CN109742477B - Method for recovering waste ternary oxide positive electrode - Google Patents

Method for recovering waste ternary oxide positive electrode Download PDF

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CN109742477B
CN109742477B CN201910019270.XA CN201910019270A CN109742477B CN 109742477 B CN109742477 B CN 109742477B CN 201910019270 A CN201910019270 A CN 201910019270A CN 109742477 B CN109742477 B CN 109742477B
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precursor
positive electrode
calcination
citric acid
lithium
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CN109742477A (en
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吴兴隆
杨洋
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Northeast Normal University
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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
    • 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
    • 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 the technical field of recovery of a lithium ion battery anode. The invention provides a method for recovering a waste ternary oxide anode, which comprises the following steps: (1) mixing a ternary oxide positive electrode, an acidic solution of hydrogen peroxide, a phosphate source, an iron source, lithium nitrate and citric acid, and drying to obtain a first precursor; the molar ratio of lithium, iron, nickel, cobalt and manganese elements in the first precursor is 1.05-1.15: x: y: z (1-x-y-z), wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and z is more than 0 and less than 1; (2) performing ball milling and first calcination on the first precursor in sequence to obtain a second precursor; (3) mixing the second precursor with citric acid, and then carrying out second calcination to obtain the lithium nickel cobalt manganese iron phosphate cathode material; the first and second calcinations are carried out in a protective atmosphere. The positive electrode material obtained by the method provided by the invention has a specific discharge capacity of more than 120 mAh/g.

Description

Method for recovering waste ternary oxide positive electrode
Technical Field
The invention relates to the technical field of recovery of anodes of lithium ion batteries, in particular to a method for recovering a waste ternary oxide anode.
Background
With the use of a large number of lithium ion batteries, a large number of waste lithium ion batteries are produced. These waste batteries are eliminated because they do not meet the corresponding energy storage requirements. If the waste batteries are directly treated like other wastes, serious environmental pollution is likely to be caused, and the hidden danger of fire caused by short circuit of the batteries also exists. Moreover, these waste batteries contain a large amount of transition metals, which are limited in the earth's reserves, and are directly disposed of as general garbage, and a large amount of transition metals are wasted.
Ternary oxide (namely nickel cobalt lithium manganate LiNi)xCoyMnzO2) Is a positive electrode material of commercial lithium ion batteries which is widely used. The waste battery contains a large amount of non-renewable metal elements such as nickel (Ni), cobalt (Co), manganese (Mn), lithium (Li) and the like. These metallic elements are not only in limited reserves on earth, but also have very limited duration of supply over a long period of time after a large amount of mining. However, the prior art has not provided a method for effectively recovering ternary oxides.
Disclosure of Invention
The invention aims to provide a method for recovering a waste ternary oxide positive electrode, which can effectively recover the ternary oxide positive electrode.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for recovering a waste ternary oxide anode, which comprises the following steps:
(1) mixing a ternary oxide positive electrode, an acidic solution of hydrogen peroxide, a phosphate source, an iron source, lithium nitrate and citric acid, and drying to obtain a first precursor; the molar ratio of lithium, iron, nickel, cobalt and manganese elements in the first precursor is 1.05-1.15: x: y: z (1-x-y-z), wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and z is more than 0 and less than 1;
(2) performing ball milling and first calcination on the first precursor in sequence to obtain a second precursor;
(3) mixing the second precursor with citric acid, and then carrying out second calcination to obtain the lithium nickel cobalt manganese iron phosphate cathode material;
the first and second calcinations are carried out in a protective atmosphere.
Preferably, the pH value of the acidic solution of hydrogen peroxide in the step (1) is less than 3, and the molar ratio of hydrogen peroxide in the acidic solution of hydrogen peroxide to lithium element in the ternary oxide positive electrode is 2.8-3.5: 1.
Preferably, the phosphate source in step (1) is at least one of ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid and ammonium phosphate.
Preferably, in the step (1), the iron source is at least one of ferric nitrate, ferric acetate, ferrous acetate, ferric oxalate and ferrous oxalate.
Preferably, in the step (1), the molar ratio of the lithium element in the first precursor to the phosphate ions and citric acid in the phosphate source is 1.05-1.15: 1: 1.
Preferably, the rotation speed of ball milling in the step (2) is 200-600 r/min, and the ball milling time is 6-20 h.
Preferably, the mass ratio of the grinding balls for ball milling to the first precursor is 15-30: 1.
Preferably, the temperature of the first calcination in the step (2) is 300-450 ℃, and the time of the first calcination is 2-5 h.
Preferably, the mass ratio of the second precursor to the citric acid in the step (3) is 1.5-3: 1.
Preferably, the temperature of the second calcination in the step (3) is 600-700 ℃, and the time of the second calcination is 8-12 h.
The invention provides a method for recovering a waste ternary oxide anode, which comprises the following steps: (1) mixing a ternary oxide positive electrode, an acidic solution of hydrogen peroxide, a phosphate source, an iron source, lithium nitrate and citric acid, and drying to obtain a first precursor; the molar ratio of lithium, iron, nickel, cobalt and manganese elements in the first precursor is 1.05-1.15: x: y: z (1-x-y-z), wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and z is more than 0 and less than 1; (2) performing ball milling and first calcination on the first precursor in sequence to obtain a second precursor; (3) mixing the second precursor with citric acid, and then carrying out second calcination to obtain the lithium nickel cobalt manganese iron phosphate cathode material; the first and second calcinations are carried out in a protective atmosphere. According to the method provided by the invention, a ternary oxide anode, an acidic solution of hydrogen peroxide, a phosphate source, an iron source, lithium nitrate and citric acid are mixed, the hydrogen peroxide can dissolve nickel cobalt lithium manganate in the ternary oxide anode under an acidic condition, the iron source and the lithium nitrate can adjust the proportion of each metal element, the citric acid is used as a carbon source, carbon is generated to be coated on the surface of metal particles after first calcination and second calcination, the conductivity of a product is increased, and on the other hand, the citric acid is used as a complexing agent and can be complexed with metal ions, the stability of the metal ions in the solution can be ensured to a certain extent, and meanwhile, the complexing effect can reduce the size of a finally synthesized material and ensure more uniform carbon coating on the surface; ball milling the first precursor to mix the conducting agent, the adhesive and other components, calcining to decompose the organic matter to obtain the second precursor; and in order to increase a carbon source, mixing the second precursor with citric acid, and then carrying out second calcination to fully decompose the organic matter to obtain the amorphous carbon-coated iron nickel cobalt manganese lithium phosphate cathode material. The method provided by the invention not only realizes the recovery of metal in the ternary oxide anode, but also effectively utilizes the conductive agent and the binder in the ternary oxide anode, simplifies the recovery method of the ternary oxide anode, and simultaneously obtains the anode material with good performance, and the specific discharge capacity of the obtained anode material can reach more than 120 mAh/g.
Detailed Description
The invention provides a method for recovering a waste ternary oxide anode, which comprises the following steps:
(1) mixing a ternary oxide positive electrode (namely a nickel cobalt lithium manganate positive electrode), an acidic solution of hydrogen peroxide, a phosphate source, an iron source, lithium nitrate and citric acid, and drying to obtain a first precursor; the molar ratio of lithium, iron, nickel, cobalt and manganese elements in the first precursor is 1.05-1.15: x: y: z (1-x-y-z), wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and z is more than 0 and less than 1;
(2) performing ball milling and first calcination on the first precursor in sequence to obtain a second precursor;
(3) mixing the second precursor with citric acid, and then carrying out second calcination to obtain the lithium nickel cobalt manganese iron phosphate cathode material;
the first and second calcinations are carried out in a protective atmosphere.
The method comprises the steps of mixing a ternary oxide positive electrode, an acidic solution of hydrogen peroxide, a phosphate source, an iron source, lithium nitrate and citric acid, and drying to obtain a first precursor. In the present invention, the ternary oxide positive electrode does not include a current collector.
In the invention, the nickel cobalt lithium manganate in the ternary oxide positive electrode can generate oxidation reduction reaction with hydrogen peroxide in an acidic solution of hydrogen peroxide, lithium ions can be ionized out in the solution, and nickel cobalt manganate can be reduced to generate nickel ions, cobalt ions and manganese ions.
The source of the ternary oxide anode is not particularly limited, and the ternary oxide anode can be derived from any lithium battery adopting the ternary oxide anode.
In the present invention, the pH of the acidic solution of hydrogen peroxide is preferably less than 3, and the molar ratio of hydrogen peroxide in the acidic solution of hydrogen peroxide to lithium in the ternary oxide positive electrode is preferably 2.8 to 3.5: 1.
In the present invention, the acid used for adjusting the pH of the acidic solution of hydrogen peroxide is preferably nitric acid, sulfuric acid, hydrochloric acid, or citric acid, and more preferably nitric acid.
In the present invention, the phosphate source is preferably at least one of ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid, and ammonium phosphate.
In the present invention, the iron source is preferably at least one of ferric nitrate, ferric acetate, ferrous acetate, ferric oxalate and ferrous oxalate.
In the invention, in the process of preparing the first precursor, the molar ratio of the lithium element in the first precursor to the phosphate ions and the citric acid in the phosphate source is preferably 1.05-1.15: 1: 1.
In the invention, citric acid added in the process of preparing the first precursor is used as a carbon source, and after the first calcination and the second calcination, generated carbon is coated on the surface of metal particles to increase the conductivity of the product, and on the other hand, citric acid is used as a complexing agent and can be complexed with metal ions, so that the stability of the metal ions in a solution can be ensured to a certain extent, and meanwhile, the complexing action can reduce the size of the finally synthesized material and ensure that the carbon coating on the surface is more uniform.
The mixing sequence of the ternary oxide positive electrode, the hydrogen peroxide acidic solution, the phosphate source, the iron source, the lithium nitrate and the citric acid is not particularly limited, and can be any mixing sequence. In the present embodiment, the ternary oxide positive electrode is preferably mixed with an acidic solution of hydrogen peroxide, and then mixed with other substances.
The mixing mode of the ternary oxide positive electrode, the hydrogen peroxide acidic solution, the phosphate source, the iron source, the lithium nitrate and the citric acid is not particularly limited, and a uniform mixture can be obtained. In the embodiment of the present invention, it is preferable to mix by stirring.
In the present invention, the drying method is not particularly limited, and a dried first precursor can be obtained. In the embodiment of the invention, the ternary oxide positive electrode, the acidic solution of hydrogen peroxide, the phosphate source, the iron source, the lithium nitrate and the citric acid are preferably mixed and heated to 60-100 ℃, and stirred to be dry. The stirring speed is not particularly limited, and can be conventional. In the invention, the drying adopts a mode of stirring to be dry at a higher temperature, so that various ions can be uniformly mixed.
In the present invention, the first precursor contains ionic substances such as lithium ions, iron ions, nickel ions, cobalt ions, manganese ions, and phosphate ions, and further contains a conductive agent and a binder that are insoluble in a solution.
In the invention, the molar ratio of lithium, iron, nickel, cobalt and manganese elements in the first precursor is 1.05-1.15: x: y: z (1-x-y-z), wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and z is more than 0 and less than 1. In the invention, the mass percentage of the conductive agent and the binder in the cathode material can be measured by thermogravimetry, and the molar weight of each element in the ternary oxide cathode can be obtained by mixing the ternary oxide cathode with the acidic solution of hydrogen peroxide to obtain a mixed solution, and then measuring the molar weight of the metal element in the mixed solution by using an ICP (inductively coupled atomic emission spectrometer) technology (namely, an inductively coupled atomic emission spectrometer). After the molar weight of the elements in the ternary oxide positive electrode is obtained, an iron source and lithium nitrate are added according to a design proportion.
After the first precursor is obtained, the first precursor is subjected to ball milling and first calcination in sequence to obtain a second precursor. In the invention, the ball milling can uniformly mix the conductive agent and the binder in the first precursor with other components; the first calcination can preliminarily decompose nitrate and organic substances (such as a binder and citric acid) in the first precursor.
In the present invention, the first calcination is performed in a protective atmosphere. In the present invention, the protective atmosphere ensures that the first precursor does not react with oxygen to reduce carbon loss from the first precursor. In the present invention, the protective atmosphere is preferably a nitrogen or inert gas atmosphere.
In the invention, the ball milling of the first precursor is preferably wet ball milling or dry ball milling, and more preferably wet ball milling; the rotation speed of the ball milling is preferably 200-600 r/min, and more preferably 300-500 r/min; the ball milling time is preferably 6-20 h, and more preferably 10-15 h; the dispersing agent used for wet ball milling is preferably acetone, ethanol or water; the dosage of the dispersant used for the wet ball milling is not specially limited, and the first precursor and the grinding balls used for the ball milling can be immersed.
In the invention, the particle size of the grinding balls used for ball milling is preferably 2-12 mm; the grinding balls used for ball milling are preferably graded grinding balls, the design of the grading is not particularly limited in the invention, and a person skilled in the art can adopt the common grading design.
In the invention, the mass ratio of the grinding balls to the first precursor is preferably 15-30: 1. After the ball milling is completed, the invention preferably dries the product obtained by the ball milling, and then performs the first calcination. The drying method is not particularly limited, and the dispersant in the product can be removed.
In the invention, the temperature of the first calcination is preferably 300-450 ℃, and more preferably 350-400 ℃; the first calcination time is preferably 2-5 h, and more preferably 3-4 h.
After the second precursor is obtained, the second precursor and citric acid are mixed and then subjected to second calcination to obtain the lithium nickel cobalt iron phosphate cathode material. In the invention, after the second precursor is obtained, citric acid is used as a carbon source and is mixed with the second precursor, so that the carbon content in the final obtained product can be increased, and the conductivity of the product is improved.
In the invention, the mass ratio of the second precursor to the citric acid is preferably 1.5-3: 1.
The mixing mode is not particularly limited, and the second precursor and the citric acid can be uniformly mixed.
In the embodiment of the invention, the mixing is preferably carried out in a ball milling way; the ball milling conditions are the same as those for the first precursor, and are not described herein again. In the embodiment of the present invention, after the ball milling is completed, the product obtained by the ball milling is preferably dried and then subjected to a second calcination. The drying method is not particularly limited, and the dispersant in the product can be removed. In the invention, the second precursor and the citric acid are mixed in a ball milling mode, so that the citric acid can be more uniformly distributed in the second precursor, and the intermolecular tightness can be improved.
In the invention, the temperature of the second calcination is preferably 600-700 ℃, and more preferably 650-675 ℃; the second calcination time is preferably 8-12 h, and more preferably 9-11 h. In the invention, the second calcination can further carbonize the organic matter to generate amorphous carbon to be coated on the surface of the final product.
In the present invention, the second calcination is performed in a protective atmosphere. In the present invention, the protective atmosphere ensures that the calcine does not react with oxygen to reduce carbon loss.
The following will explain the method for recovering a waste ternary oxide positive electrode provided by the present invention in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Will contain 0.02mol LiNi0.33Co0.33Mn0.33O2The ternary oxide anode is mixed with an acid solution of hydrogen peroxide with the pH value of 3, wherein the molar weight of the hydrogen peroxide is 0.003mol, so as to obtain a mixed solution; mixing the mixed solution with 0.00793mol LiNO3，0.0066molFe(NO3)3，0.02793molNH4H2PO4，0.02793molC6H8O7After mixing, the temperature is raised toStirring at 80 ℃ until the mixture is dried, thus obtaining a first precursor;
(2) ball-milling the first precursor for 12h at the speed of 500r/min, drying a product obtained by ball-milling, and calcining for 3h at the temperature of 350 ℃ in an argon atmosphere to obtain a second precursor; in the ball milling process, the mass ratio of the milling balls to the first precursor is 20:1, and a dispersing agent used for ball milling is acetone;
(3) mixing the second precursor and citric acid according to the mass ratio of 2:1, ball-milling for 12h under the condition of 500r/min, drying a product obtained by ball-milling, and calcining for 10h at 675 ℃ in an argon atmosphere to obtain LiFe0.25Ni0.25Co0.25Mn0.25PO4A positive electrode material; the mass ratio of the sum of the mass of the second precursor and the mass of the citric acid to the mass of the grinding ball is 1: 20; the dispersant used for ball milling is acetone.
The product obtained in this example was used as an active material of a positive electrode material to prepare a button cell, and LiFe obtained in this example was tested0.25Ni0.25Co0.25Mn0.25PO4The electrochemical performance of the anode material is specifically as follows:
the button-type battery comprises a positive pole piece, a negative pole piece, a diaphragm and electrolyte;
according to the active substance: conductive agent: mixing the binders in a mass ratio of 7:2:1, and coating a coating on a current collector of the positive pole piece to obtain the positive pole piece;
the negative pole piece is a metal lithium sheet; the membrane was a glass fibre membrane (available from Whatman, uk); the electrolyte is LiPF with the concentration of 1mol/L6The solvent is a mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1: 1. And assembling in a glove box to obtain the button-type battery.
Performing electrochemical analysis test on the button cell, performing charge and discharge under the conditions that the charge and discharge interval is 2.0-5.0V and the current density is 20mA/g, and obtaining LiFe0.25Ni0.25Co0.25Mn0.25PO4The capacity of the anode material can reach 125mAh/g, and the capacity does not obviously attenuate after 100 cycles of circulation. To illustrate the inventionThe metal elements in the waste ternary oxide lithium battery are recycled, and the finally obtained material has high capacity and stable cycle performance and can be used as the anode material of the lithium ion battery.
Example 2
(1) Will contain 0.04mol LiNi0.33Co0.33Mn0.33O2The ternary oxide anode is mixed with an acidic solution of hydrogen peroxide with the pH value of 3, wherein the molar weight of the hydrogen peroxide is 0.006mol, so as to obtain a mixed solution; mixing the mixed solution with 0.01586mol LiNO3，0.0132molFe(NO3)3，0.05586molNH4H2PO4，0.05586molC6H8O7After mixing, heating to 80 ℃, and stirring at 80 ℃ until drying to obtain a first precursor;
(2) ball-milling the first precursor for 12h at the speed of 500r/min, drying a product obtained by ball-milling, and calcining for 3h at the temperature of 350 ℃ in an argon atmosphere to obtain a second precursor; in the ball milling process, the mass ratio of the milling balls to the first precursor is 20:1, and a dispersing agent used for ball milling is acetone;
(3) mixing the second precursor and citric acid according to the mass ratio of 2:1, ball-milling for 12h under the condition of 500r/min, drying a product obtained by ball-milling, and calcining for 10h at 675 ℃ in an argon atmosphere to obtain LiFe0.25Ni0.25Co0.25Mn0.25PO4A positive electrode material; the mass ratio of the sum of the mass of the second precursor and the mass of the citric acid to the mass of the grinding ball is 1: 20; the dispersant used for ball milling is acetone.
The product obtained in this example was used as an active material of a positive electrode material to prepare a button cell, and LiFe obtained in this example was tested by the method described in example 10.25Ni0.25Co0.25Mn0.25PO4Electrochemical properties of the positive electrode material. The result shows that the LiFe is measured by charging and discharging under the conditions that the charging and discharging interval is 2.0-5.0V and the current density is 20mA/g0.25Ni0.25Co0.25Mn0.25PO4The capacity of the anode material can reach 123mAh/g, and the capacity of 100 cycles is unknownThe attenuation is significant.
Example 3
(1) Will contain 0.06mol LiNi0.33Co0.33Mn0.33O2The ternary oxide positive electrode is mixed with an acidic solution of hydrogen peroxide with the pH value of 3, wherein the molar weight of the hydrogen peroxide is 0.009mol, so as to obtain a mixed solution; mixing the mixed solution with 0.02379mol LiNO3，0.0198molmolFe(NO3)3，0.08379molNH4H2PO4，0.08379molC6H8O7After mixing, heating to 80 ℃, and stirring at 80 ℃ until drying to obtain a first precursor;
(2) ball-milling the first precursor for 12h at the speed of 500r/min, drying a product obtained by ball-milling, and calcining for 3h at the temperature of 350 ℃ in an argon atmosphere to obtain a second precursor; in the ball milling process, the mass ratio of the milling balls to the first precursor is 20:1, and a dispersing agent used for ball milling is acetone;
(3) mixing the second precursor and citric acid according to the mass ratio of 2:1, ball-milling for 12h under the condition of 500r/min, drying a product obtained by ball-milling, and calcining for 10h at 675 ℃ in an argon atmosphere to obtain LiFe0.25Ni0.25Co0.25Mn0.25PO4A positive electrode material; the mass ratio of the sum of the mass of the second precursor and the mass of the citric acid to the mass of the grinding ball is 1: 20; the dispersant used for ball milling is acetone.
The product obtained in this example was used as an active material of a positive electrode material to prepare a button cell, and LiFe obtained in this example was tested by the method described in example 10.25Ni0.25Co0.25Mn0.25PO4Electrochemical properties of the positive electrode material. The result shows that the LiFe is measured by charging and discharging under the conditions that the charging and discharging interval is 2.0-5.0V and the current density is 20mA/g0.25Ni0.25Co0.25Mn0.25PO4The capacity of the anode material can reach 126mAh/g, and the capacity does not obviously attenuate after 100 cycles of circulation.
Example 4
(1) Will contain 0.02mol LiNi0.33Co0.33Mn0.33O2The ternary oxide anode is mixed with an acid solution of hydrogen peroxide with the pH value of 3, wherein the molar weight of the hydrogen peroxide is 0.003mol, so as to obtain a mixed solution; mixing the mixed solution with 0.00793mol LiNO3，0.0066molmolFe(NO3)3，0.02793molNH4H2PO4，0.02793molC6H8O7After mixing, heating to 80 ℃, and stirring at 80 ℃ until drying to obtain a first precursor;
(2) ball-milling the first precursor for 12h at the speed of 500r/min, drying a product obtained by ball-milling, and calcining for 3h at the temperature of 350 ℃ in an argon atmosphere to obtain a second precursor; in the ball milling process, the mass ratio of the milling balls to the first precursor is 20:1, and a dispersing agent used for ball milling is acetone;
(3) mixing the second precursor and citric acid according to the mass ratio of 2:1, ball-milling for 12h under the condition of 500r/min, drying a product obtained by ball-milling, and calcining for 10h at 650 ℃ in argon atmosphere to obtain LiFe0.25Ni0.25Co0.25Mn0.25PO4A positive electrode material; the mass ratio of the sum of the mass of the second precursor and the mass of the citric acid to the mass of the grinding ball is 1: 20; the dispersant used for ball milling is acetone.
The product obtained in this example was used as an active material of a positive electrode material to prepare a button cell, and LiFe obtained in this example was tested by the method described in example 10.25Ni0.25Co0.25Mn0.25PO4Electrochemical properties of the positive electrode material. The result shows that the LiFe is measured by charging and discharging under the conditions that the charging and discharging interval is 2.0-5.0V and the current density is 20mA/g0.25Ni0.25Co0.25Mn0.25PO4The capacity of the anode material can reach 122mAh/g, and the capacity does not obviously attenuate after 100 cycles of circulation.
Example 5
(1) Will contain 0.02mol LiNi0.33Co0.33Mn0.33O2The ternary oxide anode is mixed with an acid solution of hydrogen peroxide with the pH value of 3, wherein the molar weight of the hydrogen peroxide is 0.003mol, so as to obtain a mixed solution; mixing the mixed solution with 0.00793mol LiNO3，0.0066molmolFe(NO3)3，0.02793molNH4H2PO4，0.02793molC6H8O7After mixing, heating to 80 ℃, and stirring at 80 ℃ until drying to obtain a first precursor;
(2) ball-milling the first precursor for 12h at the speed of 500r/min, drying a product obtained by ball-milling, and calcining for 3h at the temperature of 350 ℃ in an argon atmosphere to obtain a second precursor; in the ball milling process, the mass ratio of the milling balls to the first precursor is 20:1, and a dispersing agent used for ball milling is acetone;
(3) mixing the second precursor and citric acid according to the mass ratio of 2:1, ball-milling for 12h under the condition of 500r/min, drying a product obtained by ball-milling, and calcining for 10h in an argon atmosphere at 625 ℃ to obtain LiFe0.25Ni0.25Co0.25Mn0.25PO4A positive electrode material; the mass ratio of the sum of the mass of the second precursor and the mass of the citric acid to the mass of the grinding ball is 1: 20; the dispersant used for ball milling is acetone.
The product obtained in this example was used as an active material of a positive electrode material to prepare a button cell, and LiFe obtained in this example was tested by the method described in example 10.25Ni0.25Co0.25Mn0.25PO4Electrochemical properties of the positive electrode material. The result shows that the LiFe is measured by charging and discharging under the conditions that the charging and discharging interval is 2.0-5.0V and the current density is 20mA/g0.25Ni0.25Co0.25Mn0.25PO4The capacity of the anode material can reach 121mAh/g, and the capacity does not obviously attenuate after 100 cycles of circulation.
Example 6
(1) Will contain 0.02mol LiNi0.33Co0.33Mn0.33O2The ternary oxide anode is mixed with an acid solution of hydrogen peroxide with the pH value of 3, wherein the molar weight of the hydrogen peroxide is 0.003mol, so as to obtain a mixed solution; mixing the mixed solution with 0.00793mol LiNO3，0.0066molmolFe(NO3)3，0.02793molNH4H2PO4，0.02793molC6H8O7After mixing, literHeating to 80 ℃, and stirring to dry at 80 ℃ to obtain a first precursor;
(2) ball-milling the first precursor for 12h at the speed of 500r/min, drying a product obtained by ball-milling, and calcining for 3h at the temperature of 350 ℃ in an argon atmosphere to obtain a second precursor; in the ball milling process, the mass ratio of the milling balls to the first precursor is 20:1, and a dispersing agent used for ball milling is acetone;
(3) mixing the second precursor and citric acid according to the mass ratio of 2:1, ball-milling for 12h under the condition of 500r/min, drying a product obtained by ball-milling, and calcining for 10h in the argon atmosphere at 700 ℃ to obtain LiFe0.25Ni0.25Co0.25Mn0.25PO4A positive electrode material; the mass ratio of the sum of the mass of the second precursor and the mass of the citric acid to the mass of the grinding ball is 1: 20; the dispersant used for ball milling is acetone.
The product obtained in this example was used as an active material of a positive electrode material to prepare a button cell, and LiFe obtained in this example was tested by the method described in example 10.25Ni0.25Co0.25Mn0.25PO4Electrochemical properties of the positive electrode material. The result shows that the LiFe is measured by charging and discharging under the conditions that the charging and discharging interval is 2.0-5.0V and the current density is 20mA/g0.25Ni0.25Co0.25Mn0.25PO4The capacity of the anode material can reach 119mAh/g, and the capacity does not obviously attenuate after 100 cycles of circulation.
Example 7
(1) Will contain 0.02mol LiNi0.33Co0.33Mn0.33O2The ternary oxide anode is mixed with an acid solution of hydrogen peroxide with the pH value of 3, wherein the molar weight of the hydrogen peroxide is 0.003mol, so as to obtain a mixed solution; mixing the mixed solution with 0.00793mol LiNO3，0.0066molmolFe(NO3)3，0.02793molNH4H2PO4，0.02793molC6H8O7After mixing, heating to 80 ℃, and stirring at 80 ℃ until drying to obtain a first precursor;
(2) ball-milling the first precursor for 12h at the speed of 500r/min, drying a product obtained by ball-milling, and calcining for 3h at the temperature of 350 ℃ in an argon atmosphere to obtain a second precursor; in the ball milling process, the mass ratio of the milling balls to the first precursor is 20:1, and a dispersing agent used for ball milling is acetone;
(3) mixing the second precursor and citric acid according to the mass ratio of 2:1, ball-milling for 12h under the condition of 500r/min, drying a product obtained by ball-milling, and calcining for 8h at 675 ℃ in argon atmosphere to obtain LiFe0.25Ni0.25Co0.25Mn0.25PO4A positive electrode material; the mass ratio of the sum of the mass of the second precursor and the mass of the citric acid to the mass of the grinding ball is 1: 20; the dispersant used for ball milling is acetone.
The product obtained in this example was used as an active material of a positive electrode material to prepare a button cell, and LiFe obtained in this example was tested by the method described in example 10.25Ni0.25Co0.25Mn0.25PO4Electrochemical properties of the positive electrode material. The result shows that the LiFe is measured by charging and discharging under the conditions that the charging and discharging interval is 2.0-5.0V and the current density is 20mA/g0.25Ni0.25Co0.25Mn0.25PO4The capacity of the anode material can reach 121mAh/g, and the capacity does not obviously attenuate after 100 cycles of circulation.
Example 8
(1) Will contain 0.02mol LiNi0.33Co0.33Mn0.33O2The ternary oxide anode is mixed with an acid solution of hydrogen peroxide with the pH value of 3, wherein the molar weight of the hydrogen peroxide is 0.003mol, so as to obtain a mixed solution; mixing the mixed solution with 0.00793mol LiNO3，0.0066molmolFe(NO3)3，0.02793molNH4H2PO4，0.02793molC6H8O7After mixing, heating to 80 ℃, and stirring at 80 ℃ until drying to obtain a first precursor;
(2) ball-milling the first precursor for 12h at the speed of 500r/min, drying a product obtained by ball-milling, and calcining for 3h at the temperature of 350 ℃ in an argon atmosphere to obtain a second precursor; in the ball milling process, the mass ratio of the milling balls to the first precursor is 20:1, and a dispersing agent used for ball milling is acetone;
(3) mixing the second precursor and citric acid according to the mass ratio of 2:1, ball-milling for 12h under the condition of 500r/min, drying a product obtained by ball-milling, and calcining for 9h at 675 ℃ in argon atmosphere to obtain LiFe0.25Ni0.25Co0.25Mn0.25PO4A positive electrode material; the mass ratio of the sum of the mass of the second precursor and the mass of the citric acid to the mass of the grinding ball is 1: 20; the dispersant used for ball milling is acetone.
The product obtained in this example was used as an active material of a positive electrode material to prepare a button cell, and LiFe obtained in this example was tested by the method described in example 10.25Ni0.25Co0.25Mn0.25PO4Electrochemical properties of the positive electrode material. The result shows that the LiFe is measured by charging and discharging under the conditions that the charging and discharging interval is 2.0-5.0V and the current density is 20mA/g0.25Ni0.25Co0.25Mn0.25PO4The capacity of the anode material can reach 120mAh/g, and the capacity does not obviously attenuate after 100 cycles of circulation.
Example 9
(1) Will contain 0.02mol LiNi0.33Co0.33Mn0.33O2The ternary oxide anode is mixed with an acid solution of hydrogen peroxide with the pH value of 3, wherein the molar weight of the hydrogen peroxide is 0.003mol, so as to obtain a mixed solution; mixing the mixed solution with 0.00793mol LiNO3，0.0066molmolFe(NO3)3，0.02793molNH4H2PO4，0.02793molC6H8O7After mixing, heating to 80 ℃, and stirring at 80 ℃ until drying to obtain a first precursor;
(2) ball-milling the first precursor for 12h at the speed of 500r/min, drying a product obtained by ball-milling, and calcining for 3h at the temperature of 350 ℃ in an argon atmosphere to obtain a second precursor; in the ball milling process, the mass ratio of the milling balls to the first precursor is 20:1, and a dispersing agent used for ball milling is acetone;
(3) mixing the second precursor and citric acid according to the mass ratio of 2:1, ball-milling for 12 hours under the condition of 500r/min, and drying the product obtained by ball-millingAfter drying, calcining for 11h at 675 ℃ in an argon atmosphere to obtain LiFe0.25Ni0.25Co0.25Mn0.25PO4A positive electrode material; the mass ratio of the sum of the mass of the second precursor and the mass of the citric acid to the mass of the grinding ball is 1: 20; the dispersant used for ball milling is acetone.
The product obtained in this example was used as an active material of a positive electrode material to prepare a button cell, and LiFe obtained in this example was tested by the method described in example 10.25Ni0.25Co0.25Mn0.25PO4Electrochemical properties of the positive electrode material. The result shows that the LiFe is measured by charging and discharging under the conditions that the charging and discharging interval is 2.0-5.0V and the current density is 20mA/g0.25Ni0.25Co0.25Mn0.25PO4The capacity of the anode material can reach 122mAh/g, and the capacity does not obviously attenuate after 100 cycles of circulation.
Example 10
(1) Will contain 0.02mol LiNi0.33Co0.33Mn0.33O2The ternary oxide anode is mixed with an acid solution of hydrogen peroxide with the pH value of 3, wherein the molar weight of the hydrogen peroxide is 0.003mol, so as to obtain a mixed solution; mixing the mixed solution with 0.00793mol LiNO3，0.0066molmolFe(NO3)3，0.02793molNH4H2PO4，0.02793molC6H8O7After mixing, heating to 80 ℃, and stirring at 80 ℃ until drying to obtain a first precursor;
(2) ball-milling the first precursor for 12h at the speed of 500r/min, drying a product obtained by ball-milling, and calcining for 3h at the temperature of 350 ℃ in an argon atmosphere to obtain a second precursor; in the ball milling process, the mass ratio of the milling balls to the first precursor is 20:1, and a dispersing agent used for ball milling is acetone;
(3) mixing the second precursor and citric acid according to the mass ratio of 2:1, ball-milling for 12h under the condition of 500r/min, drying a product obtained by ball-milling, and calcining for 12h at 675 ℃ in an argon atmosphere to obtain LiFe0.25Ni0.25Co0.25Mn0.25PO4A positive electrode material; the second precursor and lemonThe mass ratio of the sum of the masses of the citric acid to the grinding ball is 1: 20; the dispersant used for ball milling is acetone.
The product obtained in this example was used as an active material of a positive electrode material to prepare a button cell, and LiFe obtained in this example was tested by the method described in example 10.25Ni0.25Co0.25Mn0.25PO4Electrochemical properties of the positive electrode material. The result shows that the LiFe is measured by charging and discharging under the conditions that the charging and discharging interval is 2.0-5.0V and the current density is 20mA/g0.25Ni0.25Co0.25Mn0.25PO4The capacity of the anode material can reach 120mAh/g, and the capacity does not obviously attenuate after 100 cycles of circulation.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. A method for recovering a waste ternary oxide positive electrode comprises the following steps:
(1) mixing a ternary oxide positive electrode, an acidic solution of hydrogen peroxide, a phosphate source, an iron source, lithium nitrate and citric acid, and drying to obtain a first precursor; the molar ratio of lithium, iron, nickel, cobalt and manganese elements in the first precursor is 1.05-1.15: x: y: z (1-x-y-z), wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and z is more than 0 and less than 1; the molar ratio of the lithium element to phosphate ions and citric acid in the phosphate source is 1.05-1.15: 1: 1;
(2) performing ball milling and first calcination on the first precursor in sequence to obtain a second precursor;
(3) mixing the second precursor with citric acid, and then carrying out second calcination to obtain the lithium nickel cobalt manganese iron phosphate cathode material; the mass ratio of the second precursor to the citric acid is 1.5-3: 1;
the first and second calcinations are carried out in a protective atmosphere.
2. The recovery method according to claim 1, wherein the pH of the acidic solution of hydrogen peroxide in the step (1) is less than 3, and the molar ratio of hydrogen peroxide in the acidic solution of hydrogen peroxide to lithium element in the ternary oxide positive electrode is 2.8-3.5: 1.
3. The recycling method according to claim 1, wherein the phosphate source in step (1) is at least one of ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, phosphoric acid, and ammonium phosphate.
4. The recycling method according to claim 1, wherein the iron source in the step (1) is at least one of ferric nitrate, ferric acetate, ferrous acetate, ferric oxalate and ferrous oxalate.
5. The recycling method according to claim 1, wherein the rotation speed of the ball milling in the step (2) is 200-600 r/min, and the time of the ball milling is 6-20 h.
6. The recovery method according to claim 5, wherein the mass ratio of the ball milling balls to the first precursor is preferably 15 to 30: 1.
7. The recycling method according to any one of claims 1, 5 and 6, wherein the temperature of the first calcination in the step (2) is 300 to 450 ℃ and the time of the first calcination is 2 to 5 hours.
8. The recycling method according to claim 1, wherein the temperature of the second calcination in the step (3) is 600 to 700 ℃, and the time of the second calcination is 8 to 12 hours.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101719546A (en) * 2009-11-26 2010-06-02 上海大学 Method for preparing lithium ion battery anode material doped with nanometer oxide
CN101789504A (en) * 2010-03-17 2010-07-28 中南大学 Preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material
JP2014064566A (en) * 2012-09-07 2014-04-17 National Univ Corp Shizuoka Univ Substance capable of charging/discharging as well as secondary battery and microbial secondary battery using the same
CN106953073A (en) * 2016-12-29 2017-07-14 蔚来汽车有限公司 Iron phosphate lithium positive pole composite and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101673859B (en) * 2009-09-25 2011-08-17 北京理工大学 Method for recovering and preparing lithium cobalt oxide by using disused lithium battery
KR101708149B1 (en) * 2016-05-20 2017-02-20 (주)이엠티 A Method For Recovering Lithium Compound From An Anode Material In Spent Lithium Batteries By Wet-Milling
CN106997975B (en) * 2017-06-06 2019-12-10 安徽安凯汽车股份有限公司 method for recycling waste lithium iron phosphate battery and lithium manganate battery
CN107699692A (en) * 2017-09-18 2018-02-16 北京理工大学 A kind of recovery and the method for regenerating waste used anode material for lithium-ion batteries

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101719546A (en) * 2009-11-26 2010-06-02 上海大学 Method for preparing lithium ion battery anode material doped with nanometer oxide
CN101789504A (en) * 2010-03-17 2010-07-28 中南大学 Preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material
JP2014064566A (en) * 2012-09-07 2014-04-17 National Univ Corp Shizuoka Univ Substance capable of charging/discharging as well as secondary battery and microbial secondary battery using the same
CN106953073A (en) * 2016-12-29 2017-07-14 蔚来汽车有限公司 Iron phosphate lithium positive pole composite and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Li-storage in LiFe1/4Mn1/4Co1/4Ni1/4PO4 solid solution;X.J. Wang，X.Q. Yu等;《Electrochemistry Communications》;20080710;第1347-1350页 *
溶胶－凝胶法在锂离子电池正极材料制备中的应用与发展;吕睿，王晓清等;《材料导报》;20120930;第154-158页 *

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