CN108996484A - The preparation method of the recoverying and utilizing method of waste lithium iron phosphate battery, iron manganese phosphate for lithium and lithium iron phosphate positive material - Google Patents
The preparation method of the recoverying and utilizing method of waste lithium iron phosphate battery, iron manganese phosphate for lithium and lithium iron phosphate positive material Download PDFInfo
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
- C01B25/305—Preparation from phosphorus-containing compounds by alkaline treatment
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
The present invention provides a kind of recoverying and utilizing methods of waste lithium iron phosphate battery, comprising: waste lithium iron phosphate battery is discharged, disassembles to obtain positive plate；Positive plate is dissolved in acid, after filtering, obtains filtrate and filter residue；Ammonium hydroxide is added into filtrate, stirs simultaneously, until resulting pH value of solution is 1.0-1.6, obtains precipitating containing the mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate；Ammonium hydroxide is added into mixed solution B, stirs simultaneously, until resulting pH value of solution is 5.4-7.0, obtains lithium sulfate filtrate and aluminum hydroxide precipitation；Addition phosphorus-containing compound and alkali into lithium sulfate filtrate, stirring are obtained by filtration drying after precipitating, obtain lithium phosphate until acquired solution pH is 9.0-14.0.The present invention also provides the preparation methods of a kind of iron manganese phosphate for lithium or lithium iron phosphate positive material, and iron manganese phosphate for lithium or lithium iron phosphate positive material is made as raw material using lithium phosphate obtained above and ferric phosphate.
Description
Technical field
The present invention relates to waste lithium iron phosphate battery recycling fields, and in particular to a kind of recycling of waste lithium iron phosphate battery
Utilize the preparation method of method, iron manganese phosphate for lithium and lithium iron phosphate positive material.
Background technique
Currently, being the lithium ion secondary battery of positive electrode due to the spies such as at low cost and have a safety feature using LiFePO4
Point has started the power battery for being widely used in electric tool and electric vehicle.The quantity of waste and old lithium ion battery also will simultaneously
Increase year by year.Therefore, for recycling and reusing material, save the cost and environment is protected, recycling LiFePO4 waste material becomes to have very much
It is necessary.
The problems such as there are higher cost, recycling for traditional recovery method not exclusively, the rate of recovery is bad, seriously polluted, therefore,
It is necessary to provide a kind of recoverying and utilizing methods of new waste lithium iron phosphate battery.
Summary of the invention
To solve the above problems, the present invention provides a kind of recoverying and utilizing method of waste lithium iron phosphate battery, described time
The receiving method rate of recovery is higher, and environmentally friendly, and cost recovery is lower.Recycling obtained substance can be used for preparing iron manganese phosphate for lithium
With the positive electrodes such as LiFePO4.
First aspect present invention provides a kind of recoverying and utilizing method of waste lithium iron phosphate battery, comprising:
(1) waste lithium iron phosphate battery discharged, disassemble to obtain positive plate；
(2) positive plate is dissolved in acid and obtains mixed solution A, after filtering, obtain filtrate and filter residue；
(3) ammonium hydroxide is added into the filtrate, stirs simultaneously, until resulting pH value of solution is 1.0-1.6, is obtained by filtration and contains
There are the mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate precipitating；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4) ammonium hydroxide is added into the mixed solution B, stirs simultaneously, until resulting pH value of solution is 5.4-7.0, filtering
Obtain lithium sulfate filtrate and aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5) phosphorus-containing compound and alkali, stirring are added into the lithium sulfate filtrate, until acquired solution pH is 9.0-
14.0, it is dried after precipitating is obtained by filtration, obtains lithium phosphate.
Wherein, the acid includes at least one of sulfuric acid, hydrochloric acid and nitric acid.
Wherein, the phosphorus-containing compound includes at least one of phosphoric acid, diammonium hydrogen phosphate and ammonium dihydrogen phosphate.
Wherein, the alkali includes at least one of ammonium hydroxide, sodium hydroxide and potassium hydroxide.
Wherein, the mixing speed of the step (3), step (4) and step (5) is respectively 100-400r/min.
Wherein, in the step (3), the ammonium hydroxide is added after resulting pH value of solution is 1.0-1.6, continues to stir
It is filtered after 30-60min；In the step (4), the ammonium hydroxide is added after resulting pH value of solution is 5.4-7.0, continues to stir
It is filtered after 30-60min.
The recoverying and utilizing method for the waste lithium iron phosphate battery that first aspect present invention provides can recycle LiFePO4 electricity
Phosphorus, iron, elemental lithium in pond, the rate of recovery is higher, wherein phosphorus, iron, lithium the rate of recovery can achieve 85% or more.Meanwhile this hair
Bright method is environmentally friendly, and waste liquid, the waste residue that pollution is generated to environment are not generated during extracting phosphorus, iron, lithium.In addition,
The method is easy to operate, and cost is relatively low.
Second aspect of the present invention provides a kind of preparation method of lithium iron manganese phosphate anode material, comprising:
(1) waste lithium iron phosphate battery discharged, disassemble to obtain positive plate；
(2) positive plate is dissolved in acid and obtains mixed solution A, after filtering, obtain filtrate and filter residue；
(3) ammonium hydroxide is added into the filtrate, stirs simultaneously, until resulting pH value of solution is 1.0-1.6, is obtained by filtration and contains
There are the mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate precipitating；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4) ammonium hydroxide is added into the mixed solution B, stirs simultaneously, until resulting pH value of solution is 5.4-7.0, filtering
Obtain lithium sulfate filtrate and aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5) phosphorus-containing compound and alkali, stirring are added into the lithium sulfate filtrate, until acquired solution pH is 9.0-
14.0, it is dried after precipitating is obtained by filtration, obtains lithium phosphate；
(6) according to the molar ratio of each element in iron manganese phosphate for lithium, by the lithium phosphate, the ferric phosphate, phosphorus source and manganese source
Mixing, and carbon source and solvent is added, obtain mixing material；
(7) iron manganese phosphate for lithium presoma will be obtained after the mixing material ball milling, drying；
(8) lithium iron manganese phosphate anode material will be obtained after iron manganese phosphate for lithium presoma calcining.
Wherein, the preparation method of the lithium iron manganese phosphate anode material further include:
According to molar ratio nAl:nLi:nFe:nP:nMn=(0.002-0.02): (1.0-1.1): (0.18-0.498):
(0.95-1): (0.5-0.8) mixes the aluminium hydroxide, the lithium phosphate, the ferric phosphate, phosphorus source and the manganese source
It closes, and carbon source and solvent is added, obtain mixing material；Technique by step (7) and step (8) obtains the manganese phosphate of aluminium doping
Iron lithium anode material.
The preparation method for the lithium iron manganese phosphate anode material that second aspect of the present invention provides, by the way that waste lithium iron phosphate is electric
Phosphorus, iron, elemental lithium recycling and reusing in pond, and as the iron manganese phosphate for lithium of Material synthesis electrochemical performance, it realizes
The effective use of waste lithium iron phosphate battery, with good economic efficiency and environmental benefit.Meanwhile preparation method is simply easy
Operation.
Third aspect present invention provides a kind of preparation method of lithium iron phosphate positive material, comprising:
(1), waste lithium iron phosphate battery discharged, disassemble to obtain positive plate；
(2), the positive plate is dissolved in acid and obtains mixed solution A, after filtering, obtain filtrate and filter residue；
(3), ammonium hydroxide is added into the filtrate, stirs simultaneously, until resulting pH value of solution is 1.0-1.6, is obtained by filtration
It is precipitated containing the mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4), ammonium hydroxide is added into the mixed solution B, stirs simultaneously, until resulting pH value of solution is 5.4-7.0, filtering
Obtain lithium sulfate filtrate and aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5), phosphorus-containing compound and alkali, stirring are added into the lithium sulfate filtrate, until acquired solution pH is 9.0-
14.0, it is dried after precipitating is obtained by filtration, obtains lithium phosphate；
(6), according to the molar ratio of each element in lithium iron phosphate positive material, by the lithium phosphate, the ferric phosphate and phosphorus
Source mixing, and carbon source and solvent is added, obtain mixing material；
(7), ferric lithium phosphate precursor will be obtained after the mixing material ball milling, drying；
(8), lithium iron phosphate positive material will be obtained after iron manganese phosphate for lithium presoma calcining.
Wherein, the preparation method of the lithium iron phosphate positive material further include:
According to molar ratio nAl:nLi:nFe:nP=(0.002-0.02): (1.0-1.1): (0.98-0.998): (0.95-
1), the aluminium hydroxide, the lithium phosphate, the ferric phosphate and source of iron are mixed, and carbon source and solvent is added, obtains mixing material
Material；Technique by step (7) and step (8) obtains the lithium iron phosphate positive material of aluminium doping.
The preparation method for the lithium iron phosphate positive material that third aspect present invention provides, by by waste lithium iron phosphate battery
In phosphorus, iron, elemental lithium recycling and reusing realizes useless and as the LiFePO4 of Material synthesis electrochemical performance
The effective use of old ferric phosphate lithium cell, with good economic efficiency and environmental benefit.Meanwhile preparation method is simply easily grasped
Make.
To sum up, beneficial effect of the present invention includes the following aspects:
1, the recoverying and utilizing method of the waste lithium iron phosphate battery can recycle phosphorus in ferric phosphate lithium cell, iron, lithium member
Element, the rate of recovery is higher, wherein phosphorus, iron, lithium the rate of recovery can achieve 85% or more；
2, the recoverying and utilizing method of the waste lithium iron phosphate battery, it is environmentally friendly, during extracting phosphorus, iron, lithium
Waste liquid, the waste residue that pollution is generated to environment are not generated.In addition, the method is easy to operate, cost is relatively low；
3, the preparation method of lithium iron manganese phosphate anode material provided by the invention, by will be in waste lithium iron phosphate battery
Phosphorus, iron, elemental lithium recycling and reusing, and as the iron manganese phosphate for lithium of Material synthesis electrochemical performance, have good
Economic benefit and environmental benefit；
4, by by the phosphorus in waste lithium iron phosphate battery, iron, elemental lithium recycling and reusing, and as Material synthesis electricity
The excellent ferric phosphate of chemical property.
Detailed description of the invention
Fig. 1 is the process flow chart of an embodiment of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of lithium iron manganese phosphate anode material made from the embodiment of the present invention 7；
Fig. 3 is the X ray diffracting spectrum of lithium iron manganese phosphate anode material made from the embodiment of the present invention 7；
Fig. 4 is the charging and discharging curve figure of lithium iron manganese phosphate anode material made from the embodiment of the present invention 7.
Specific embodiment
The following is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Referring to Fig.1, Fig. 1 is the process flow chart of an embodiment of the present invention；The present invention provides a kind of waste and old ferric phosphates
The recoverying and utilizing method of lithium battery, comprising:
(1), waste lithium iron phosphate battery discharged, disassemble to obtain positive plate；
(2), the positive plate is dissolved in acid and obtains mixed solution A, after filtering, obtain filtrate and filter residue；
(3), ammonium hydroxide is added into the filtrate, stirs simultaneously, until resulting pH value of solution is 1.0-1.6, is obtained by filtration
It is precipitated containing the mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4), ammonium hydroxide is added into the mixed solution B, stirs simultaneously, until resulting pH value of solution is 5.4-7.0, filtering
Obtain lithium sulfate filtrate and aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5), phosphorus-containing compound and alkali, stirring are added into the lithium sulfate filtrate, until acquired solution pH is 9.0-
14.0, filtering is dry after being precipitated, and obtains lithium phosphate.
In embodiment of the present invention, in step (1), after waste lithium iron phosphate battery is discharged, battery is disassembled, is obtained just
Pole piece.Then the positive plate washed, dried.It include aluminium foil in the positive plate.Optionally, using deionized water pair
The positive plate is washed to remove the entrained electrolyte in positive plate.
In embodiment of the present invention, in step (2), the acid includes at least one of sulfuric acid, hydrochloric acid and nitric acid.It is optional
Ground makes the pH < 0.8 of the mixed solution A by the way that the acid is added.Specifically, the pH of the mixed solution A is 0.4-0.6.
It mainly include binder and conduction not soluble in water in the filter residue in step (2) in embodiment of the present invention
Carbon.
In embodiment of the present invention, in step (3), ammonium hydroxide is added into the filtrate, stirs simultaneously, until resulting molten
Liquid pH is 1.0-1.6, i.e., until resulting pH value of solution is in the range of 1.0-1.6.Optionally, until resulting pH value of solution
It can be 1.0,1.1,1.2,1.3,1.4,1.5 or 1.6 etc..
In embodiment of the present invention, in step (3), until continuing to stir 30- after resulting pH value of solution is 1.0-1.6
It is filtered after 60min.Reaction can be made more abundant in this way.
In embodiment of the present invention, in step (3), it is dried after obtaining ferric phosphate precipitating D, obtains ferric phosphate.
In embodiment of the present invention, in step (3), the mixing speed is 100-400r/min.
In embodiment of the present invention, in step (3) and (4), the concentration of the ammonium hydroxide is regular industrial ammonia concn.
In embodiment of the present invention, in step (4), ammonium hydroxide will be added in the mixed solution, until resulting pH value of solution
For 6.5-7.0.
In embodiment of the present invention, in step (3), ammonium hydroxide is added into the mixed solution B, stirs simultaneously, until institute
The pH value of solution obtained is 5.4-7.0, i.e., until resulting pH value of solution is in the range of 5.4-7.0.Optionally, until it is resulting
PH value of solution can be 5.4,5.5,5.6,5.7,5.8,5.9,6.0,6.5 or 7.0 etc..
In embodiment of the present invention, in step (4), until continuing to stir 30- after resulting pH value of solution is 5.4-7.0
It is filtered after 60min.Reaction can be made more abundant in this way.
In embodiment of the present invention, in step (4), the mixing speed is 100-400r/min.
In embodiment of the present invention, in step (5), phosphorus-containing compound and alkali are added into the lithium sulfate filtrate, stirs,
Until acquired solution pH is 9.0-14.0, i.e., until resulting pH value of solution is in the range of 9.0-14.0.Optionally, until
Resulting pH value of solution can be 9.0,10.0,11.0,12.0,13.0 or 14.0 etc..
In embodiment of the present invention, in step (5), by lithium: phosphorus molar ratio, which is added for 3:1 into the lithium sulfate filtrate, to be contained
Phosphorus compound.Optionally, described that the sulphur is measured according to ICP (inductively coupled plasma body) or AAS (atomic absorption spectrography (AAS))
The concentration of Li in sour lithium filtrate, then according to lithium: phosphorus molar ratio is that phosphorus-containing compound is added into the lithium sulfate filtrate in 3:1.
In embodiment of the present invention, in step (5), the phosphorus-containing compound includes phosphoric acid, diammonium hydrogen phosphate and di(2-ethylhexyl)phosphate
At least one of hydrogen ammonium.
In embodiment of the present invention, in step (5), the alkali include in ammonium hydroxide, sodium hydroxide and potassium hydroxide at least
It is a kind of.The alkali is added until acquired solution pH is 9.0-14.0.It is added sodium hydroxide and what potassium hydroxide when was added is
Solid sodium hydroxide and potassium hydroxide.
In embodiment of the present invention, in step (5), the mixing speed is 100-400r/min.
In embodiment of the present invention, in each step, the operation of the drying is common process, and this will not be repeated here.
In embodiment of the present invention, the recoverying and utilizing method of waste lithium iron phosphate battery provided by the invention is at room temperature
It carries out.
The present invention provides the phosphorus in ferric phosphate lithium cell, iron, elemental lithium whole recycling and reusing to a kind of high-recovery
Method recycles phosphorus, iron, lithium in ferric phosphate lithium cell, while the method for the present invention is environmentally friendly, extracts the process of phosphorus, iron, lithium
In do not generate to environment generate pollution waste liquid, waste residue.In addition, the recovery method is simple to operation, cost is relatively low.Recycling
Obtained phosphorus, iron, elemental lithium can be used for preparing anode material for lithium-ion batteries or other industrial materials.
Second aspect of the present invention provides a kind of preparation method of lithium iron manganese phosphate anode material, comprising:
(1), waste lithium iron phosphate battery discharged, disassemble to obtain positive plate；
(2), the positive plate is dissolved in acid and obtains mixed solution A, after filtering, obtain filtrate and filter residue；
(3), ammonium hydroxide is added into the filtrate, stirs simultaneously, until resulting pH value of solution is 1.0-1.6, is obtained by filtration
It is precipitated containing the mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4), ammonium hydroxide is added into the mixed solution B, stirs simultaneously, until resulting pH value of solution is 5.4-7.0, filtering
Obtain lithium sulfate filtrate and aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5), phosphorus-containing compound and alkali, stirring are added into the lithium sulfate filtrate, until acquired solution pH is 9.0-
14.0, it is dried after precipitating is obtained by filtration, obtains lithium phosphate；
(6), according to the molar ratio of each element in iron manganese phosphate for lithium, by the lithium phosphate, the ferric phosphate, phosphorus source and manganese source
Mixing, and carbon source and solvent is added, obtain mixing material；
(7), iron manganese phosphate for lithium presoma will be obtained after the mixing material ball milling, drying；
(8), lithium iron manganese phosphate anode material will be obtained after iron manganese phosphate for lithium presoma calcining.
In embodiment of the present invention, the chemical formula of the lithium iron manganese phosphate anode material is LiFe1-xMnxPO4, wherein x
Range is 0.5≤x≤0.8.
In embodiment of the present invention, in step (6), according to each element molar ratio nLi:nFe:nP:nMn=(1.0-1.1):
(0.2-0.5): (0.95-1): the lithium phosphate, the ferric phosphate, phosphorus source and manganese source are mixed, and carbon are added by (0.5-0.8)
Source and solvent, obtain mixing material；
In embodiment of the present invention, in step (6), using lithium phosphate made from above-mentioned first aspect as lithium source, ferric phosphate
Phosphorus source of the P elements as part as source of iron, in lithium phosphate and ferric phosphate.In addition, a part of phosphorus source is added additionally with completion
The amount of phosphorus in iron manganese phosphate for lithium.
In embodiment of the present invention, in step (6), phosphorus source is phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and phosphoric acid
At least one of dihydro lithium.The P elements in P elements and lithium phosphate and ferric phosphate in phosphorus source together constitute phosphoric acid
Phosphorus in manganese iron lithium.
In embodiment of the present invention, in step (6), the manganese source be manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide,
At least one of manganese oxalate, manganese acetate and manganese nitrate.
In embodiment of the present invention, in step (6), the carbon source is citric acid, malic acid, tartaric acid, oxalic acid, bigcatkin willow
At least one of acid, succinic acid, glycine, ethylenediamine tetra-acetic acid, sucrose and glucose.Optionally, the quality of the carbon source
For the 10%-50% of target product iron manganese phosphate for lithium quality.After carbon source is added in the present invention, the carbon source can be in iron manganese phosphate for lithium table
Face forms carbon coating layer, improves the electric conductivity of iron manganese phosphate for lithium.
In embodiment of the present invention, in step (6), the solvent includes water, methanol, ethyl alcohol, propyl alcohol, isopropanol, positive fourth
Alcohol, isobutanol, n-amyl alcohol, n-hexyl alcohol, n-heptanol, acetone, butanone, diacetyl, pentanone, cyclopentanone, ketone, cyclohexanone, cycloheptyl
One of ketone or a variety of combinations.Optionally, the solid content of the mixing material is 30%-60%.
In embodiment of the present invention, the preparation method of the lithium iron manganese phosphate anode material further include: step (4) is taken to be made
Aluminium hydroxide, according to molar ratio nAl:nLi:nFe:nP:nMn=(0.002-0.02): (1.0-1.1): (0.18-0.498):
(0.95-1): (0.5-0.8) mixes the aluminium hydroxide, the lithium phosphate, the ferric phosphate, phosphorus source and the manganese source
It closes, and carbon source and solvent is added, obtain mixing material；Technique by step (7) and step (8) obtains the manganese phosphate of aluminium doping
Iron lithium anode material, chemical formula LiAlyFe1-x-yMnxPO4, wherein the range of x is 0.5≤x≤0.8, and the range of y is 0.002
≤y≤0.02。
Optionally, it will be mixed after aluminium hydroxide dissolution with other materials such as the lithium phosphates.The aluminium hydroxide is made
For the addition of doping metals source, the subsequent available lithium iron manganese phosphate anode material doped with metallic aluminium is realized to waste and old phosphoric acid
The recycling of aluminium in lithium iron battery, while the chemical property of lithium iron manganese phosphate anode material can be improved.Optionally, by institute
It states aluminium hydroxide to be dissolved in nitric acid, then be mixed with other materials such as the lithium phosphates.
In embodiment of the present invention, the Ball-milling Time is 10-48 hours.
In embodiment of the present invention, it is dried the mixing material after ball milling to obtain powder.Optionally, the drying
Operation includes: that the temperature drying that the mixing material after ball milling is placed in 80-300 DEG C of air dry oven is obtained powder in 2-20 hours.
In embodiment of the present invention, after gained powder is crushed with disintegrating apparatus 400-600 DEG C at a temperature of pre-process
2-10 hours, obtain iron manganese phosphate for lithium presoma.Optionally, the partial size of the iron manganese phosphate for lithium presoma is nanoscale.
It is in embodiment of the present invention, the iron manganese phosphate for lithium presoma is small in 500-900 DEG C of temperature sintering 10-30
When, obtain iron manganese phosphate for lithium powder body material (LiFe1-xMnxPO4) or aluminium doping iron manganese phosphate for lithium powder body material (LiAlyFe1-x- yMnxPO4) wherein the range of x be 0.5≤x≤0.8, the range of y is 0.002≤y≤0.02.
In embodiment of the present invention, the pretreatment and calcine technology are carried out under protective atmosphere, the protection gas
The gas of atmosphere includes at least one of nitrogen and argon gas.
In embodiment of the present invention, the partial size of the lithium iron manganese phosphate anode material is nanoscale.Optionally, the phosphoric acid
The partial size of manganese iron lithium anode material is 100-200nm.
The present invention prepares phosphoric acid as lithium source, source of iron and partial phosphorus source by lithium phosphate obtained above and ferric phosphate
Manganese iron lithium anode material will not introduce other impurities in preparation process, obtained lithium iron manganese phosphate anode material energy density compared with
Height, electrochemical performance.
It is understood that the lithium phosphate, the phosphorus that the present invention recycles waste lithium iron phosphate battery
Sour iron and aluminium hydroxide can be used to prepare other anode material for lithium-ion batteries such as LiFePO4 etc..
Third aspect present invention provides a kind of preparation method of lithium iron phosphate positive material, comprising:
(1), waste lithium iron phosphate battery discharged, disassemble to obtain positive plate；
(2), the positive plate is dissolved in acid and obtains mixed solution A, after filtering, obtain filtrate and filter residue；
(3), ammonium hydroxide is added into the filtrate, stirs simultaneously, until resulting pH value of solution is 1.0-1.6, is obtained by filtration
It is precipitated containing the mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4), ammonium hydroxide is added into the mixed solution B, stirs simultaneously, until resulting pH value of solution is 5.4-7.0, filtering
Obtain lithium sulfate filtrate and aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5), phosphorus-containing compound and alkali, stirring are added into the lithium sulfate filtrate, until acquired solution pH is 9.0-
14.0, it is dried after precipitating is obtained by filtration, obtains lithium phosphate；
(6), according to the molar ratio of each element in lithium iron phosphate positive material, by the lithium phosphate, the ferric phosphate and phosphorus
Source mixing, and carbon source and solvent is added, obtain mixing material；
(7), ferric lithium phosphate precursor will be obtained after the mixing material ball milling, drying；
(8), lithium iron phosphate positive material will be obtained after iron manganese phosphate for lithium presoma calcining.
In embodiment of the present invention, phosphorus source, carbon source and solvent can for phosphorus source, carbon source described in above-mentioned second aspect and
Solvent.
In embodiment of the present invention, the preparation method of the lithium iron phosphate positive material further include:
According to molar ratio nAl:nLi:nFe:nP=(0.002-0.02): (1.0-1.1): (0.98-0.998): (0.95-
1), the aluminium hydroxide, the lithium phosphate, the ferric phosphate and source of iron are mixed, and carbon source and solvent is added, obtains mixing material
Material；Technique by step (7) and step (8) obtains the lithium iron phosphate positive material of aluminium doping.
The present invention prepares ferric phosphate as lithium source, phosphorus source and part source of iron by lithium phosphate obtained above and ferric phosphate
Lithium anode material, in addition, a part of source of iron is added additionally with the amount of iron in completion LiFePO4.
In embodiment of the present invention, the source of iron is ferrous carbonate, ferrous hydroxide, ferrous nitrate, ferrous oxalate, hydrogen-oxygen
Change one of iron, ferric nitrate, ironic citrate and di-iron trioxide or a variety of combinations.
In embodiment of the present invention, the preparation method of the lithium iron phosphate positive material and lithium iron manganese phosphate anode material
Preparation method is similar, can specifically be adjusted according to the actual situation.
The preparation method for the lithium iron phosphate positive material that third aspect present invention provides, by by waste lithium iron phosphate battery
In phosphorus, iron, elemental lithium recycling and reusing realizes useless and as the LiFePO4 of Material synthesis electrochemical performance
The effective use of old ferric phosphate lithium cell, with good economic efficiency and environmental benefit.Meanwhile preparation method is simply easily grasped
Make.
Embodiment 1:
A kind of recoverying and utilizing method of waste lithium iron phosphate battery, comprising:
(1) after being discharged waste lithium iron phosphate battery, battery is disassembled, after obtaining positive plate, positive plate is washed,
Drying；
(2) positive plate after washing and drying is directly used into sulfuric acid dissolution, obtains mixed solution A, the pH < of mixed solution A
0.8, mixed solution A is filtered, filtrate and filter residue are obtained (filter residue is mainly binder and conductive carbon not soluble in water)；
(3) ammonium hydroxide is added into filtrate, side ammoniates waterside stirring, mixing speed 400r/min, at the end of control reaction
PH continues to filter after stirring 60min, obtains the mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate in the range of 1.0-1.6
Precipitating；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4) ammonium hydroxide is added into the mixed solution B of lithium sulfate and aluminum sulfate, side ammoniates waterside stirring, and mixing speed is
400r/min, pH continues to filter after stirring 60min, obtains lithium sulfate filtrate in the range of 5.4-7.0 at the end of control reaction
And aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5) it is stirring after diammonium hydrogen phosphate is added in 3:1 by lithium phosphorus molar ratio into lithium sulfate filtrate, and hydroxide is added
Sodium, mixing speed 400r/min, pH is filtered after complete reaction in the range of 9.0-14.0, is dry at the end of control reaction
It is dry, obtain lithium phosphate.
In this embodiment, phosphorus, iron, lithium, aluminium the rate of recovery can achieve 85% or more.
Embodiment 2:
A kind of recoverying and utilizing method of waste lithium iron phosphate battery, comprising:
(1) after being discharged waste lithium iron phosphate battery, battery is disassembled, after obtaining positive plate, positive plate is washed,
Drying；
(2) positive plate after washing and drying is directly used into sulfuric acid dissolution, obtains mixed solution A, the pH < of mixed solution A
0.8, mixed solution A is filtered, filtrate and filter residue are obtained (filter residue is mainly binder and conductive carbon not soluble in water)；
(3) ammonium hydroxide is added into filtrate, side ammoniates waterside stirring, mixing speed 100r/min, at the end of control reaction
PH continues to filter after stirring 60min, obtains the mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate in the range of 1.0-1.6
Precipitating；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4) ammonium hydroxide is added into the mixed solution B of lithium sulfate and aluminum sulfate, side ammoniates waterside stirring, and mixing speed is
100r/min, pH continues to filter after stirring 60min, obtains lithium sulfate filtrate in the range of 5.4-7.0 at the end of control reaction
And aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5) it is stirring after phosphoric acid is added in 3:1 by lithium phosphorus molar ratio into lithium sulfate filtrate E, and ammonium hydroxide is added, stirring speed
Degree is 100r/min, and pH filters after complete reaction in the range of 9.0-14.0, is dry, obtaining phosphorus at the end of control reaction
Sour lithium.
In this embodiment, phosphorus, iron, lithium, aluminium the rate of recovery can achieve 85% or more.
Embodiment 3:
A kind of recoverying and utilizing method of waste lithium iron phosphate battery, comprising:
(1) after being discharged waste lithium iron phosphate battery, battery is disassembled, after obtaining positive plate, positive plate is washed,
Drying；
(2) positive plate after washing and drying is directly used into sulfuric acid dissolution, obtains mixed solution A, the pH < of mixed solution A
0.8, mixed solution A is filtered, filtrate and filter residue are obtained (filter residue is mainly binder and conductive carbon not soluble in water)；
(3) ammonium hydroxide is added into filtrate, side ammoniates waterside stirring, mixing speed 200r/min, at the end of control reaction
PH continues to filter after stirring 60min within the scope of 1.0-1.6, and the mixed solution B and ferric phosphate for obtaining lithium sulfate and aluminum sulfate are heavy
It forms sediment；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4) ammonium hydroxide is added into the mixed solution B of lithium sulfate and aluminum sulfate, side ammoniates waterside stirring, and mixing speed is
200r/min, control reaction at the end of pH within the scope of 5.4-7.0, continue stir 60min after filter, obtain lithium sulfate filtrate and
Aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5) it is stirring after ammonium dihydrogen phosphate is added in 3:1 by lithium phosphorus molar ratio into lithium sulfate filtrate, and hydroxide is added
Potassium, mixing speed 200r/min, pH is filtered after complete reaction within the scope of 9.0-14.0, is dry at the end of control reaction,
Obtain lithium phosphate.
In this embodiment, phosphorus, iron, lithium, aluminium the rate of recovery can achieve 85% or more.
Embodiment 4:
A kind of preparation method of lithium iron manganese phosphate anode material, comprising:
(1) lithium phosphate and phosphorus made from embodiment 1 is added in nLi:nFe:nP:nMn=1.0:0.2:1:0.8 in molar ratio
Sour iron, and manganese dioxide, phosphoric acid and citric acid is added, obtain mixing material；
(2) powder was obtained by temperature dry 20 hours that after mixing material ball milling 10 hours, are placed in 80 DEG C of air dry oven,
As for Temperature pre-treatment 10 hours of 400 DEG C in atmosphere furnace after gained powder is crushed with disintegrating apparatus, nano manganese phosphate is obtained
Iron lithium presoma；
(3) temperature that nano lithium iron manganese presoma is placed in nitrogen furnace at 500 DEG C is sintered 30 hours, obtains nanometer
Iron manganese phosphate for lithium powder body material LiFe0.2Mn0.8PO4。
Embodiment 5:
A kind of preparation method of lithium iron manganese phosphate anode material, comprising:
(1) nLi:nFe:nP:nMn=1.1:0.5:0.95:0.5 in molar ratio, be added lithium phosphate made from embodiment 2 and
Ferric phosphate, and manganese sesquioxide managnic oxide, diammonium hydrogen phosphate and malic acid is added, obtain mixing material；
(2) powder was obtained by temperature dry 2 hours that after mixing material ball milling 48 hours, are placed in 300 DEG C of air dry oven,
As for Temperature pre-treatment 2 hours of 600 DEG C in atmosphere furnace after gained powder is crushed with disintegrating apparatus, nano manganese phosphate iron is obtained
Lithium presoma；
(3) temperature that nano lithium iron manganese presoma is placed in nitrogen furnace at 900 DEG C is sintered 10 hours, obtains nanometer
Iron manganese phosphate for lithium powder body material LiFe0.5Mn0.5PO4。
Embodiment 6:
A kind of preparation method of lithium iron manganese phosphate anode material, comprising:
(1) lithium phosphate and phosphorus made from embodiment 3 is added in nLi:nFe:nP:nMn=1.0:0.4:1.0:0.6 in molar ratio
Sour iron, and mangano-manganic oxide, ammonium dihydrogen phosphate and oxalic acid is added, obtain mixing material；
(2) powder was obtained by temperature dry 10 hours that after mixing material ball milling 30 hours, are placed in 200 DEG C of air dry oven
Material obtains a nanometer phosphoric acid as Temperature pre-treatment 8 hours of 500 DEG C in atmosphere furnace after crushing gained powder with disintegrating apparatus
Manganese iron lithium presoma；
(3) temperature that nano lithium iron manganese presoma is placed in nitrogen furnace at 700 DEG C is sintered 20 hours, obtains nanometer
Iron manganese phosphate for lithium powder body material LiFe0.4Mn0.6PO4。
Embodiment 7:
A kind of preparation method of lithium iron manganese phosphate anode material, comprising:
(1) embodiment 1 of nAl:nLi:nFe:nP:nMn=0.005:1.0:0.195:1.0:0.8 addition in molar ratio is made
Aluminium hydroxide, lithium phosphate and ferric phosphate, and manganese oxalate, lithium dihydrogen phosphate and salicylic acid is added, obtains mixing material；
(2) powder was obtained by temperature dry 10 hours that after mixing material ball milling 30 hours, are placed in 200 DEG C of air dry oven
Material obtains a nanometer phosphoric acid as Temperature pre-treatment 8 hours of 500 DEG C in atmosphere furnace after crushing gained powder with disintegrating apparatus
Manganese iron lithium presoma；
(3) temperature that nano lithium iron manganese presoma is placed in nitrogen furnace at 700 DEG C is sintered 20 hours, obtains nanometer
Iron manganese phosphate for lithium powder body material LiAl0.005Fe0.195Mn0.8PO4。
Fig. 2 is the scanning electron microscope (SEM) photograph of lithium iron manganese phosphate anode material made from the embodiment of the present invention 7；It can from Fig. 2
Out, the partial size of lithium iron manganese phosphate anode material is 100-200nm.
Fig. 3 is the X ray diffracting spectrum of iron manganese phosphate for lithium (XRD) positive electrode made from the embodiment of the present invention 7；It will implement
Positive electrode obtained by example 7 and standard card compare, it is seen that obtain iron manganese phosphate for lithium peak, illustrate to have prepared manganese phosphate
Iron lithium anode material, and the peak of the XRD obtained is more sharp, illustrates that crystallinity is relatively good.
Effect example
Lithium iron manganese phosphate anode material, polyvinylidene fluoride binder and carbon black conductive agent obtained above are taken, by the phosphorus
Sour manganese iron lithium anode material, described adhesive and the conductive agent are mixed with mass ratio for the ratio of 93:3:4, are mixed
Object is closed, and the mixture is added in NMP (N-Methyl pyrrolidone) solvent, obtains mixed slurry, it then will be described mixed
The surface that slurry is coated in aluminium base is closed, obtains positive plate after dry；Wherein, according to the ratio of mixture content 60% in the solution
Nmp solvent is added in example, and ball grinding stirring 1 hour is mixed into slurry.Drying temperature is 110 DEG C；
The positive plate, cathode pole piece, diaphragm and electrolyte are assembled into lithium ion battery, the electrolyte includes carbonic acid
Vinyl acetate, methyl ethyl carbonate and lithium hexafluoro phosphate, wherein the volume ratio of the ethylene carbonate and the methyl ethyl carbonate is 3:
7, the concentration of the lithium hexafluoro phosphate is 1M.
Electrochemical property test is carried out to the battery that nano lithium iron manganese phosphate anode material prepared by the present invention is assembled into, is surveyed
Test result is as shown in the following table 1 and Fig. 4.From table 1 and Fig. 4 it can be seen that battery 1.0C discharges gram volume up to 140mAh/g,
Mean voltage can achieve 3.85V or more, illustrate the excellent material performance.
The performance test results of the battery as made from the positive electrode of embodiment 4-7 of table 1
Lithium iron phosphate positive material is prepared according to the similar method of above-described embodiment 4-7, and just by LiFePO4 obtained
The battery that pole material is assembled into carries out electrochemical property test, according to test result it is found that lithium iron phosphate positive material obtained
Performance is also very excellent.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of recoverying and utilizing method of waste lithium iron phosphate battery characterized by comprising
(1), waste lithium iron phosphate battery discharged, disassemble to obtain positive plate；
(2), the positive plate is dissolved in acid and obtains mixed solution A, after filtering, obtain filtrate and filter residue；
(3), ammonium hydroxide is added into the filtrate, stirs simultaneously, until resulting pH value of solution be 1.0-1.6, be obtained by filtration containing
The mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate precipitating；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4), ammonium hydroxide is added into the mixed solution B, stirs simultaneously, until resulting pH value of solution is 5.4-7.0, be obtained by filtration
Lithium sulfate filtrate and aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5), phosphorus-containing compound and alkali, stirring are added into the lithium sulfate filtrate, until acquired solution pH is 9.0-14.0, mistake
Filter is dried after being precipitated, and obtains lithium phosphate.
2. recoverying and utilizing method as described in claim 1, which is characterized in that the acid includes in sulfuric acid, hydrochloric acid and nitric acid
It is at least one.
3. recoverying and utilizing method as described in claim 1, which is characterized in that the phosphorus-containing compound includes phosphoric acid, phosphoric acid hydrogen
At least one of diammonium and ammonium dihydrogen phosphate.
4. recoverying and utilizing method as described in claim 1, which is characterized in that the alkali includes ammonium hydroxide, sodium hydroxide and hydrogen-oxygen
Change at least one of potassium.
5. recoverying and utilizing method as described in claim 1, which is characterized in that the step (3), step (4) and step (5)
Mixing speed is respectively 100-400r/min.
6. recoverying and utilizing method as described in claim 1, which is characterized in that in the step (3), be added the ammonium hydroxide until
After resulting pH value of solution is 1.0-1.6, continue to filter after stirring 30-60min；In the step (4), be added the ammonium hydroxide until
After resulting pH value of solution is 5.4-7.0, continue to filter after stirring 30-60min.
7. a kind of preparation method of lithium iron manganese phosphate anode material characterized by comprising
(1), waste lithium iron phosphate battery discharged, disassemble to obtain positive plate；
(2), the positive plate is dissolved in acid and obtains mixed solution A, after filtering, obtain filtrate and filter residue；
(3), ammonium hydroxide is added into the filtrate, stirs simultaneously, until resulting pH value of solution be 1.0-1.6, be obtained by filtration containing
The mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate precipitating；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4), ammonium hydroxide is added into the mixed solution B, stirs simultaneously, until resulting pH value of solution is 5.4-7.0, be obtained by filtration
Lithium sulfate filtrate and aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5), phosphorus-containing compound and alkali, stirring are added into the lithium sulfate filtrate, until acquired solution pH is 9.0-14.0, mistake
Filter is dried after being precipitated, and obtains lithium phosphate；
(6), according to the molar ratio of each element in iron manganese phosphate for lithium, the lithium phosphate, the ferric phosphate, phosphorus source and manganese source are mixed
It closes, and carbon source and solvent is added, obtain mixing material；
(7), iron manganese phosphate for lithium presoma will be obtained after the mixing material ball milling, drying；
(8), lithium iron manganese phosphate anode material will be obtained after iron manganese phosphate for lithium presoma calcining.
8. preparation method as claimed in claim 7, which is characterized in that the preparation method of the lithium iron manganese phosphate anode material is also
Include:
According to molar ratio nAl:nLi:nFe:nP:nMn=(0.002-0.02): (1.0-1.1): (0.18-0.498): (0.95-
1): (0.5-0.8) mixes the aluminium hydroxide, the lithium phosphate, the ferric phosphate, phosphorus source and the manganese source, and adds
Enter carbon source and solvent, obtains mixing material；Technique by step (7) and step (8) is obtaining the iron manganese phosphate for lithium of aluminium doping just
Pole material.
9. a kind of preparation method of lithium iron phosphate positive material characterized by comprising
(1), waste lithium iron phosphate battery discharged, disassemble to obtain positive plate；
(2), the positive plate is dissolved in acid and obtains mixed solution A, after filtering, obtain filtrate and filter residue；
(3), ammonium hydroxide is added into the filtrate, stirs simultaneously, until resulting pH value of solution be 1.0-1.6, be obtained by filtration containing
The mixed solution B and ferric phosphate of lithium sulfate and aluminum sulfate precipitating；Ferric phosphate will be obtained after ferric phosphate precipitating drying；
(4), ammonium hydroxide is added into the mixed solution B, stirs simultaneously, until resulting pH value of solution is 5.4-7.0, be obtained by filtration
Lithium sulfate filtrate and aluminum hydroxide precipitation；Aluminium hydroxide will be obtained after aluminum hydroxide precipitation drying；
(5), phosphorus-containing compound and alkali, stirring are added into the lithium sulfate filtrate, until acquired solution pH is 9.0-14.0, mistake
Filter is dried after being precipitated, and obtains lithium phosphate；
(6), according to the molar ratio of each element in lithium iron phosphate positive material, the lithium phosphate, the ferric phosphate and phosphorus source are mixed
It closes, and carbon source and solvent is added, obtain mixing material；
(7), ferric lithium phosphate precursor will be obtained after the mixing material ball milling, drying；
(8), lithium iron phosphate positive material will be obtained after iron manganese phosphate for lithium presoma calcining.
10. preparation method as claimed in claim 9, which is characterized in that the preparation method of the lithium iron phosphate positive material is also
Include:
According to molar ratio nAl:nLi:nFe:nP=(0.002-0.02): (1.0-1.1): (0.98-0.998): (0.95-1), it will
The aluminium hydroxide, the lithium phosphate, the ferric phosphate and source of iron mixing, and carbon source and solvent is added, obtain mixing material；Through
The technique for crossing step (7) and step (8) obtains the lithium iron phosphate positive material of aluminium doping.
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| CN115535987B (en) * | 2022-10-24 | 2024-01-30 | 中南大学 | Method for recycling valuable elements from lithium iron manganese phosphate positive electrode waste |
| CN115784191A (en) * | 2022-12-12 | 2023-03-14 | 厦门厦钨新能源材料股份有限公司 | Method for recycling lithium iron phosphate from waste lithium iron phosphate anode material |
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Application publication date: 20181214 |