CN109742477A - A kind of recovery method of waste and old ternary oxide anode - Google Patents
A kind of recovery method of waste and old ternary oxide anode Download PDFInfo
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- CN109742477A CN109742477A CN201910019270.XA CN201910019270A CN109742477A CN 109742477 A CN109742477 A CN 109742477A CN 201910019270 A CN201910019270 A CN 201910019270A CN 109742477 A CN109742477 A CN 109742477A
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention belongs to lithium ion cell positive recovery technology fields.The present invention provides a kind of recovery methods of waste and old ternary oxide anode, after including the following steps: that (1) mixes ternary oxide anode, the acid solution of hydrogen peroxide, phosphoric acid root, source of iron, lithium nitrate and citric acid, through drying, the first presoma is obtained;The molar ratio of lithium, iron, nickel, cobalt and manganese element in first presoma is 1.05~1.15:x:y:z:(1-x-y-z), wherein 0 < x < 1,0 < y < 1,0 < z < 1;(2) first presoma is successively subjected to ball milling and the first calcining, obtains the second presoma;(3) after mixing second presoma and citric acid, the second calcining is carried out, ferric phosphate nickel cobalt manganese lithium anode material is obtained;First calcining and the second calcining carry out in protective atmosphere.The electric discharge specific volume for the positive electrode that method provided by the invention obtains is up to 120mAh/g or more.
Description
Technical field
Positive the present invention relates to lithium ion cell positive recovery technology field more particularly to a kind of waste and old ternary oxide
Recovery method.
Background technique
With a large amount of uses of lithium ion battery, a large amount of waste and old lithium ion battery is produced.These old and useless batterys due to
It can not meet corresponding energy storage demand and be eliminated.If directly these old and useless batterys handled as Other Waste, very
It is likely to result in serious environmental pollution, there is also the hidden danger that battery short circuit brings fire.Moreover, containing in these old and useless batterys
A large amount of transition metal, these transition metal reserves in the earth are limited, directly as conventional rubbish processing, can also waste a large amount of
Transition metal.
Ternary oxide (i.e. nickle cobalt lithium manganate LiNixCoyMnzO2) it is a kind of commercial li-ion battery largely used
Positive electrode.Contain the non-renewable metal member such as a large amount of nickel (Ni), cobalt (Co), manganese (Mn) and lithium (Li) in old and useless battery
Element.Not only reserves are limited on earth for these metallic elements, by a large amount of prolonged exploitations, continue supply time then very
It is limited.But the method that the prior art can effectively recycle ternary oxide not yet.
Summary of the invention
The purpose of the present invention is to provide a kind of recovery method of waste and old ternary oxide anode, this method can be returned effectively
Receive ternary oxide anode.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of recovery methods of waste and old ternary oxide anode, include the following steps:
(1) by ternary oxide anode, the acid solution of hydrogen peroxide, phosphoric acid root, source of iron, lithium nitrate and lemon acid-mixed
After conjunction, through drying, the first presoma is obtained;The molar ratio of lithium, iron, nickel, cobalt and manganese element in first presoma is
1.05~1.15:x:y:z:(1-x-y-z), wherein 0 < x < 1,0 < y < 1,0 < z < 1;
(2) first presoma is successively subjected to ball milling and the first calcining, obtains the second presoma;
(3) after mixing second presoma and citric acid, the second calcining is carried out, obtains ferric phosphate nickel cobalt manganese lithium anode
Material;
First calcining and the second calcining carry out in protective atmosphere.
Preferably, the pH value of the acid solution of hydrogen peroxide is less than 3 in the step (1), the acidity of the hydrogen peroxide
The molar ratio of hydrogen peroxide in solution and the elemental lithium in ternary oxide anode is 2.8~3.5:1.
Preferably, phosphoric acid root is in monoammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid and ammonium phosphate in the step (1)
It is at least one.
Preferably, source of iron is in ferric nitrate, ferric acetate, ferrous acetate, ferric oxalate and ferrous oxalate in the step (1)
It is at least one.
Preferably, the elemental lithium in the step (1) in the first presoma and the phosphate anion in phosphoric acid root, lemon
The molar ratio of acid is 1.05~1.15:1:1.
Preferably, the revolving speed of ball milling is 200~600r/min in the step (2), and the time of the ball milling is 6~20h.
Preferably, the mass ratio of ball milling abrading-ball and the first presoma is preferably 15~30:1.
Preferably, the temperature of the first calcining is 300~450 DEG C in the step (2), and the time of first calcining is 2
~5h.
Preferably, the mass ratio of the second presoma and citric acid is 1.5~3:1 in the step (3).
Preferably, the temperature of the second calcining is 600~700 DEG C in the step (3), and the time of second calcining is 8
~12h.
The present invention provides a kind of recovery methods of waste and old ternary oxide anode, include the following steps: (1) by ternary oxygen
After compound anode, the acid solution of hydrogen peroxide, phosphoric acid root, source of iron, lithium nitrate and citric acid mixing, through drying, the is obtained
One presoma;The molar ratio of lithium, iron, nickel, cobalt and manganese element in first presoma is 1.05~1.15:x:y:z:(1-
X-y-z), wherein 0 < x < 1,0 < y < 1,0 < z < 1;(2) first presoma is successively subjected to ball milling and the first calcining, obtains the
Two presomas;(3) after mixing second presoma and citric acid, the second calcining is carried out, is obtaining ferric phosphate nickel cobalt manganese lithium just
Pole material;First calcining and the second calcining carry out in protective atmosphere.Method provided by the present invention is by ternary oxide
Anode, the acid solution of hydrogen peroxide, phosphoric acid root, source of iron, lithium nitrate and citric acid mixing, hydrogen peroxide is in acid condition
Nickle cobalt lithium manganate in ternary oxide anode can be dissolved, and the ratio of each metallic element is adjusted in source of iron and lithium nitrate, lemon
On the one hand lemon acid is used as carbon source, after the first calcining and the second calcining, generate carbon coating in surface of metal particles, increase product
Electric conductivity, on the other hand, citric acid can be complexed with metal ion as complexing agent, can protect to a certain extent
The stability of metal ion in the solution is demonstrate,proved, while this complexing can make the scantling finally synthesized become smaller, surface
Carbon coating is more uniform;First presoma can be such that conductive agent and binder is uniformly mixed with other compositions, then pass through through ball milling
First calcining, organic matter occur preliminary exposition, obtain the second presoma;In order to increase carbon source, by the second presoma and citric acid
Then mixing carries out the second calcining, decomposes organic matter sufficiently, obtain agraphitic carbon package ferric phosphate nickel cobalt manganese lithium anode material
Material.Method provided by the present invention not only realizes the recycling of metal in ternary oxide anode, while also by ternary oxide
Conductive agent and binder in anode have carried out effective utilization, simplify the recovery method of ternary oxide anode, simultaneously
Positive electrode of good performance is arrived, the electric discharge specific volume of gained positive electrode is up to 120mAh/g or more.
Specific embodiment
The present invention provides a kind of recovery methods of waste and old ternary oxide anode, include the following steps:
(1) by ternary oxide anode (i.e. nickle cobalt lithium manganate anode), the acid solution of hydrogen peroxide, phosphoric acid root, iron
After source, lithium nitrate and citric acid mixing, through drying, the first presoma is obtained;Lithium, iron, nickel, cobalt in first presoma and
The molar ratio of manganese element is 1.05~1.15:x:y:z:(1-x-y-z), wherein 0 < x < 1,0 < y < 1,0 < z < 1;
(2) first presoma is successively subjected to ball milling and the first calcining, obtains the second presoma;
(3) after mixing second presoma and citric acid, the second calcining is carried out, obtains ferric phosphate nickel cobalt manganese lithium anode
Material;
First calcining and the second calcining carry out in protective atmosphere.
The present invention is by ternary oxide anode, the acid solution of hydrogen peroxide, phosphoric acid root, source of iron, lithium nitrate and lemon
After acid-mixed is closed, through drying, the first presoma is obtained.In the present invention, the ternary oxide anode does not include collector.
In the present invention, the nickle cobalt lithium manganate in ternary oxide anode can in the acid solution of hydrogen peroxide
Hydrogen peroxide occur redox reaction, lithium ion in the solution it is ionizable come out, nickel cobalt manganese acid group can be reduced, generate
Nickel ion, cobalt ions and manganese ion.
The present invention is not particularly limited the source of the ternary oxide anode, can derive from and ternary oxygen is used arbitrarily
The lithium battery of compound anode.
In the present invention, the pH value of the acid solution of the hydrogen peroxide is preferably smaller than 3, and the acidity of the hydrogen peroxide is molten
The molar ratio of hydrogen peroxide in liquid and the elemental lithium in ternary oxide anode is preferably 2.8~3.5:1.
In the present invention, adjusting acid used in the pH value of the acid solution of the hydrogen peroxide is preferably nitric acid, sulfuric acid, salt
Acid or citric acid, more preferably nitric acid.
In the present invention, the phosphoric acid root be preferably in monoammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid and ammonium phosphate extremely
Few one kind.
In the present invention, the source of iron is preferably in ferric nitrate, ferric acetate, ferrous acetate, ferric oxalate and ferrous oxalate
It is at least one.
In the present invention, elemental lithium and phosphoric acid root during preparing first presoma, in the first presoma
In phosphate anion, citric acid molar ratio be preferably 1.05~1.15:1:1.
In the present invention, on the one hand the citric acid added during preparing first presoma is used as carbon source, pass through
After first calcining and the second calcining, carbon coating is generated in surface of metal particles, increases the electric conductivity of product, on the other hand, lemon
Acid is used as complexing agent, can be complexed with metal ion, can guarantee metal ion in the solution steady to a certain extent
It is qualitative, while this complexing can make the scantling finally synthesized become smaller, material with carbon-coated surface is more uniform.
The present invention to the ternary oxide anode, the acid solution of hydrogen peroxide, phosphoric acid root, source of iron, lithium nitrate and
The order by merging of citric acid is not particularly limited, and can be any order by merging.In embodiments of the present invention, preferably by ternary oxygen
Compound anode is mixed with the acid solution of hydrogen peroxide, then, then with other material mixings.
The present invention to the ternary oxide anode, the acid solution of hydrogen peroxide, phosphoric acid root, source of iron, lithium nitrate and
The hybrid mode of citric acid is not particularly limited, and can obtain uniform mixture.In embodiments of the present invention, it preferably adopts
It is mixed with the mode of stirring.
The present invention is not particularly limited dry mode, can obtain the first dry presoma.In the present invention
In embodiment, it is preferred to use by the ternary oxide anode, the acid solution of hydrogen peroxide, phosphoric acid root, source of iron, lithium nitrate
60~100 DEG C are warming up to the mixed liquor of citric acid, is stirred to dry.The present invention is not particularly limited the revolving speed of the stirring,
It can be conventional rotating speed.In the present invention, it is described it is dry stir using in higher temperature to by the way of dry, various ions can be made
It is uniformly mixed.
In the present invention, lithium ion, iron ion, nickel ion, cobalt ions, manganese ion, phosphorus are contained in first presoma
Acid group plasma species, also containing the conductive agent and binder insoluble in solution.
In the present invention, the molar ratio of the lithium in first presoma, iron, nickel, cobalt and manganese element is 1.05~1.15:
X:y:z:(1-x-y-z), wherein 0 < x < 1,0 < y < 1,0 < z < 1.In the present invention, the conductive agent and bonding in the positive electrode
The mass percentage of agent can be measured by thermogravimetric, and the mole of each element in the ternary oxide anode can pass through
It is (i.e. electric using ICP technology after the acid solution of the ternary oxide anode and the hydrogen peroxide is mixed to get mixed liquor
Sense linking atom emission spectrometer) measurement mixed liquor in metallic element mole obtain.It obtains in ternary oxide anode
After element mole, according to design proportion, source of iron and lithium nitrate are added.
After obtaining the first presoma, first presoma is successively carried out ball milling and the first calcining by the present invention, obtains the
Two presomas.In the present invention, the ball milling can by the first presoma conductive agent and binder mix with other compositions
Uniformly;It is described first calcining can by the first presoma nitrate and organic matter (such as binder, citric acid) carry out just
Step is decomposed.
In the present invention, first calcining carries out in protective atmosphere.In the present invention, the protective atmosphere can be true
It protects the first presoma not react with oxygen, to reduce the carbon loss in the first presoma.In the present invention, the protective atmosphere is excellent
It is selected as nitrogen or atmosphere of inert gases.
It in the present invention, is preferably wet ball grinding or dry ball milling to the ball milling of first presoma, it is more preferably wet
Method ball milling;The revolving speed of the ball milling is preferably 200~600r/min, more preferably 300~500r/min;The time of the ball milling
Preferably 6~20h, more preferably 10~15h;Dispersing agent used in the wet ball grinding is preferably acetone, ethyl alcohol or water;The present invention
The dosage of dispersing agent used in the wet ball grinding is not particularly limited, abrading-ball used in the first presoma and ball milling can be submerged i.e.
It can.
In the present invention, the partial size of abrading-ball used in the ball milling is preferably 2~12mm;The abrading-ball that the ball milling uses is preferred
For the abrading-ball of gradation, the present invention is not particularly limited the design of the gradation, and those skilled in the art can be using common
Gradation design.
In the present invention, the mass ratio of the abrading-ball and the first presoma is preferably 15~30:1.After the completion of the ball milling,
The product that the present invention preferably obtains ball milling is dried, and then carries out the first calcining.The present invention does not have the mode of the drying
There is particular determination, the dispersing agent in product can be removed.
In the present invention, the temperature of first calcining is preferably 300~450 DEG C, and more preferably 350~400 DEG C;It is described
The time of first calcining is preferably 2~5h, more preferably 3~4h.
After obtaining the second presoma, after the present invention mixes second presoma and citric acid, the second calcining is carried out, is obtained
To ferric phosphate nickel cobalt manganese lithium anode material.In the present invention, after obtaining the second presoma, using citric acid as carbon source, with second
Presoma mixing, can increase the carbon content in final products obtained therefrom, improve the electric conductivity of product.
In the present invention, the mass ratio of second presoma and citric acid is preferably 1.5~3:1.
The present invention is not particularly limited the mixed mode, can be uniformly mixed the second presoma i.e. with citric acid
It can.
It is preferably mixed by the way of ball milling in embodiments of the present invention;The condition of the ball milling with to the first forerunner
The ball milling condition of body is identical, and details are not described herein.In embodiments of the present invention, after the completion of the ball milling, the present invention is preferably by ball
It grinds obtained product to be dried, then carries out the second calcining.The present invention is not particularly limited the mode of the drying, can
By the dispersing agent removal in product.In the present invention, the second presoma and citric acid are mixed by the way of ball milling, it can be with
It is more evenly distributed in citric acid in the second presoma, while being also beneficial to improve intermolecular compactness.
In the present invention, the temperature of second calcining is preferably 600~700 DEG C, and more preferably 650~675 DEG C;It is described
The time of second calcining is preferably 8~12h, more preferably 9~11h.In the present invention, second calcining can be by organic matter
Further carbonization generates agraphitic carbon and is wrapped in final product surface.
In the present invention, second calcining carries out in protective atmosphere.In the present invention, the protective atmosphere can be true
It protects calcined material not react with oxygen, to reduce carbon loss.
It is detailed to a kind of recovery method progress of waste and old ternary oxide anode provided by the invention below with reference to embodiment
Explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) 0.02molLiNi will be contained0.33Co0.33Mn0.33O2Ternary oxide anode and pH value be 3 hydrogen peroxide
Acid solution mixing, the mole of the hydrogen peroxide is 0.003mol, obtains mixed liquor;By the mixed liquor with
0.00793molLiNO3, 0.0066molFe (NO3)3, 0.02793molNH4H2PO4, 0.02793molC6H8O7After mixing, heating
To 80 DEG C, in 80 DEG C of stirrings to drying, the first presoma is obtained;
(2) by first presoma 500r/min condition ball milling 12h, then by ball milling products therefrom it is dry after,
3h is calcined in 350 DEG C of argon atmospheres, obtains the second presoma;In the mechanical milling process, the quality of abrading-ball and the first presoma
Than for 20:1, dispersing agent used in ball milling is acetone;
(3) second presoma and citric acid are mixed according to the ratio that mass ratio is 2:1, in the condition of 500r/min
Ball milling 12h calcines 10h in 675 DEG C of argon atmospheres, obtains then by after the drying of ball milling products therefrom
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode;The quality of the quality sum and abrading-ball of second presoma and citric acid
Than for 1:20;Dispersing agent used in ball milling is acetone.
It is prepared into button-type battery using the present embodiment products therefrom as the active material of positive electrode, tests the present embodiment
Gained LiFe0.25Ni0.25Co0.25Mn0.25PO4The chemical property of positive electrode, the specific method is as follows:
The button-type battery includes anode pole piece, cathode pole piece, diaphragm and electrolyte;
According to active material: conductive agent: the ratio that the mass ratio of binder is 7:2:1 mixes, in the afflux of anode pole piece
Applying coating on body, obtains anode pole piece;
The cathode pole piece is lithium metal thin slice;The diaphragm is glass fibre membrane (being purchased from Britain Whatman company);Institute
Stating electrolyte is the LiPF that concentration is 1mol/L6Solution, the ethylene carbonate and dimethyl carbonate mixing that solvent is volume ratio 1:1
Liquid.It is assembled to obtain button-type battery in glove box.
Electrochemical analysis test is carried out to above-mentioned button-type battery, is 2.0~5.0V in charge and discharge section, current density is
The condition of 20mA/g carries out charge and discharge, measures LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode capacity up to 125mAh/g, and
100 circle capacity of circulation is without obvious decaying.Illustrate that the present invention can carry out the metallic element in waste and old ternary oxide lithium battery
Recycling and reusing, and final resulting materials capacity with higher and stable cycle performance, can be used as lithium ion battery
Positive electrode uses.
Embodiment 2
(1) 0.04mol LiNi will be contained0.33Co0.33Mn0.33O2Ternary oxide anode and pH value be 3 peroxidating
The acid solution of hydrogen mixes, and the mole of the hydrogen peroxide is 0.006mol, obtains mixed liquor;By the mixed liquor with
0.01586molLiNO3, 0.0132molFe (NO3)3, 0.05586molNH4H2PO4, 0.05586molC6H8O7After mixing, heating
To 80 DEG C, in 80 DEG C of stirrings to drying, the first presoma is obtained;
(2) by first presoma 500r/min condition ball milling 12h, then by ball milling products therefrom it is dry after,
3h is calcined in 350 DEG C of argon atmospheres, obtains the second presoma;In the mechanical milling process, the quality of abrading-ball and the first presoma
Than for 20:1, dispersing agent used in ball milling is acetone;
(3) second presoma and citric acid are mixed according to the ratio that mass ratio is 2:1, in the condition of 500r/min
Ball milling 12h calcines 10h in 675 DEG C of argon atmospheres, obtains then by after the drying of ball milling products therefrom
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode;The quality of the quality sum and abrading-ball of second presoma and citric acid
Than for 1:20;Dispersing agent used in ball milling is acetone.
It is prepared into button-type battery using the present embodiment products therefrom as the active material of positive electrode, according to embodiment 1
The method tests LiFe obtained by the present embodiment0.25Ni0.25Co0.25Mn0.25PO4The chemical property of positive electrode.As a result table
It is bright, it is 2.0~5.0V in charge and discharge section, the condition that current density is 20mA/g carries out charge and discharge, measures
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode capacity recycles 100 circle capacity without obvious decaying up to 123mAh/g.
Embodiment 3
(1) 0.06molLiNi will be contained0.33Co0.33Mn0.33O2Ternary oxide anode and pH value be 3 hydrogen peroxide
Acid solution mixing, the mole of the hydrogen peroxide is 0.009mol, obtains mixed liquor;By the mixed liquor with
0.02379molLiNO3, 0.0198molmolFe (NO3)3, 0.08379molNH4H2PO4, 0.08379molC6H8O7After mixing,
80 DEG C are warming up to, in 80 DEG C of stirrings to drying, obtains the first presoma;
(2) by first presoma 500r/min condition ball milling 12h, then by ball milling products therefrom it is dry after,
3h is calcined in 350 DEG C of argon atmospheres, obtains the second presoma;In the mechanical milling process, the quality of abrading-ball and the first presoma
Than for 20:1, dispersing agent used in ball milling is acetone;
(3) second presoma and citric acid are mixed according to the ratio that mass ratio is 2:1, in the condition of 500r/min
Ball milling 12h calcines 10h in 675 DEG C of argon atmospheres, obtains then by after the drying of ball milling products therefrom
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode;The quality of the quality sum and abrading-ball of second presoma and citric acid
Than for 1:20;Dispersing agent used in ball milling is acetone.
It is prepared into button-type battery using the present embodiment products therefrom as the active material of positive electrode, according to embodiment 1
The method tests LiFe obtained by the present embodiment0.25Ni0.25Co0.25Mn0.25PO4The chemical property of positive electrode.As a result table
It is bright, it is 2.0~5.0V in charge and discharge section, the condition that current density is 20mA/g carries out charge and discharge, measures
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode capacity recycles 100 circle capacity without obvious decaying up to 126mAh/g.
Embodiment 4
(1) 0.02molLiNi will be contained0.33Co0.33Mn0.33O2Ternary oxide anode and pH value be 3 hydrogen peroxide
Acid solution mixing, the mole of the hydrogen peroxide is 0.003mol, obtains mixed liquor;By the mixed liquor with
0.00793molLiNO3, 0.0066molmolFe (NO3)3, 0.02793molNH4H2PO4, 0.02793molC6H8O7After mixing,
80 DEG C are warming up to, in 80 DEG C of stirrings to drying, obtains the first presoma;
(2) by first presoma 500r/min condition ball milling 12h, then by ball milling products therefrom it is dry after,
3h is calcined in 350 DEG C of argon atmospheres, obtains the second presoma;In the mechanical milling process, the quality of abrading-ball and the first presoma
Than for 20:1, dispersing agent used in ball milling is acetone;
(3) second presoma and citric acid are mixed according to the ratio that mass ratio is 2:1, in the condition of 500r/min
Ball milling 12h calcines 10h in 650 DEG C of argon atmospheres, obtains then by after the drying of ball milling products therefrom
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode;The quality of the quality sum and abrading-ball of second presoma and citric acid
Than for 1:20;Dispersing agent used in ball milling is acetone.
It is prepared into button-type battery using the present embodiment products therefrom as the active material of positive electrode, according to embodiment 1
The method tests LiFe obtained by the present embodiment0.25Ni0.25Co0.25Mn0.25PO4The chemical property of positive electrode.As a result table
It is bright, it is 2.0~5.0V in charge and discharge section, the condition that current density is 20mA/g carries out charge and discharge, measures
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode capacity recycles 100 circle capacity without obvious decaying up to 122mAh/g.
Embodiment 5
(1) 0.02molLiNi will be contained0.33Co0.33Mn0.33O2Ternary oxide anode and pH value be 3 hydrogen peroxide
Acid solution mixing, the mole of the hydrogen peroxide is 0.003mol, obtains mixed liquor;By the mixed liquor with
0.00793molLiNO3, 0.0066molmolFe (NO3)3, 0.02793molNH4H2PO4, 0.02793molC6H8O7After mixing,
80 DEG C are warming up to, in 80 DEG C of stirrings to drying, obtains the first presoma;
(2) by first presoma 500r/min condition ball milling 12h, then by ball milling products therefrom it is dry after,
3h is calcined in 350 DEG C of argon atmospheres, obtains the second presoma;In the mechanical milling process, the quality of abrading-ball and the first presoma
Than for 20:1, dispersing agent used in ball milling is acetone;
(3) second presoma and citric acid are mixed according to the ratio that mass ratio is 2:1, in the condition of 500r/min
Ball milling 12h calcines 10h in 625 DEG C of argon atmospheres, obtains then by after the drying of ball milling products therefrom
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode;The quality of the quality sum and abrading-ball of second presoma and citric acid
Than for 1:20;Dispersing agent used in ball milling is acetone.
It is prepared into button-type battery using the present embodiment products therefrom as the active material of positive electrode, according to embodiment 1
The method tests LiFe obtained by the present embodiment0.25Ni0.25Co0.25Mn0.25PO4The chemical property of positive electrode.As a result table
It is bright, it is 2.0~5.0V in charge and discharge section, the condition that current density is 20mA/g carries out charge and discharge, measures
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode capacity recycles 100 circle capacity without obvious decaying up to 121mAh/g.
Embodiment 6
(1) 0.02molLiNi will be contained0.33Co0.33Mn0.33O2Ternary oxide anode and pH value be 3 hydrogen peroxide
Acid solution mixing, the mole of the hydrogen peroxide is 0.003mol, obtains mixed liquor;By the mixed liquor with
0.00793molLiNO3, 0.0066molmolFe (NO3)3, 0.02793molNH4H2PO4, 0.02793molC6H8O7After mixing,
80 DEG C are warming up to, in 80 DEG C of stirrings to drying, obtains the first presoma;
(2) by first presoma 500r/min condition ball milling 12h, then by ball milling products therefrom it is dry after,
3h is calcined in 350 DEG C of argon atmospheres, obtains the second presoma;In the mechanical milling process, the quality of abrading-ball and the first presoma
Than for 20:1, dispersing agent used in ball milling is acetone;
(3) second presoma and citric acid are mixed according to the ratio that mass ratio is 2:1, in the condition of 500r/min
Ball milling 12h calcines 10h in 700 DEG C of argon atmospheres, obtains then by after the drying of ball milling products therefrom
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode;The quality of the quality sum and abrading-ball of second presoma and citric acid
Than for 1:20;Dispersing agent used in ball milling is acetone.
It is prepared into button-type battery using the present embodiment products therefrom as the active material of positive electrode, according to embodiment 1
The method tests LiFe obtained by the present embodiment0.25Ni0.25Co0.25Mn0.25PO4The chemical property of positive electrode.As a result table
It is bright, it is 2.0~5.0V in charge and discharge section, the condition that current density is 20mA/g carries out charge and discharge, measures
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode capacity recycles 100 circle capacity without obvious decaying up to 119mAh/g.
Embodiment 7
(1) 0.02molLiNi will be contained0.33Co0.33Mn0.33O2Ternary oxide anode and pH value be 3 hydrogen peroxide
Acid solution mixing, the mole of the hydrogen peroxide is 0.003mol, obtains mixed liquor;By the mixed liquor with
0.00793molLiNO3, 0.0066molmolFe (NO3)3, 0.02793molNH4H2PO4, 0.02793molC6H8O7After mixing,
80 DEG C are warming up to, in 80 DEG C of stirrings to drying, obtains the first presoma;
(2) by first presoma 500r/min condition ball milling 12h, then by ball milling products therefrom it is dry after,
3h is calcined in 350 DEG C of argon atmospheres, obtains the second presoma;In the mechanical milling process, the quality of abrading-ball and the first presoma
Than for 20:1, dispersing agent used in ball milling is acetone;
(3) second presoma and citric acid are mixed according to the ratio that mass ratio is 2:1, in the condition of 500r/min
Ball milling 12h calcines 8h in 675 DEG C of argon atmospheres, obtains then by after the drying of ball milling products therefrom
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode;The quality of the quality sum and abrading-ball of second presoma and citric acid
Than for 1:20;Dispersing agent used in ball milling is acetone.
It is prepared into button-type battery using the present embodiment products therefrom as the active material of positive electrode, according to embodiment 1
The method tests LiFe obtained by the present embodiment0.25Ni0.25Co0.25Mn0.25PO4The chemical property of positive electrode.As a result table
It is bright, it is 2.0~5.0V in charge and discharge section, the condition that current density is 20mA/g carries out charge and discharge, measures
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode capacity recycles 100 circle capacity without obvious decaying up to 121mAh/g.
Embodiment 8
(1) 0.02molLiNi will be contained0.33Co0.33Mn0.33O2Ternary oxide anode and pH value be 3 hydrogen peroxide
Acid solution mixing, the mole of the hydrogen peroxide is 0.003mol, obtains mixed liquor;By the mixed liquor with
0.00793molLiNO3, 0.0066molmolFe (NO3)3, 0.02793molNH4H2PO4, 0.02793molC6H8O7After mixing,
80 DEG C are warming up to, in 80 DEG C of stirrings to drying, obtains the first presoma;
(2) by first presoma 500r/min condition ball milling 12h, then by ball milling products therefrom it is dry after,
3h is calcined in 350 DEG C of argon atmospheres, obtains the second presoma;In the mechanical milling process, the quality of abrading-ball and the first presoma
Than for 20:1, dispersing agent used in ball milling is acetone;
(3) second presoma and citric acid are mixed according to the ratio that mass ratio is 2:1, in the condition of 500r/min
Ball milling 12h calcines 9h in 675 DEG C of argon atmospheres, obtains then by after the drying of ball milling products therefrom
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode;The quality of the quality sum and abrading-ball of second presoma and citric acid
Than for 1:20;Dispersing agent used in ball milling is acetone.
It is prepared into button-type battery using the present embodiment products therefrom as the active material of positive electrode, according to embodiment 1
The method tests LiFe obtained by the present embodiment0.25Ni0.25Co0.25Mn0.25PO4The chemical property of positive electrode.As a result table
It is bright, it is 2.0~5.0V in charge and discharge section, the condition that current density is 20mA/g carries out charge and discharge, measures
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode capacity recycles 100 circle capacity without obvious decaying up to 120mAh/g.
Embodiment 9
(1) 0.02molLiNi will be contained0.33Co0.33Mn0.33O2Ternary oxide anode and pH value be 3 hydrogen peroxide
Acid solution mixing, the mole of the hydrogen peroxide is 0.003mol, obtains mixed liquor;By the mixed liquor with
0.00793molLiNO3, 0.0066molmolFe (NO3)3, 0.02793molNH4H2PO4, 0.02793molC6H8O7After mixing,
80 DEG C are warming up to, in 80 DEG C of stirrings to drying, obtains the first presoma;
(2) by first presoma 500r/min condition ball milling 12h, then by ball milling products therefrom it is dry after,
3h is calcined in 350 DEG C of argon atmospheres, obtains the second presoma;In the mechanical milling process, the quality of abrading-ball and the first presoma
Than for 20:1, dispersing agent used in ball milling is acetone;
(3) second presoma and citric acid are mixed according to the ratio that mass ratio is 2:1, in the condition of 500r/min
Ball milling 12h calcines 11h in 675 DEG C of argon atmospheres, obtains then by after the drying of ball milling products therefrom
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode;The quality of the quality sum and abrading-ball of second presoma and citric acid
Than for 1:20;Dispersing agent used in ball milling is acetone.
It is prepared into button-type battery using the present embodiment products therefrom as the active material of positive electrode, according to embodiment 1
The method tests LiFe obtained by the present embodiment0.25Ni0.25Co0.25Mn0.25PO4The chemical property of positive electrode.As a result table
It is bright, it is 2.0~5.0V in charge and discharge section, the condition that current density is 20mA/g carries out charge and discharge, measures
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode capacity recycles 100 circle capacity without obvious decaying up to 122mAh/g.
Embodiment 10
(1) 0.02molLiNi will be contained0.33Co0.33Mn0.33O2Ternary oxide anode and pH value be 3 hydrogen peroxide
Acid solution mixing, the mole of the hydrogen peroxide is 0.003mol, obtains mixed liquor;By the mixed liquor with
0.00793molLiNO3, 0.0066molmolFe (NO3)3, 0.02793molNH4H2PO4, 0.02793molC6H8O7After mixing,
80 DEG C are warming up to, in 80 DEG C of stirrings to drying, obtains the first presoma;
(2) by first presoma 500r/min condition ball milling 12h, then by ball milling products therefrom it is dry after,
3h is calcined in 350 DEG C of argon atmospheres, obtains the second presoma;In the mechanical milling process, the quality of abrading-ball and the first presoma
Than for 20:1, dispersing agent used in ball milling is acetone;
(3) second presoma and citric acid are mixed according to the ratio that mass ratio is 2:1, in the condition of 500r/min
Ball milling 12h calcines 12h in 675 DEG C of argon atmospheres, obtains then by after the drying of ball milling products therefrom
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode;The quality of the quality sum and abrading-ball of second presoma and citric acid
Than for 1:20;Dispersing agent used in ball milling is acetone.
It is prepared into button-type battery using the present embodiment products therefrom as the active material of positive electrode, according to embodiment 1
The method tests LiFe obtained by the present embodiment0.25Ni0.25Co0.25Mn0.25PO4The chemical property of positive electrode.As a result table
It is bright, it is 2.0~5.0V in charge and discharge section, the condition that current density is 20mA/g carries out charge and discharge, measures
LiFe0.25Ni0.25Co0.25Mn0.25PO4Positive electrode capacity recycles 100 circle capacity without obvious decaying up to 120mAh/g.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of recovery method of waste and old ternary oxide anode, includes the following steps:
(1) ternary oxide anode, the acid solution of hydrogen peroxide, phosphoric acid root, source of iron, lithium nitrate and citric acid are mixed
Afterwards, through drying, the first presoma is obtained;The molar ratio of lithium, iron, nickel, cobalt and manganese element in first presoma is 1.05
~1.15:x:y:z:(1-x-y-z), wherein 0 < x < 1,0 < y < 1,0 < z < 1;
(2) first presoma is successively subjected to ball milling and the first calcining, obtains the second presoma;
(3) after mixing second presoma and citric acid, the second calcining is carried out, ferric phosphate nickel cobalt manganese lithium anode material is obtained
Material;
First calcining and the second calcining carry out in protective atmosphere.
2. recovery method according to claim 1, which is characterized in that the acid solution of hydrogen peroxide in the step (1)
PH value less than 3, hydrogen peroxide in the acid solution of the hydrogen peroxide rubs with the elemental lithium in ternary oxide anode
You are than being 2.8~3.5:1.
3. recovery method according to claim 1, which is characterized in that phosphoric acid root is one hydrogen of phosphoric acid in the step (1)
At least one of ammonium, ammonium dihydrogen phosphate, phosphoric acid and ammonium phosphate.
4. recovery method according to claim 1, which is characterized in that source of iron is ferric nitrate, acetic acid in the step (1)
At least one of iron, ferrous acetate, ferric oxalate and ferrous oxalate.
5. recovery method according to claim 1, which is characterized in that the lithium member in the step (1) in the first presoma
The molar ratio of element and phosphate anion, citric acid in phosphoric acid root is 1.05~1.15:1:1.
6. recovery method according to claim 1, which is characterized in that in the step (2) revolving speed of ball milling be 200~
600r/min, the time of the ball milling are 6~20h.
7. recovery method according to claim 6, which is characterized in that the quality of the ball milling abrading-ball and the first presoma
Than being preferably 15~30:1.
8. according to claim 1,6 and 7 described in any item recovery methods, which is characterized in that the first calcining in the step (2)
Temperature be 300~450 DEG C, first calcining time be 2~5h.
9. recovery method according to claim 1, which is characterized in that the second presoma and citric acid in the step (3)
Mass ratio be 1.5~3:1.
10. recovery method according to claim 1, which is characterized in that the temperature of the second calcining is in the step (3)
600~700 DEG C, the time of the second calcining is 8~12h.
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