery is stepped up with the hurricane of the metal prices such as cobalt lithium, moves
It is the higher link of New Energy Industry chain attention rate that the recycling of power battery and echelon, which utilize,.Industry, state are recycled for power battery
Family has put into effect many policies and regulations.On July 25th, 2018, seven ministries and commissions such as Ministry of Industry and Information, Department of Science and Technology combine and have issued " new about carrying out
The notice of energy automobile power accumulator recycling pilot work ".
According to the data of EVTank, for new-energy automobile to the demand of power battery, the year two thousand twenty will be more than 120Gwh,
2022 will be more than 210Gwh, and wherein NCM ternary battery will be more than 70%.However, average life (the decaying of power battery
To 80%) being 4 years or so, it will welcome later within 2018 and eliminate tide.The yield of Chinese theoretical power battery, the year two thousand twenty are up to
25.7 ten thousand tons, reach 42.2 ten thousand tons within 2022.With the increase of electric car ownership, the quantity for scrapping power battery will continue
Increase.
It has been reported that by disassemble extract scrap lithium in ternary power battery, cobalt, nickel, manganese, copper, aluminium, graphite, every
The materials such as film can theoretically realize the economic well-being of workers and staff of about 4.29 ten thousand yuan (changing with the fluctuation of metal price) per ton, dismantling
Recycling has economic feasibility.
The dismantling recycling of power battery includes the pretreatment process such as refuse battery electric discharge, dismantling, sorting, pyrolysis degumming, then is passed through
It crosses specific recovery process and obtains metal values material.Existing recovery process, including dry method, wet process and Bioleaching method
More Deng, research at present and application is wet process.
Chinese patent (CN104659438A) discloses a kind of method for preparing ternary precursor using refuse battery, including elder generation
Nickel cobalt is leached with sulfuric acid dissolution positive electrode, then removes other metal impurities with the method for extraction, and again by extraction
Cobaltous sulfate and nickel sulfate are separated, nickel sulfate, cobaltous sulfate are finally mixed and supplements manganese sulfate and prepares ternary precursor.Although this method
Realize nickel, cobalt recycles, but the recycling for not solving the problems, such as lithium and manganese.
Chinese patent (CN102665912A) also by the method for extraction from refuse battery tertiary cathode material Call Provision and
Manganese, and the extract of cobalt and manganese is prepared into Co-Mn-Br liquid-phase catalyst (abbreviation CMB catalyst).Similarly, this method
Realize the recycling of the part metals element such as cobalt and manganese.Moreover extraction is related to solvent extraction and solvent elution, process are numerous
It is trivial, it is big to the demand of organic solvent and water.How to realize the purified treatment and recycling of water, and is a great problem.
Chinese patent (CN102956935A) passes through " precipitation method " for the metallic element one in useless power battery ternary material
One is separated and recovered from.Although this method realizes in ternary material the recycling of whole metallic elements, but be related to multi-step chemical reaction,
A variety of chemical reagent need repeatedly the accurately pH value of control solution, and the inorganic salts of the metallic element recycled cannot be directly used to three
The preparation of first material, wherein the lithium salts recycled, cobalt salt, nickel salt, manganese salt are generally lithium phosphate, cobalt sulfide, nickel oxalate and carbon respectively
Sour manganese.
Chinese patent (CN106785174A) discloses one kind and is based on electrochemical method from useless ternary material for metal one
One technique for leaching and recycling.Anode waste powder is compressed into tablet form as cathode by the technique, to contain H+ and K+ and/or Na+
Solution as electrolyte, at a dc voltage, carry out electrochemical reduction leaching, obtain the electrolyte containing each metal ion.It should
Process metal leaching rate is high, without secondary pollution, still, when the cathode plate of anode waste powder compacting is thicker (10cm), pressure
Real powder gradually falls off, and pole plate failure cannot achieve electrochemical leaching.Production efficiency is low, and large-scale production is difficult to realize.
Chinese patent (CN104868190A) disclose it is a kind of in the organic acid soln containing reducing agent by useless positive material
The method that metal in material leaches one by one and realizes closed loop cycle.This method is using generations such as organic acids such as formic acid, trichloroacetic acid
For inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, to avoid the secondary pollution caused by environment；Use hydrogen peroxide, sodium sulfite etc.
The less soluble metal ion of high-valence state is reduced into the ion soluble easily in water of lower valency, improves metal by conventional reduction agent
Leaching rate.Organic acid price is higher, leads to this method cost increase, and introduce organic pollutant in water, and purification is difficult；Peroxide
Compound reducing agent is unstable, a large amount of to use, and is security risk；Using sodium sulfite as reducing agent, then a large amount of sodium sulphate of by-product.
In short, up to now, not finding a kind of tertiary cathode of waste and old power battery at low cost and short process route also
The reclaiming technology of material.And for the valuable element high efficiency extraction of waste and old ternary material, material property reparation, residue
The core technologies such as matter harmless treatment are especially deficient.
Summary of the invention
The present invention proposes that a kind of recycling of lithium ion battery anode material waste material and regeneration method are asked to solve above-mentioned technology
Topic.
In order to achieve the above object, the technical scheme adopted by the invention is as follows:
According to a first aspect of the embodiments of the present invention, a kind of recycling side of lithium ion battery anode material waste material is provided
Lithium ion battery anode material waste material is reacted with the acid solution containing reducing agent, is separated by solid-liquid separation after reaction by method,
Leachate and filter residue are obtained, realizes the leaching of metallic element in lithium ion cell anode waste；
The reducing agent includes at least one compound with following molecular structural formula:
Wherein, R1, R2, R3, R4 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl；Or R1, R2,
R3, R4 are independently selected from the group containing at least one of boron, silicon, nitrogen, phosphorus, oxygen, sulphur, fluorine, chlorine, bromine and iodine element；Its
In, R1, R2, R3, R4 are independent substituent group or in which two adjacent group joint cyclization.
Preferably, R1, R2, R3, R4 are independent substituent group in the molecular structural formula of the compound, and R1, R2,
The alkyl that R3, R4 are respectively hydrogen or carbon atom number is 1~4.
Preferably, the reducing agent further includes that following substance is any one or more of: sulfur dioxide, sulfurous acid, Asia
Sodium sulphate, ammonium sulfite, sodium thiosulfate, hydrogen peroxide, glucose, sucrose, cellulose, cornstalk.
As a preference, the lithium ion battery anode material waste material has general formula Li1+δ[Ni1-x-y-zCoxMnyMz]
O2-βPβ, wherein doped chemical M be metallic element Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu,
At least one of Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm, doped chemical P be F or S, 0≤δ≤0.2,0≤β≤
0.5,0≤x≤1,0≤y≤1,0≤z≤0.2, and 0 < x+y+z≤1.
There is general formula Li as another preferred, described lithium ion battery anode material waste material1+η[Mn2-aM′a]O4-mPm,
In, doped chemical M ' be metallic element Ni, Co, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu,
At least one of Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm, doped chemical P be F or S, 0≤η≤0.2,0≤a≤
2,0≤m≤0.5.
There is general formula xLi as another preferred, described lithium ion battery anode material waste material2MnO3·(1-x)LiNO2,
Wherein, doped chemical N be metallic element Ni, Co, Mn, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe,
At least one of Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm, 0 < x < 1.
Preferably, the acid solution is inorganic acid and/or organic acid.
As a further preference, the inorganic acid is that sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid are any one or more of.
As a further preference, the organic acid is oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid
It is any one or more of.
Preferably, further comprising the steps of: residue washing several times after obtaining leachate and filter residue, washing lotion is obtained after washing
With washing filter residue, washing lotion is put into leachate mixing.
Washing filter residue is reacted with the acid solution containing reducing agent preferably, further comprising the steps of:, stirs simultaneously water
Bath heating, is separated by solid-liquid separation after reaction, obtains secondary leachate and secondary response filter residue, realizes metallic element in washing filter residue
Leaching.
Preferably, the solid-to-liquid ratio of the lithium ion battery anode material waste material and the acid solution containing reducing agent is 10
~2000g/L.
Preferably, reaction temperature is 0~120 DEG C, the reaction time is 0.1~24 hour.
According to a second aspect of the embodiments of the present invention, a kind of regeneration method of anode material for lithium-ion batteries is provided, is wrapped
Include following steps:
(1) recycling of positive material waste: according to claim 1 to lithium ion cell positive material described in 13 any one
Expect that the recovery method of waste material handles lithium ion battery anode material waste material, obtains leachate and filter residue；
(2) preparation of precursor solution: according to the element composition and content in leachate, each metal member in leachate is adjusted
The content of element, keeps the molar ratio of each metallic element consistent with the chemical formula of target positive electrode, obtains precursor solution；
(3) target the preparation of target positive electrode material precursor: is being prepared just by precursor preparation technique precursor solution
Pole material precursor, while obtaining solution containing lithium ion；
(4) elemental lithium in reclaim liquid phase, obtains Li source compound；
(5) preparation of target positive electrode: by positive electrode burning process, the target anode material in step (3) is utilized
Target positive electrode is made in the Li source compound recycled in material precursor and step (4).
Preferably, the chemical formula of target positive electrode is Li in the step (2)1+δ[Ni1-x-y-zCoxMnyMz]O2、
Li1+η[Mn2-aMa]O4Or xLi2MnO3·(1-x)LiNO2, according to the chemical formula of target positive electrode, it is added into leachate
Nickel, cobalt, the water soluble salt of manganese and M, M or N one or more of water soluble salt to adjust each metal in leachate
The content of element, wherein doped chemical M, M or N be metallic element Ni, Co, Mn, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In,
Any one of Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm.
Preferably, the preparation method of target positive electrode material precursor is coprecipitation in the step (3).
Preferably, the step of coprecipitation are as follows: ammonia spirit is added into precursor solution and/or buck is molten
Coprecipitation reaction occurs for liquid, metal ion in addition to lithium, after separation of solid and liquid, respectively obtain target positive electrode material precursor and
Solution containing lithium ion.
Preferably, the ammonia spirit be containing in ammonia, ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate and ammonium sulfate extremely
A kind of few aqueous solution, concentration are 0.1~1mol/L.
Preferably, the aqueous alkali be containing in sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate at least
A kind of aqueous solution, concentration are 0.5~5mol/L.
Preferably, the pH value of mixed solution is 9~12.5, the temperature of reaction is 30~80 DEG C, mixing speed when reaction
For 100~2000rpm, the reaction time is 1~24 hour.
Preferably, being passed through inert gas or nitrogen protection in reaction process.
Preferably, the method for the elemental lithium in the step (4) in reclaim liquid phase, including lead into solution containing lithium ion
Enter carbon dioxide or carbonate, phosphate, fluoride salt is added.
Preferably, the Li source compound obtained in the step (4) is the hydroxyl oxidation of the hydroxide of lithium, lithium
Object, the oxide of lithium, the sulfide of lithium, the carbonate of lithium, the nitrate of lithium, the acetate of lithium and lithium halide at least
It is a kind of.
Preferably, being further comprised the steps of: after the step (5) in the cladding Louis's alkalization of target positive electrode outer surface
Close object.
Compared with prior art, the reducing agent reactivity that the present invention uses is big, nontoxic, environmentally protective, can incite somebody to action
The less soluble metal ion of high-valence state is reduced into the ion soluble easily in water of lower valency, by-product after reaction in useless positive electrode
It is gas or low boiling point small organic molecule, is easy to remove from system；It is short and at low cost to leach recovery process route, passes through
Single step reaction can leach the metal ion in useless positive electrode, and leaching rate is high, and extraction time is short；The present invention is based on metals
Element closed loop cycle, the main metal element in useless positive electrode technology can recycle and be regenerated through the invention, and applicable
Range is wide, and the positive electrode of recuperable lithium ion secondary battery includes layer structure, spinel structure and polyanion class
Equal positive electrodes.
Detailed description of the invention
Fig. 1 is a kind of flow chart of the recovery method of lithium ion battery anode material waste material of the present invention；
Fig. 2 is a kind of flow chart of the regeneration method of anode material for lithium-ion batteries of the present invention.
Specific embodiment
Below with reference to specific embodiment shown in the drawings, the present invention will be described in detail.But these embodiments are simultaneously
The present invention is not limited, structure that those skilled in the art are made according to these embodiments, method or functionally
Transformation is included within the scope of protection of the present invention.
It is only to be not intended to limit the invention merely for for the purpose of describing particular embodiments in terminology used in the present invention.
It is also intended in the present invention and the "an" of singular used in the attached claims, " described " and "the" including majority
Form, unless the context clearly indicates other meaning.It is also understood that term "and/or" used herein refers to and wraps
It may be combined containing one or more associated any or all of project listed.
The embodiment of the present invention in a first aspect, a kind of recovery method of lithium ion battery anode material waste material, including it is as follows
Step:
(a) lithium ion battery anode material waste material is reacted with the acid solution containing reducing agent, heating water bath；
(b) it is separated by solid-liquid separation, obtains leachate and filter residue, realize the leaching of metallic element in lithium ion cell anode waste
Out；The reducing agent includes at least one compound with following molecular structural formula:
Wherein, R1, R2, R3, R4 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl；Or R1, R2,
R3, R4 are independently selected from the group containing at least one of boron, silicon, nitrogen, phosphorus, oxygen, sulphur, fluorine, chlorine, bromine and iodine element；Its
In, R1, R2, R3, R4 are independent substituent group or in which two adjacent group joint cyclization.
The present invention provides a kind of reducing agent and extract technology, under the action of acidic environment and the reducing agent, lithium-ion electric
The metal ions such as nickel, cobalt, manganese, lithium in the positive material waste of pond can be leached one by one, and leaching rate is high, can achieve 98%
More than.
Reducing agent of the present invention contains at least two hydroxyls in molecule, and two hydroxyls therein must distinguish position
In on adjacent carbon atom, including but not limited to following compounds:
Preferably, R1, R2, R3, R4 are independent substituent group in the molecular structural formula of compound, and R1, R2, R3, R4
It can be respectively the alkyl that hydrogen or carbon atom number are 1~4.The reducing agent of above structure is easy purchase and cost on the market
It is low, meet industrial production demand；In addition, the reducing agent of above structure be oxidized after product, molecule is small and structure is simple, example
Such as gas molecule, by-product can be removed by the method for gas-liquid separation, for another example low-boiling compound, by distilling or subtracting
The method of pressure distillation is removed from system.
Reducing agent can be one of above compound or a variety of, can also include any one of following substance or more
Kind: sulfur dioxide, sulfurous acid, sodium sulfite, ammonium sulfite, sodium thiosulfate, hydrogen peroxide, glucose, sucrose, cellulose,
Cornstalk.For example, reducing agent can be single compound glycerine, it is also possible to the mixture of ethylene glycol and 1,2-PD,
It can also be that ethylene glycol and sulfur dioxide or glycerine and hydrogen peroxide etc. combine.The selection of reducing agent, with environmental protection, be efficiently
Standard.
As raw material, the signified lithium ion battery anode material waste material of the present invention may include in waste and old lithium ion battery
The positive material waste generated in positive electrode and positive electrode preparation or lithium ion battery manufacturing process.
Currently, the positive electrode of power battery is mainly lithium transition-metal oxide, the LiCoO including layer structure2、
Li1+δ[Ni1-x-y-zCoxMnyMz]O2、Li1+δ[Ni1-x-yCoxAly]O2, the LiMn of spinel structure2O4, polyanion class anode material
The LiFePO of material such as olivine structural4, instantly also in the lithium-rich manganese-based anode material such as xLi in research and development stage2MnO3.(1-
x)LiMO2(M=Ni, Co, Mn etc. and 5V positive electrode such as LiNi0.5Mn1.5O4、LiNiPO4、LiCoPO4Equal materials.
In addition, being to improve one of the important means of material electrochemical performance to positive electrode surface coating modification.Commonly
Covering material has ZnO, ZrO2、AlPO4、Li3PO4、Al2O3、AlF3、SiO2、TiO2, MgO and boron lithium compound Li2O-2B2O3
Deng going back organic polymer material such as polyaniline.
Other than element composition and crystal structure are different, positive electrode can also be there are many geometry: such as nucleocapsid knot
The ball part of structure, positive electrode powder particle is made of the nickelic positive electrode of high capacity, such as LiNi0.8Co0.2O2Or
LiNi0.8Co0.1Mn0.1O2, the spherical shell part of powder particle is made of the positive electrode that thermal stability is good and has extended cycle life, example
Such as LiNi0.5Mn0.5O2；It is open that there are also United States Patent (USP) (application No. is US13/978067 and application No. is US13/978041 etc.)
A kind of high capacity concentration gradient positive electrode.
Lithium ion battery anode material waste material of the present invention includes all positive material wastes mentioned above.Lithium from
Sub- battery anode material waste material can substantially be divided into following three types.
The lithium ion battery anode material waste material of the first kind has general formula Li1+δ[Ni1-x-y-zCoxMnyMz]O2-βPβ, wherein
Doped chemical M be metallic element Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb,
At least one of Mo, Cd, W, La, Ce, Nd and Sm, doped chemical P be F or S, 0≤δ≤0.2,0≤β≤0.5,0≤x≤1,
0≤y≤1,0≤z≤0.2, and 0 < x+y+z≤1.
As β=0, general formula shows as Li1+δ[Ni1-x-y-zCoxMnyMz]O2.At this point, common material is such as:
LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.5Co0.25Mn0.25O2、LiNi0.5Co0.2Mn0.3O2、
LiNi0.815Co0.15Al0.035O2Deng.
As 0 < β≤0.5, nonmetalloid such as F or S adulterate oxygen position, and the thermal stability and circulation of material can be improved
Stability.It is generally preferable that the doping for control F or S accounts within 5% (molar content) of oxygen element amount.Doping
Very few, unobvious to the performance improvement of material, doping is excessive, may reduce the electronic capability of leading of material, can also inhibit material
The capacity of material plays.
The lithium ion battery anode material waste material of second class has general formula Li1+η[Mn2-aM′a]O4-mPm, wherein doped chemical
M ' be metallic element Ni, Co, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb,
At least one of Mo, Cd, W, La, Ce, Nd and Sm, doped chemical P are F or S, 0≤η≤0.2,0≤a≤2,0≤m≤0.5.
As m=0, general formula shows as Li1+η[Mn2-aM′a]O4.As 0 < m≤0.5, nonmetalloid such as F or S mix
The thermal stability and cyclical stability of material can be improved in miscellaneous oxygen position.
The lithium ion battery anode material waste material of third class has general formula xLi2MnO3·(1-x)LiNO2, wherein doping member
Plain N be metallic element Ni, Co, Mn, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr,
At least one of Nb, Mo, Cd, W, La, Ce, Nd and Sm, 0 < x < 1.In addition, it can include with nonmetalloid such as F or S
Adulterate the lithium-rich manganese base material of oxygen position.
The extraction of lithium ion battery anode material waste material can make lithium-ion electric by processes such as dismantling, cracking, screenings
The powder of pond positive material waste is separated with collector；After old and useless battery can also being disassembled, pass through the side of organic solution immersion
Formula separates the powder of lithium ion battery anode material waste material with collector.How the present invention is to obtaining lithium ion cell positive
The method of material waste is not construed as limiting.
It generally, will also by way of carbonic ester immersion or rinse when the extraction of lithium ion battery anode material waste material
Electrolyte residual component such as lithium hexafluoro phosphate in the lithium ion battery anode material waste feed powder end is removed and is recycled.The present invention
The method of the electrolyte residual component how removed in lithium ion battery anode material waste material is not construed as limiting.
Generally, it when the extraction of lithium ion battery anode material waste material, also needs to lithium ion battery anode material waste material
Powder is dried, to remove remaining organic solvent in powder.
There is provided the acid solution of reaction media for lithium ion battery anode material waste material what reducing agent can be inorganic acid, have
The mixture of machine acid or organic acid and inorganic acid.The usage amount of acid is related to the molecular formula of lithium ion battery anode material waste material.
Generally, excessive acid is conducive to the raising of leaching rate.But it neutralizes excessive acid to need to consume alkali and generate solid by-product for example
Sodium sulphate, ammonium sulfate.For a variety of different lithium ion battery anode material waste material, sour usage amount be must optimize it is main
One of technological parameter.
The inorganic acid can be carborane acid (H [CHB11Cl11]), hydrosulphuric acid (H2S), Perthiocarbonate (H2CS4), sulphur
For carbonic acid (H2CS3), hydrogen cyanide (HCN), selenium cyanic acid (HSeCN), thiocyanic acid (HSCN), fluoboric acid (HBF4), fluosilicic acid
(H2SiF6), hexafluorophosphoric acid (HPF6), hydrofluoric acid (HF), hydrochloric acid (HCl), hydrobromic acid (HBr), hydroiodic acid (HI), meta-aluminic acid
(HAlO2), tetrahydroxy close aluminium (III) acid (HAl (OH)4), arsenic acid (H3AsO4), metaarsenous acid (HAsO2), arsenious acid (H3AsO3)、
Pyroarsenic acid (H4As2O7), boric acid (H3BO3), metaboric acid ((HBO2)n), tetraboric acid (H2B4O7), perboric acid (HBO3), 12 tungsten boron
Acid (H5BW12O40), bromic acid (HBrO3), bromous acid (HBrO2), hypobromous acid (HBrO), hyperbromic acid (HBrO4), orthocarbonic acid
(H4CO4), cross two carbonic acid (H2C2O6), percarbonic acid (H2CO4Or H2CO3·H2O2), it is chloric acid (HClO3), perchloric acid (HClO4), sub-
Chloric acid (HClO2), hypochlorous acid (HClO), fulminic acid (HONC), cyanic acid (HOCN), isocyanic acid (HNCO), acid iodide (HIO3), hypoiodous acid
(HIO or IOH), metaperiodic acid (HIO4), periodic acid (H5IO6), burnt periodic acid (H4I2O9), nitric acid (HNO3), nitrous acid
(HNO2), phosphoric acid (H3PO4), former phosphoric acid (H5PO5), metaphosphoric acid (HPO3)n, phosphorous acid (H3PO3), pyrophosphorous acid (H4P2O5), partially
Phosphorous acid (HPO2), hypophosphorous acid (H3PO2), hypophosphoric acid (H4P2O6), pyrophosphoric acid (H4P2O7), sulfuric acid (H2SO4), sulfurous acid
(H2SO3), thiosulfuric acid (H2S2O3), pyrosulfuric acid (H2S2O7), sulphoxylic acid (H2SO2), polythionic acid (H2SxO6, x=2~6), it is former
Sulfuric acid (H6SO6), hydrosulfurous acid (H2S2O4), permonosulphuric acid (H2SO5), peroxy-disulfuric acid (H2S2O8), chlorosulfonic acid (HSO3Cl), fluorine
Sulfonic acid (HSO3F), metasilicic acid (H2SiO3Or SiO2·H2O), orthosilicic acid (H4SiO4), two metasilicic acid (H2Si2O5Or 2SiO2·
H2) and disilicic acid (H O6Si2O7Or 2SiO2·3H2O) any one or more of, preferably sulfuric acid, hydrochloric acid, nitric acid, in phosphoric acid
It is any one or more.
The organic acid can be oxalic acid, formic acid, acetic acid, propionic acid, succinic acid, trifluoracetic acid, trifluoromethanesulfonic acid, methylsulphur
Acid, mandelic acid, methylsulfuric acid, ethyl sulfuric acid, oleic acid, stearic acid, acrylic acid, maleic acid, citric acid, bis- (catechol) boron
Sour, double oxalic acid boric acid, dimalonic acid boric acid, three (pentafluoroethyl group) three fluorophosphoric acid, three fluorophosphoric acid of triethyl group, four cyano boric acid, wine
At least one in stone acid, malic acid, citric acid, ascorbic acid, benzoic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, salicylic acid and caffeic acid
Kind, preferably oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of.
The removal process of lithium ion battery anode material waste material, lithium ion battery anode material waste material and contains reducing agent
The solid-to-liquid ratio of acid solution can be 10~2000g/L, preferably 100~1000g/L, further preferred 200~600g/L.Though
Right solid-to-liquid ratio is low can to accelerate reaction progress, be conducive to the leaching of metallic element, but water consumption is big, worth choosing；Solid-to-liquid ratio is too high,
It then may cause reaction not exclusively, metallic element cannot be leached all.
The reducing leaching of lithium ion battery anode material waste feed powder material carries out in the acid solution containing reducing agent, reduction
The usage amount of agent is related to the molecular formula of lithium ion battery anode material waste material, and different lithium ion battery anode material waste material needs
The amount for the reducing agent wanted is different.The additive amount of reducing agent is according to the reaction equation of reducing agent and lithium ion battery anode material waste material
Stoichiometrically calculate.In order to guarantee that Leach reaction carries out completely it is contemplated that reducing agent is slightly excessive.It can after fully reacting
Extra reducing agent is removed in a manner of by distilling or being evaporated under reduced pressure.If the boiling point of reducing agent is higher, by distilling or subtracting
The method of pressure distillation is not easy to remove, it may be considered that lithium ion battery anode material waste material is suitably excessive.
The removal process of lithium ion battery anode material waste material, reaction temperature may be controlled to 0~120 DEG C, preferably 25~
99 DEG C, further preferred 45~95 DEG C.Generally, reducing leaching reaction is exothermic reaction, maintains reaction less energy intensive.If anti-
It answers heat release obvious, controls the addition speed of reducing agent, reducing agent is preferably added portionwise, or give and cool down.
The removal process of lithium ion battery anode material waste material, reaction time may be controlled to 0.1~24 hour, preferably 1
~6 hours, further preferred 2~4 hours.Reaction rate is big, reaction can be completed, within a very short time usually in order to ensure anti-
It should be completely general that the reaction time is appropriately extended.
Reducing leaching reaction carries out under stiring, and agitating mode and mixing speed are not particularly limited.
Reducing leaching reaction consersion unit used, however, it would be possible to use all applicable containers and pressure vessel,
The material of container need to be selected according to the physico-chemical property of reactant, preferably with the material with acid-resistant property.The useless positive material
The reducing leaching reaction of feed powder material can in batches, it is semicontinuous or be carried out continuously.
By above-mentioned reaction equation (1) it is found that reducing leaching may generate by-product CO2.With the continuous progress of reaction,
CO2Amount be continuously increased, will lead to pressure in reaction vessel and constantly rise.Consider to keep the safety in production and reduce the manufacture of equipment at
This, can be slowly added into a certain reactant on one side to control reaction rate, pass through release CO on one side2Method so that reaction hold
Pressure in device is stablized in certain level.
It, can modes remove unreacted reactant or reaction is secondary by distilling, being evaporated under reduced pressure etc. after fully reacting
Product；It can also connecting next process without any processing.
It, can be to obtain washing lotion and washing after washing comprising steps of residue washing is multiple after obtaining leachate and filter residue
Filter residue, washing lotion are put into leachate mixing.Washing filter residue run up to it is a certain amount of after, washing and can be contained into the acid of reducing agent at filter residue
Property solution carry out secondary response, stir and heating water bath, be separated by solid-liquid separation after reaction, obtain secondary leachate and secondary response
Filter residue realizes the leaching of metallic element in washing filter residue.
It is described further below by recovery method of the specific embodiment to above-mentioned lithium ion battery anode material waste material.
Embodiment 1
Piece of fetching is used for the spent lithium-ion secondary batteries of electric car, and the chemical formula of positive electrode active materials is
LiNi0.5Co0.2Mn0.3O2.Salt water disassembles battery after impregnating battery discharge, and is dissolved out by way of solvent soaking and remain on pole
Electrolyte in piece dries pole piece in an oven, and the binder being then pyrolyzed in pole piece obtains lithium ion battery anode material waste
The powder (mixing conductive carbon material) of material.
The sulfuric acid solution that mass percentage is 50% is prepared, the reducing agent ethylene glycol of stoichiometry is added, is measured
Acid solution of the 1010mL containing reducing agent is in container；The useless positive electrode powder of 500.0g is weighed, is slowly added in said vesse
In, solid-to-liquid ratio about 500g/L.Stirring and heating in water bath for reaction container are opened, bath temperature is 95 DEG C, cooling after reaction 4 hours
Cooling.Filtering is separated by solid-liquid separation with realizing, respectively obtains leachate and filter residue.It washs filter residue for several times, collects washing lotion and and leachate
Mixing.Liquid phase sample is taken, with the concentration of the metallic elements such as ICP-OES analysis nickel, cobalt, manganese, lithium, calculates the leaching of each metallic element
Extracting rate, is as a result respectively as follows: Ni, and 99.2%；Co, 98.1%；Mn, 98.3%；Li, 99.5%.Filtered filter residue is collected, is accumulated
To a certain amount, reducing leaching again.
Embodiment 2
The unqualified lithium ion secondary battery product in two panels production process is taken, the chemical formula of positive electrode active materials is
LiNi0.6Co0.2Mn0.2O2.Salt water disassembles battery after impregnating battery discharge, and is dissolved out by way of solvent soaking and remain on pole
Electrolyte in piece dries pole piece in an oven, and the binder being then pyrolyzed in pole piece obtains lithium ion battery anode material waste
The powder (mixing conductive carbon material) of material.
100.0g powder is weighed, is incorporated in reaction vessel.The sulfuric acid solution that mass percentage is 30% is prepared, is added
Reducing agent glycerine, the mass percentage of reducing agent are 5.0%.Acid solution containing reducing agent is slowly added into above-mentioned anti-
Answer container, solid-to-liquid ratio about 200g/L.It opens stirring simultaneously and heats reaction vessel, heat source temperature is 120 DEG C, is reacted 24 hours
Afterwards, it cools.Filtering is separated by solid-liquid separation with realizing, respectively obtains leachate and filter residue.It washs filter residue for several times, collects washing lotion simultaneously
It is mixed with leachate.Liquid phase sample is taken, with the concentration of the metallic elements such as ICP-OES analysis nickel, cobalt, manganese, lithium, calculates each metal
The leaching rate of element, is as a result respectively as follows: Ni, and 95.2%；Co, 95.8%；Mn, 95.3%；Li, 98.7%.It collects filtered
A certain amount is arrived in filter residue, accumulation, again reducing leaching.
Embodiment 3
The lithium ion battery anode material waste material for taking 1kg to generate in Material Manufacturing Process, the change of positive electrode active materials
Formula is LiNi0.5Co0.2Mn0.3O2。
The sulfuric acid solution that mass percentage is 50% is prepared, reducing agent 1,2- pentanediol, the quality hundred of reducing agent is added
Dividing content is 10.0%, measures acid solution of the 1000mL containing reducing agent in container；Solid-to-liquid ratio about 1000g/L.Open stirring
And heating in water bath for reaction container, bath temperature are 45 DEG C, after reaction 1 hour, are cooled.Filtering is separated by solid-liquid separation with realizing, point
Leachate and filter residue are not obtained.It washs filter residue for several times, collect washing lotion and is mixed with leachate.Liquid phase sample is taken, ICP-OES is used
The concentration for analyzing nickel, cobalt, the metallic elements such as manganese, calculates the leaching rate of each metallic element, is as a result respectively as follows: Ni, and 53.2%；Co,
55.1%；Mn, 53.3%；Li, 73.5%.
Filtered filter residue is collected, carries out Leach reaction again.The sulfuric acid solution that mass percentage is 50% is prepared, is added
Enter the reducing agent ethylene glycol of stoichiometry, measures acid solution of the about 500mL containing reducing agent in container；It is above-mentioned to weigh 300.0g
Filter residue (accurate to weigh, to carry out drying and processing), is slowly added in said vesse, solid-to-liquid ratio about 600g/L.Open stirring simultaneously
Heating in water bath for reaction container, bath temperature are 95 DEG C, after reaction 2 hours, are cooled.Filtering is separated by solid-liquid separation with realizing, respectively
Obtain leachate and filter residue.It washs filter residue for several times, collect washing lotion and is mixed with leachate.Liquid phase sample is taken, with ICP-OES points
The concentration for analysing the metallic elements such as nickel, cobalt, manganese, lithium, calculates the leaching rate of each metallic element, and second of leaching result is respectively as follows: Ni,
99.2%；Co, 99.1%；Mn, 99.5%；Li, 99.3%.
Embodiment 4
Piece of fetching is used for the spent lithium-ion secondary batteries of electric car, the change of the main positive electrode active materials of percentage of batteries
Formula is LiNi0.5Co0.2Mn0.3O2, the chemical formula of the main positive electrode active materials of percentage of batteries is LiMn2O4.Salt water impregnates electricity
Battery is disassembled after tank discharge, and dissolves out the electrolyte remained in pole piece by way of solvent soaking, dries pole in an oven
Piece, the binder being then pyrolyzed in pole piece, the mixture for obtaining the powder of two kinds of lithium ion battery anode material waste material (mix and lead
Electrical carbon material).Sampling, with the content of the elements such as nickel, cobalt, manganese, lithium in ICP-OES analysis mixed powder.
The sulfuric acid solution that mass percentage is 50% is prepared, reducing agent ethylene glycol is added, the quality percentage of reducing agent contains
Amount is 5%.Acid solution of the 1000mL containing reducing agent is measured in container；100.0g powder is weighed, is slowly added in above-mentioned appearance
In device, solid-to-liquid ratio about 100g/L.Stirring and heating in water bath for reaction container are opened, bath temperature is 99 DEG C, cold after reaction 1 hour
But cool down.Filtering is separated by solid-liquid separation with realizing, respectively obtains leachate and filter residue.Wash filter residue for several times, collect washing lotion and with leaching
Liquid mixing.Liquid phase sample is taken, with the concentration of the metallic elements such as ICP-OES analysis nickel, cobalt, manganese, lithium, calculates each metallic element
Leaching rate, is as a result respectively as follows: Ni, and 98.2%；Co, 98.5%；Mn, 98.1%；Li, 99.1%.
Embodiment 5
Access piece spent lithium-ion secondary batteries, the chemical formula of positive electrode active materials are as follows: LiNi0.8Co0.1Mn0.1O2.Salt
Water disassembles battery after impregnating battery discharge, and the electrolyte remained in pole piece is dissolved out by way of solvent soaking, in baking oven
Middle dry pole piece, the binder being then pyrolyzed in pole piece, the powder for obtaining lithium ion battery anode material waste material (mix conductive carbon
Material).
500mL acetic acid is taken, the reducing agent 1,2-PD and sodium sulfite (molar ratio 3:1) of stoichiometry is added.It measures
The above-mentioned acid solution containing reducing agent is in reaction vessel.The powder of 5.0g lithium ion battery anode material waste material is weighed, slowly
It is incorporated in said vesse, solid-to-liquid ratio about 10g/L.Stirring is opened, temperature is 25 DEG C, and after reaction 6 hours, filtering is solid to realize
Liquid separation, respectively obtains leachate and filter residue.It washs filter residue for several times, collect washing lotion and is mixed with leachate.Liquid phase sample is taken, is used
ICP-OES analyzes the concentration of the metallic elements such as nickel, cobalt, manganese, lithium, calculates the leaching rate of each metallic element, is as a result respectively as follows: Ni,
56.8%；Co, 55.4%；Mn, 51.6%；Li, 75.0%.
Embodiment 6
Access piece spent lithium-ion secondary batteries, can not determine the chemical formula of positive electrode.After salt water impregnates battery discharge
Battery is disassembled, and dissolves out the electrolyte remained in pole piece by way of solvent soaking, dries pole piece in an oven, it is then hot
The binder in pole piece is solved, the powder (mixing conductive carbon material) of lithium ion battery anode material waste material is obtained, is sampled, is used
ICP-OES analyzes the content of the elements such as nickel, cobalt, manganese, lithium, aluminium, zirconium, yttrium, iron in mixed powder.
The sulfuric acid solution that preparation mass percentage is 20%, addition reducing agent ethylene glycol, mass percentage 5%,
Acid solution of the 1000mL containing reducing agent is measured in container；The powder of 200.0g lithium ion battery anode material waste material is weighed,
It is slowly added in said vesse, solid-to-liquid ratio about 200g/L.Open stirring and heating in water bath for reaction container, reaction temperature 80
DEG C, after reaction 4 hours, cool.Filtering is separated by solid-liquid separation with realizing, respectively obtains leachate and filter residue.Wash filter residue number
It is secondary, it collects washing lotion and is mixed with leachate.Liquid phase sample is taken, analyzes the dense of the metallic elements such as nickel, cobalt, manganese, lithium with ICP-OES
Degree, calculates the leaching rate of each metallic element, is as a result respectively as follows: Ni, and 99.3%；Co, 98.0%；Mn, 99.1%；Li, 99.0%.
Embodiment 7
It fetches piece spent lithium-ion secondary batteries, positive electrode is lithium-rich manganese base material, the mass percentage of lithium is 8~
10%, nickel, cobalt, manganese gross mass percentage composition be 50~60%.Salt water disassembles battery after impregnating battery discharge, and passes through solvent
The mode of immersion dissolves out the electrolyte remained in pole piece, dries pole piece in an oven, and the binder being then pyrolyzed in pole piece obtains
To the powder (mixing conductive carbon material) of lithium ion battery anode material waste material, sampling, in ICP-OES analysis mixed powder
The content of the elements such as nickel, cobalt, manganese, lithium, aluminium, zirconium, yttrium, iron.
The mixed aqueous solution of oxalic acid and sulfuric acid is prepared, the mass percentage of oxalic acid is 10%, and the quality percentage of sulfuric acid contains
Amount is 30%, and reducing agent cyclohexanediol is added, and the mass percentage of reducing agent is 10%, measures acid of the 500mL containing reducing agent
Property solution is in container；The powder for weighing 50.0g lithium ion battery anode material waste material, is slowly added in said vesse, Gu
Liquor ratio about 100g/L.Stirring and heating in water bath for reaction container are opened, reaction temperature is 90 DEG C, after reaction 4 hours, is cooled.
Filtering is separated by solid-liquid separation with realizing, respectively obtains leachate and filter residue.It washs filter residue for several times, collect washing lotion and is mixed with leachate.
Liquid phase sample is taken, with the concentration of the metallic elements such as ICP-OES analysis nickel, cobalt, manganese, lithium, calculates the leaching rate of each metallic element,
As a result it is respectively as follows: Ni, 98.3%；Co, 97.6%；Mn, 97.1%；Li, 98.9%.
In conclusion the reducing agent reactivity that the present invention uses is big, and it is nontoxic, it is environmentally protective, it can be by useless positive material
The less soluble metal ion of high-valence state is reduced into the ion soluble easily in water of lower valency in material, after reaction by-product be gas or
Person's low boiling point small organic molecule is easy to remove from system, and the reducing agent；It is short and at low cost to leach recovery process route,
The metal ion in useless positive electrode can be leached by single step reaction, leaching rate is high, and extraction time is short.
The second aspect of the embodiment of the present invention provides a kind of regeneration method of anode material for lithium-ion batteries, including such as
Lower five steps.
(1) recycling of positive material waste: according to the recovery method of lithium ion battery anode material waste material as described above
Lithium ion battery anode material waste material is handled, leachate and filter residue are obtained.The recovery method of lithium ion battery anode material waste material
It sees above, details are not described herein again.
(2) preparation of precursor solution: according to the element composition and content in leachate, each metal member in leachate is adjusted
The content of element, keeps the molar ratio of each metallic element consistent with the chemical formula of target positive electrode, obtains precursor solution.
The chemical formula of target positive electrode can be Li1+δ[Ni1-x-y-zCoxMnyMz]O2、Li1+η[Mn2-aMa]O4Or
xLi2MnO3·(1-x)LiNO2.The chemical formula of target positive electrode can be with the lithium ion battery anode material waste material of recycling
Main component is identical, can also be different, that is, can add the unexistent metallic element of salvage material when regenerating.According to target anode
The chemical formula of material adjusts the content of each metallic element in leachate, obtains precursor solution, the concentration range of precursor solution
Generally 0.5~3mol/L.Generally, the water soluble salt of nickel, cobalt or/and manganese is added into leachate；If metal from
The presoma of son doping, then be added one of water soluble salt of M, M or N or two or more.Doped chemical M, M or N
For metallic element Ni, Co, Mn, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb,
Any one of Mo, Cd, W, La, Ce, Nd and Sm.
It is preferred that the anion of above-mentioned soluble-salt is chloride ion, sulfate ion, nitrate ion, oxalate denominationby, phosphorus
Sour hydrogen radical ion, dihydrogen phosphate ions or acetate ion.Generally, as preferred plan, the anion of soluble-salt
It is consistent with anion sour in leachate.The preferably sulfuric acid radical ion from the point of view of save the cost.
(3) target the preparation of target positive electrode material precursor: is being prepared just by precursor preparation technique precursor solution
Pole material precursor, while obtaining solution containing lithium ion.
Wherein, the preparation method of target positive electrode material precursor can be coprecipitation.
The step of coprecipitation are as follows: ammonia spirit and/or aqueous alkali, the gold in addition to lithium are added into precursor solution
Belong to ion and coprecipitation reaction occurs, after separation of solid and liquid, respectively obtains target positive electrode material precursor and solution containing lithium ion.Instead
It can be passed through inert gas or nitrogen protection during answering, be oxidized to avoid core metal element, influence the vibration density of material
Degree.
Wherein, ammonia spirit can be to contain in ammonia, ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate and ammonium sulfate at least one
The aqueous solution of kind, concentration are 0.1~1mol/L；Aqueous alkali can be to contain sodium hydroxide, potassium hydroxide, sodium carbonate and carbon
The aqueous solution of at least one of sour hydrogen sodium, concentration are 0.5~5mol/L.
The pH value of mixed solution is 9~12.5, and the temperature of reaction is 30~80 DEG C, when reaction mixing speed be 100~
2000rpm, reaction time are 1~24 hour.Reaction temperature is preferably controlled to 50 DEG C or so, takes into account the property of production efficiency and material
Can, the control reaction time is preferably 2~12 hours.
If aqueous solution or aqueous alkali that ammonia spirit is hydroxide are the aqueous solution of hydroxide, mesh is thus made
The presoma for marking positive electrode is complex hydroxide, and presoma can use general formula such as [Ni1-x-y-zCoxMnyMz](OH)2Table
Show.If ammonia spirit be ammonium carbonate aqueous solution or aqueous alkali be sodium carbonate aqueous solution, target of the invention is being made just
The presoma of pole material is compound carbonate, can use general formula such as [Ni1-x-y-zCoxMnyMz]CO3It indicates.Be filtered, washed and
The presoma or the above-mentioned compound oxyhydroxide of heat treatment that target positive electrode is made in dry above-mentioned complex chemical compound are to obtain phase
The composite oxides answered.By being heat-treated the water or CO that can remove in compound oxyhydroxide2.Heat treatment temperature is preferred
400~1000 DEG C, heat treatment time preferably 0.5~10 hour.
(4) elemental lithium in reclaim liquid phase, obtains Li source compound.
The method of elemental lithium in reclaim liquid phase, including carbon dioxide or addition carbonic acid are passed through into solution containing lithium ion
Salt, phosphate, fluoride salt.The lithium salts of recycling, further processing hydrate are used further to positive electrode or other lithium electricity materials
The preparation of material or the preparation for being directly used in positive electrode.
The Li source compound can for the hydroxide of lithium, the oxyhydroxide of lithium, lithium oxide, lithium vulcanization
Object, the carbonate of lithium, the nitrate of lithium, the acetate of lithium and lithium halide in it is at least one.Li source compound can be
Lithium hydroxide (or lithium hydroxide containing the crystallization water), lithium carbonate, lithium nitrate, lithium acetate, lithium fluoride it is one or more, generally
It is preferred that lithium carbonate or lithium hydroxide.
(5) preparation of target positive electrode: by positive electrode burning process, the target anode material in step (3) is utilized
Target positive electrode is made in the Li source compound recycled in material precursor and step (4).
As a preferred embodiment, firing can roast 1~24 hour prior to 300~800 DEG C, then 700~1050
DEG C roasting 1~24 hour；Calcination atmosphere is the oxidizing atmosphere of air or oxygen content > 30% when the roasting.
For the performance for optimizing material, target positive electrode can also be modified by various methods.Such as step (5)
It further comprises the steps of: later and coats lewis base compound, including mixing oxides method, liquid phase chelating in target positive electrode outer surface
Method etc..Such as, lewis base compound and target positive electrode are mixed by mechanical method and are heat-treated, material outside
Implement point cladding in surface.For another example, the method chemically reacted by the hydroxyl of metal alky I oxides and positive electrode surface
Lewis base compound is coated in outer surface.
It is described further below by recovery method of the specific embodiment to above-mentioned lithium ion battery anode material waste material.
Based on the leachate that previous embodiment 1 recycles, according to the concentration conversion of the metallic elements such as nickel, cobalt, manganese in embodiment 1
The content of each metallic element in leachate, according to chemical formula [Ni0.5Co0.2Mn0.265Al0.035](OH)2Regulate and control each gold in solution
Belong to the content of element.Wherein, metal Al is cheap element, can not consider that recycling is leached, when regeneration considers further that addition.To leachate
Aluminum sulfate is added in right amount, and adjusts each metal member by the amount that water is added in control for middle addition nickel sulfate or cobaltous sulfate or manganese sulfate
The concentration of element, obtains the precursor solution for being used to prepare target positive electrode.
It is passed through N in the reactor2It is bubbled, to remove air, makes entire reaction process in N2It is carried out in atmosphere.N herein2
Rare gas can be changed into.Precursor solution, ammonia spirit and aqueous alkali are each led into reactor, while opening and stirring
It mixes.Aqueous alkali is sodium hydrate aqueous solution, concentration 4mol/L, in reaction process, adjust the pH value range 9 of solution~
12, early period, nucleation stage pH value was high, and grain growth later period, pH value stage is lower.50 DEG C of reaction temperature or so of control, when reaction
Between about 12 hours.It is filtered, washed to obtain presoma complex hydroxide, while obtaining the filtrate containing lithium.
It is passed through carbon dioxide into the filtrate containing lithium, recycles carbonic acid crystalline lithium, filtering, drying.
Dry presoma complex hydroxide.1:1.03 weighs presoma and lithium carbonate in molar ratio, using dry mixed,
Tube furnace is then transferred to fire in air atmosphere.It after firing, is cooled to room temperature in furnace, is obtained after coming out of the stove by break process
Target positive electrode.
The target positive electrode obtained using button cell evaluation.By the positive electrode being prepared, conductive agent acetylene black
And binder Kynoar (PVDF) 80:10:10 in mass ratio mixing, and solvent N-methyl pyrilidone is added, slurry is made
Material.Slurry is coated on a thickness of on 20 μm of aluminium foil, is then dried in vacuo at 120 DEG C, strikes out the circle that diameter is about 14mm
Anode is made in piece.Use metal lithium sheet as cathode, electrolyte solvent forms DMC/EC/EMC=1:1:1 (volume ratio), contains lithium
Salt LiPF61.0mol/L, diaphragm are porous polyethylene membranes, and 20 μm of thickness, 2025 types are assembled into the glove box of Ar gas shielded
Button cell.
Button cell obtained, the chemical formula of main chemical compositions are LiNi0.5Co0.2Mn0.265Al0.035O2, electrification
It is as follows to learn performance: discharge capacity is 162mAh/g for the first time, and discharging efficiency is 90% for the first time, circulation volume conservation rate (room temperature,
0.2C, 100 weeks) it is 97%.
Based on the leachate that previous embodiment 4 recycles, leached according to the concentration conversion of the metallic elements such as nickel, cobalt, manganese in table 1
The content of each metallic element in liquid, according to chemical formula [Ni0.6Co0.2Mn0.2](OH)2Each metallic element contains in regulation solution
Amount.Nickel sulfate or cobaltous sulfate or manganese sulfate are added into leachate, and each metallic element is adjusted by the amount that water is added in control
Concentration obtains precursor solution.
It is passed through N in the reactor2It is bubbled, to remove air, makes entire reaction process in N2It is carried out in atmosphere.N herein2
Rare gas can be changed into.The precursor solution, ammonia spirit and aqueous alkali that are used to prepare target positive electrode are led to respectively
Enter into reactor, while opening stirring.Aqueous alkali is sodium hydrate aqueous solution, concentration 4mol/L, in reaction process,
The pH value range 9~12 of solution is adjusted, early period, nucleation stage pH value was high, and grain growth later period, pH value stage is lower.Control is anti-
Temperature 50 C or so is answered, the reaction time is about 12 hours.It is filtered, washed to obtain presoma complex hydroxide, while being contained
The filtrate of lithium.
Ammonium carbonate is added into the filtrate containing lithium, recycles carbonic acid crystalline lithium, filtering, drying.
Dry presoma complex hydroxide.1:1.05 weighs presoma and lithium carbonate in molar ratio, using dry mixed,
Tube furnace is then transferred to fire in air atmosphere.It after firing, is cooled to room temperature in furnace, is obtained after coming out of the stove by break process
Target positive electrode.
Positive electrode obtained, the chemical formula of main chemical compositions are LiNi0.6Co0.2Mn0.2O2, chemical property
As follows: discharge capacity is 178mAh/g for the first time, and discharging efficiency is 89% for the first time, and circulation volume conservation rate (room temperature, 0.2C, 100
Week) it is 96%.
The present invention is based on metallic element closed loop cycle, the main metal element in the positive electrode that gives up can be through the invention
Technology is recycled and is regenerated, and applied widely, and the positive electrode of recuperable lithium ion secondary battery includes layer structure, point
The positive electrodes such as spinel structure and polyanion class.
Those skilled in the art after considering the specification and implementing the invention disclosed here, will readily occur to of the invention its
Its embodiment.This application is intended to cover any variations, uses, or adaptations of the invention, these modifications, purposes or
Person's adaptive change follows general principle of the invention and including the undocumented common knowledge in the art of the present invention
Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are by the application
Claim point out.
It should be understood that the invention is not limited to the contents for being described above and being shown in the accompanying drawings, and can
To carry out various modifications and change without departing from the scope.The scope of the present invention is limited only by the attached claims.
Claims (24)
1. a kind of recovery method of lithium ion battery anode material waste material, which comprises the steps of: by lithium-ion electric
Pond positive material waste is reacted with the acid solution containing reducing agent, is separated by solid-liquid separation after reaction, obtain leachate and
Filter residue realizes the leaching of metallic element in lithium ion cell anode waste；
The reducing agent includes at least one compound with following molecular structural formula:
Wherein, R1, R2, R3, R4 are independently selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl；Or R1, R2, R3, R4
It is independently selected from the group containing at least one of boron, silicon, nitrogen, phosphorus, oxygen, sulphur, fluorine, chlorine, bromine and iodine element；Wherein, R1,
R2, R3, R4 are independent substituent group or in which two adjacent group joint cyclization.
2. the recovery method of lithium ion battery anode material waste material according to claim 1, which is characterized in that the chemical combination
R1, R2, R3, R4 are independent substituent group in the molecular structural formula of object, and R1, R2, R3, R4 are respectively hydrogen or carbon atom number
For 1~4 alkyl.
3. the recovery method of lithium ion battery anode material waste material according to claim 1 or 2, which is characterized in that described
Reducing agent further includes that following substance is any one or more of:
Sulfur dioxide, sulfurous acid, sodium sulfite, ammonium sulfite, sodium thiosulfate, hydrogen peroxide, glucose, sucrose, cellulose,
Cornstalk.
4. the recovery method of lithium ion battery anode material waste material according to claim 1, which is characterized in that the lithium
Ion battery positive material waste has general formula Li1+δ[Ni1-x-y-zCoxMnyMz]O2-βPβ, wherein doped chemical M is metallic element
Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm
At least one of, doped chemical P be F or S, 0≤δ≤0.2,0≤β≤0.5,0≤x≤1,0≤y≤1,0≤z≤0.2, and
0<x+y+z≤1。
5. the recovery method of lithium ion battery anode material waste material according to claim 1, which is characterized in that the lithium
Ion battery positive material waste has general formula Li1+η[Mn2-aMa]O4-mPm, wherein doped chemical M be metallic element Ni, Co,
Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr, Nb, Mo, Cd, W, La, Ce, Nd and Sm
At least one of, doped chemical P is F or S, 0≤η≤0.2,0≤a≤2,0≤m≤0.5.
6. the recovery method of lithium ion battery anode material waste material according to claim 1, which is characterized in that the lithium
Ion battery positive material waste has general formula xLi2MnO3·(1-x)LiNO2, wherein doped chemical N be metallic element Ni,
Co、Mn、Na、K、Mg、Ca、Sr、Ba、Al、Ga、In、Ge、Sn、Ti、V、Cr、Fe、Cu、Zn、Y、Zr、Nb、Mo、Cd、W、La、Ce、
At least one of Nd and Sm, 0 < x < 1.
7. the recovery method of lithium ion battery anode material waste material according to claim 1, which is characterized in that the acidity
Solution is inorganic acid and/or organic acid.
8. the recovery method of lithium ion battery anode material waste material according to claim 7, which is characterized in that described inorganic
Acid is that sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid are any one or more of.
9. the recovery method of lithium ion battery anode material waste material according to claim 7, which is characterized in that described organic
Acid is that oxalic acid, formic acid, acetic acid, trichloroacetic acid, propionic acid, butyric acid or valeric acid are any one or more of.
10. the recovery method of lithium ion battery anode material waste material according to claim 1, which is characterized in that soaked
It is further comprised the steps of: out by residue washing several times after liquid and filter residue, washing lotion and washing filter residue is obtained after washing, washing lotion is put into leaching
Liquid mixing.
11. the recovery method of lithium ion battery anode material waste material according to claim 10, which is characterized in that further include
Step: washing filter residue is reacted with the acid solution containing reducing agent, simultaneously heating water bath is stirred, solid-liquid point is carried out after reaction
From obtaining secondary leachate and secondary response filter residue, realize the leaching of metallic element in washing filter residue.
12. the recovery method of lithium ion battery anode material waste material according to claim 1, which is characterized in that the lithium
The solid-to-liquid ratio of ion battery positive material waste and the acid solution containing reducing agent is 10~2000g/L.
13. the recovery method of lithium ion battery anode material waste material according to claim 1, which is characterized in that reaction temperature
Degree is 0~120, and the reaction time is 0.1~24 hour.
14. a kind of regeneration method of anode material for lithium-ion batteries, which comprises the steps of:
(1) recycling of positive material waste: according to claim 1 to lithium ion battery anode material waste described in 13 any one
The recovery method of material handles lithium ion battery anode material waste material, obtains leachate and filter residue；
(2) preparation of precursor solution: according to the element composition and content in leachate, each metallic element in leachate is adjusted
Content keeps the molar ratio of each metallic element consistent with the chemical formula of target positive electrode, obtains precursor solution；
(3) target anode material the preparation of target positive electrode material precursor: is prepared by precursor preparation technique precursor solution
Material precursor, while obtaining solution containing lithium ion；
(4) elemental lithium in reclaim liquid phase, obtains Li source compound；
(5) preparation of target positive electrode: through positive electrode burning process, before the target positive electrode in step (3)
The Li source compound recycled in body and step (4) is driven, target positive electrode is made.
15. the regeneration method of anode material for lithium-ion batteries according to claim 14, which is characterized in that the step
(2) in, the chemical formula of target positive electrode is Li1+δ[Ni1-x-y-zCoxMnyMz]O2、Li1+η[Mn2-aMa]O4Or xLi2MnO3·
(1-x)LiNO2, according to the chemical formula of target positive electrode, be added into leachate nickel, cobalt, the water soluble salt of manganese and M, M or
One or more of water soluble salt of person N to adjust the content of each metallic element in leachate, wherein doped chemical M, M or
Person N be metallic element Ni, Co, Mn, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Ge, Sn, Ti, V, Cr, Fe, Cu, Zn, Y, Zr,
Any one of Nb, Mo, Cd, W, La, Ce, Nd and Sm.
16. the regeneration method of anode material for lithium-ion batteries according to claim 14, which is characterized in that the step
(3) in, the preparation method of target positive electrode material precursor is coprecipitation.
17. the regeneration method of anode material for lithium-ion batteries according to claim 16, which is characterized in that the co-precipitation
The step of method are as follows: ammonia spirit and/or aqueous alkali are added into precursor solution, the metal ion in addition to lithium occurs coprecipitated
It forms sediment and reacts, after separation of solid and liquid, respectively obtain target positive electrode material precursor and solution containing lithium ion.
18. the regeneration method of anode material for lithium-ion batteries according to claim 17, which is characterized in that the ammonium hydroxide is molten
Liquid be the aqueous solution containing at least one of ammonia, ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate and ammonium sulfate, concentration be 0.1~
1mol/L。
19. the regeneration method of anode material for lithium-ion batteries according to claim 17, which is characterized in that the buck is molten
Liquid be the aqueous solution containing at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and sodium bicarbonate, concentration be 0.5~
5mol/L。
20. the regeneration method of anode material for lithium-ion batteries according to claim 17, which is characterized in that mixed solution
PH value is 9~12.5, and the temperature of reaction is 30~80 DEG C, and mixing speed is 100~2000rpm when reaction, the reaction time is 1~
24 hours.
21. the regeneration method of anode material for lithium-ion batteries according to claim 17, which is characterized in that in reaction process
It is passed through inert gas or nitrogen protection.
22. the regeneration method of anode material for lithium-ion batteries according to claim 14, which is characterized in that the step
(4) method of the elemental lithium in reclaim liquid phase, including be passed through into solution containing lithium ion carbon dioxide or be added carbonate,
Phosphate, fluoride salt.
23. the regeneration method of anode material for lithium-ion batteries according to claim 14, which is characterized in that the step
(4) Li source compound obtained in be the hydroxide of lithium, the oxyhydroxide of lithium, the oxide of lithium, lithium sulfide,
The carbonate of lithium, the nitrate of lithium, the acetate of lithium and lithium halide in it is at least one.
24. the regeneration method of anode material for lithium-ion batteries according to claim 14, which is characterized in that the step
(5) it is further comprised the steps of: after and coats lewis base compound in target positive electrode outer surface.
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