CN109378540B - Preparation method of high-purity ternary precursor - Google Patents

Preparation method of high-purity ternary precursor Download PDF

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CN109378540B
CN109378540B CN201811088834.7A CN201811088834A CN109378540B CN 109378540 B CN109378540 B CN 109378540B CN 201811088834 A CN201811088834 A CN 201811088834A CN 109378540 B CN109378540 B CN 109378540B
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cobalt
waste
bark
manganese
ternary precursor
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CN109378540A (en
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高月春
毛信长
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Yuyao Xinhe Battery Materials Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to the field of electrode materials, and aims to solve the problems that the preparation cost is high, the pollution is strong and the like in the prior art of a process method for preparing a ternary precursor, and the prepared ternary precursor has low purity due to incomplete removal of magazine metal components when a waste battery is used as a raw material for preparing the ternary precursor, the invention adopts the following scheme: 1) leaching manganese from the waste battery by a crushing leaching method; 2) collecting nickel and cobalt elements in the residual materials in a leaching and redepositing mode, and mixing the nickel and cobalt elements with the manganese-containing leaching solution; 3) carrying out further trapping and precipitation on metal impurity components by using the modified biomass particles; 4) further leaching and precipitating cobalt element in the precipitate; 5) dissolving the cobalt precipitate in the filtrate containing nickel, cobalt and manganese, trapping, filtering and drying the nickel, cobalt and manganese by using the biomass filler, and removing the biomass filler by burning to obtain the ternary precursor. The method can prepare the ternary precursor with extremely high purity through three purification and impurity removal steps.

Description

Preparation method of high-purity ternary precursor
Technical Field
The invention relates to the field of electrode materials, in particular to a preparation method of a high-purity ternary precursor.
Background
The ternary precursor is used for preparing a high-efficiency lithium ion battery composite positive electrode material used for a new energy automobile, and is prepared from hydroxide Ni of nickel, cobalt and manganesexCoyMnz(OH)2Typical preparation raw materials are nickel salts, cobalt salts and manganese salts. However, nickel and cobalt are expensive metal materials with strategic value, and the preparation of a mixed solution of nickel salt, cobalt salt and manganese salt in large quantities inevitably causes great environmental pollution. Therefore, the existing process method for preparing the ternary precursor generally has the problems of high preparation cost, strong pollution and the like.
In order to reduce environmental pollution and recycle waste batteries in the prior art, a series of process methods for preparing ternary precursors by using waste batteries as raw materials are generated. Impurity metal components are removed through various leaching and deposition modes, and nickel, cobalt and manganese active ingredients for preparing the ternary precursor are left. The existing method generally has the problems of incomplete removal of magazine metal elements, low purity of the prepared ternary precursor and high impurity content. The ternary composite electrode material prepared from the ternary precursor with high purity and high impurity content has very limited performance.
The Chinese patent office discloses an invention patent application of a method for repairing and regenerating a nickel-cobalt-manganese ternary positive electrode material in a waste battery in 2017, 2 month and 15 days, wherein the application publication number is CN106410313A, and the method comprises the following steps: splitting a positive electrode material from a lithium cobaltate waste battery; laying a ternary positive pole piece on a mesh belt, controlling the mesh belt to vibrate continuously, and simultaneously controlling gas to pass through mesh holes of the mesh belt from bottom to top; under the conditions of mesh belt vibration and mesh of the mesh belt gas circulation, respectively heating the ternary positive electrode plate at 100-300 ℃ and 380-520 ℃ for 10-60 minutes, and collecting ternary positive electrode material powder I; sequentially screening the ternary cathode material powder I to remove cracked aluminum foil and electromagnetically removing iron to obtain ternary cathode material powder II, and performing ball milling to obtain ternary cathode material powder III; the ternary cathode material powder III dissolves aluminum powder under weak acidity, the surface of the ternary cathode material is corroded to form the ternary cathode material with high activity and high dispersibility, and the ternary cathode material is used as a nucleating agent to be synthesized and repaired into a spherical ternary precursor material with uniform particles. The method realizes the recycling of the ternary cathode material in the waste battery, but the recycling process flow is crude, only aluminum and iron are effectively removed, and other heavy metal components, such as calcium, copper, lead, carbon, zinc, mercury and the like, are not effectively removed, so that the prepared and repaired ternary cathode material is very limited.
The Chinese patent office also discloses an invention patent application of a method for recovering valuable metals in waste nickel-cobalt-manganese lithium ion batteries in 2018, 2.2.8978, wherein the application publication number is CN 107653378A. And removing copper by replacing iron powder in the leachate, removing iron and aluminum by using water, synthesizing an aluminum-coated nickel, cobalt and manganese ternary cathode material precursor by using the solution after impurity removal through solution preparation, evaporating and concentrating the synthesized solution, and adding carbonate or introducing carbon dioxide to recover lithium. The method can effectively extract four elements of nickel, cobalt, manganese and lithium by an acid dissolution and reducition method, and remove impurity elements such as iron, aluminum and copper, but can not effectively remove elements such as calcium, lead, carbon, zinc and mercury, so that the recovered valuable metal is doped with impurity components with high content.
Disclosure of Invention
The invention provides a preparation method of a high-purity ternary precursor, aiming at solving the problems of high preparation cost, strong pollution and the like of the conventional process method for preparing the ternary precursor, and the problems that the impurities and metal components are not completely removed and the prepared ternary precursor has low purity when the ternary precursor is prepared by taking a waste battery as a raw material. The method mainly aims to reduce the preparation cost of the ternary precursor and reduce the pollution to the environment in the preparation process. In addition, the invention takes the waste battery as the raw material, and also aims to improve the purity of the prepared ternary precursor.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-purity ternary precursor comprises the following preparation steps:
1) taking waste batteries as raw materials, performing operations of disassembling, sorting and crushing on the waste batteries to obtain slag, soaking the slag in concentrated sulfuric acid for 10-15 min, and filtering to obtain primary filtrate and excess materials;
2) adding the residual material obtained in the step 1) into 2-3 times of water by weight, slowly adding concentrated sulfuric acid, heating to 150-160 ℃, stopping adding the concentrated sulfuric acid, carrying out constant-temperature treatment for 45-60 min, filtering out filter residues, and adding the filter residues into the primary filtrate obtained in the step 1) to obtain a purified solution;
3) adding modified biomass particles into the purified liquid obtained in the step 2), stirring at a low speed for 1-2 h, and filtering and separating to obtain secondary filtrate and precipitated particles;
4) carrying out combustion treatment on the precipitate particles obtained in the step 3), dissolving the precipitate particles in 0.25-0.5 mol/L sulfuric acid after complete combustion treatment, adjusting the pH value to 1.0-1.5 by using sodium hydroxide or potassium hydroxide, and filtering to obtain a precipitate;
5) adding the precipitate obtained in the step 4) into the secondary filtrate obtained in the step 3), stirring until the precipitate is completely dissolved, adding a biomass filler, stirring at a low speed for 1-2 hours, filtering out the biomass filler, performing combustion treatment on the biomass filler until the biomass filler is completely combusted, then performing ball milling, and obtaining a ternary precursor after the ball milling is finished.
Respectively extracting and separating nickel, cobalt and manganese elements from waste batteries by dipping and deposition, taking the manganese element as the main component in primary filtrate obtained by dipping and filtering in the step 1), namely the primary filtrate contains high-purity manganese ions, the journal metal is leached in the step 2), the nickel, cobalt and iron elements are precipitated and separated from the journal metal in the process of temperature rise and constant temperature, the separated filter residue is mixed with the primary filtrate to obtain acid purified liquid with high nickel, cobalt and manganese purity, modified biomass particles are added, the purification and separation can be further realized by utilizing the specific trapping effect of the modified biomass particles, the cobalt and iron elements are separated to form precipitates, the precipitates are dissolved again after combustion, the cobalt and iron are separated, the separated cobalt is dissolved again in secondary filtrate containing nickel and manganese, and the content of the journal metal elements in the solution is at a very low level, on the basis, the specific trapping capacity of the biomass filler is utilized to specifically trap nickel, cobalt and manganese elements, and the purpose of preparing the high-purity ternary precursor is achieved in a three-step purification and metal impurity component reduction mode.
Preferably, the concentration of the concentrated sulfuric acid in the step 1) is 1.5-2 mol/L, and the pH value in the dipping process is controlled to be less than or equal to 2.
When the concentrated sulfuric acid is used for treating the slag, the metal ions of other types except the manganese ions in the slag are difficult to dissolve out due to the overhigh concentration of the sulfuric acid, and the manganese ions have extremely high solubility under the condition, so that the manganese element is efficiently extracted, the dissolution of impurity metals is reduced, and the primary filtrate has high-purity manganese sulfate;
preferably, the concentrated sulfuric acid in the step 2) is 1-1.5 mol/L, and the temperature rise rate is controlled to be 15-20 ℃/min in the temperature rise process.
When the foam slag is treated, concentrated sulfuric acid is added into water to generate a large amount of heat, so that the dissolution of each metal component in the excess material is accelerated, the temperature is continuously increased to 150-170 ℃ after the dissolution under the condition of introducing high-temperature hot air, the nickel sulfate, the cobalt sulfate and the ferric sulfate are separated out after the constant-temperature treatment, and the rest metal components are still dissolved in acid liquor. The speed of precipitation and sedimentation of the nickel, cobalt and iron elements can be effectively balanced by controlling the temperature rise rate.
Preferably, the modified biomass particles in step 3) are prepared from powder ground from waste wood.
In some woodwork processing factory, useless wooden skin is the waste material that will produce in its production process, such as leftover bits in the cutting process, the part that has the wooden scar of preparation woodwork in-process rejection, its production is very big, but has not effectively utilized for a long time always, great waste has been produced, for sparingly spending in some woodwork processing factory simultaneously, economic benefits is improved, it adopts the mode of directly burning to handle it, and toxic gas such as carbon monoxide still contains in a large amount of waste gas that a large amount of useless wooden skin burning incompletely produced, great pollution has been caused to the environment. Therefore, the method of the invention recycles the waste wood skin, not only reduces the preparation cost and produces better use effect, but also indirectly produces a better ecological transaction chain and reduces the pollution of burning the waste wood skin to the environment.
Preferably, the waste wood materials include coast cedar bark, west chuan cedar bark, cottonwood bark, and alder bark.
The coastal cedar bark, western Sichuan cedar bark, small dried pine bark and red alder bark all have good trapping effects on most metal ions, the trapping effects are limited through a certain modification process, and particularly, after the trapping capabilities of three metal ions of nickel, cobalt and manganese are inhibited and weakened, the excellent effect of removing metal impurity components can be realized.
Preferably, the mass ratio of the coast cedar bark, the west Sichuan spruce bark, the small dried pine bark and the red poplar bark is 8: 12: 5: 3.
although the bark has good trapping effect on most metal ions, the capacity of trapping single metal ions is still different, for example, the coastal redwood bark has very excellent trapping capacity on calcium and magnesium, the rest three barks do not have, and the red alder has very excellent trapping capacity on chromium ions. Therefore, the collection effect and the capability of removing metal impurity components generated by selecting proper wood bark types and dosage in the modified biomass particles are very important, and the formula of the modified biomass particles selected by the invention can effectively remove the metal impurities in the leachate of the waste battery.
Preferably, the waste wood materials are subjected to modification treatment, and the modification treatment comprises the following steps: immersing the waste wood into the modifying liquid, and carrying out ultrasonic oscillation for 20-30 min.
The modified biomass particles after modification treatment can further strengthen the effect of capturing impurity components, and can reduce the capturing effect of the modified biomass particles on three elements of nickel, cobalt and manganese by using a reasonable process, even make the capturing effect of the modified biomass particles on the three elements of nickel, cobalt and manganese in a saturated state.
Preferably, the modifying solution contains 1.5-2.5 wt% of formaldehyde, 0.2-0.5 wt% of sulfuric acid, 0.005-0.01 mol/L of nickel ions, 0.01-0.05 mol/L of cobalt ions and 0.008-0.015 mol/L of manganese ions.
The modified biomass particles treated by formaldehyde and sulfuric acid can further improve the trapping effect of the modified biomass particles, and the nickel ions, the cobalt ions and the manganese ions in the modified liquid enable the modified biomass particles to be saturated for trapping the three elements.
Preferably, the biomass filler of step 5) is prepared by grinding waste maple bark, waste maple bark and waste silver fir bark.
The biomass filler prepared by grinding the three wood barks has very obvious capturing effect and specificity, wherein the maple and the maple sugar bark have very excellent capturing effect on nickel and cobalt, the capturing effect on other metal ions is very poor, the silver cedar wood bark can have very excellent capturing effect on manganese, and the biomass filler prepared by mixing the three wood barks can have excellent capturing effect on three required elements of nickel, cobalt and manganese.
Preferably, the mass ratio of the waste maple bark, the waste maple bark and the waste silver fir bark used for preparing the biomass filler is 2: 1: 2.
the biomass filler prepared according to the proportion has the best trapping effect.
The invention has the beneficial effects that:
1) the waste batteries can be effectively recycled;
2) when the waste battery is used for preparing the ternary precursor, the ternary precursor with extremely high purity can be prepared through three purification and impurity removal steps;
3) the preparation cost of the ternary precursor is reduced, and the pollution generated in the preparation production process is reduced.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only examples of a part of the present invention, and not all examples. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Example 1
A preparation method of a high-purity ternary precursor comprises the following preparation steps:
1) taking waste batteries as raw materials, performing operations of disassembling, sorting and crushing on the waste batteries to obtain slag, soaking the slag in 1.5mol/L concentrated sulfuric acid for 10min, and filtering, wherein the pH value is kept to be less than or equal to 2 in the soaking process to obtain primary filtrate and residual materials;
2) adding the residual material obtained in the step 1) into 2 times of water by weight, slowly adding 1mol/L concentrated sulfuric acid, heating to 150 ℃ at a speed of 15 ℃/min, stopping adding the concentrated sulfuric acid, carrying out constant-temperature treatment for 60min, filtering to obtain filter residue, and adding the filter residue into the primary filtrate obtained in the step 1) to obtain a purified solution;
3) adding modified biomass particles into the purified liquid obtained in the step 2), slowly stirring at a rotating speed of 20r/min for 1h, and filtering and separating to obtain secondary filtrate and precipitated particles;
4) carrying out combustion treatment on the precipitate particles obtained in the step 3), dissolving the precipitate particles in 0.25mol/L sulfuric acid after complete combustion treatment, adjusting the pH value to 1.0 by using sodium hydroxide or potassium hydroxide, and filtering to obtain a precipitate;
5) adding the precipitate obtained in the step 4) into the secondary filtrate obtained in the step 3), stirring until the precipitate is completely dissolved, adding a biomass filler, stirring at a low speed of 15r/min for 1h, filtering the biomass filler, performing combustion treatment on the biomass filler until the biomass filler is completely combusted, then performing ball milling, and obtaining a ternary precursor after the ball milling is finished;
wherein the modified biomass particles used in the step 3) are prepared from the following raw materials in a mass ratio of 8: 12: 5: 3, the coast cedar bark, the west Sichuan spruce bark, the small dried pine bark and the red poplar bark waste wood are prepared, and the modification treatment steps are as follows: immersing waste wood in a modifying solution, and carrying out ultrasonic oscillation for 20min, wherein the modifying solution contains 1.5 wt% of formaldehyde, 0.2 wt% of sulfuric acid, 0.005mol/L of nickel ions, 0.01mol/L of cobalt ions and 0.008mol/L of manganese ions;
step 5) preparing the biomass filler from a raw material consisting of the following components in a mass ratio of 2: 1: 2, the waste maple bark, the waste sugar maple bark and the waste silver fir bark are ground into powder, and the average particle size of the powder is 0.5 mm.
Example 2
A preparation method of a high-purity ternary precursor comprises the following preparation steps:
1) taking waste batteries as raw materials, performing operations of disassembling, sorting and crushing on the waste batteries to obtain slag, soaking the slag in 2mol/L concentrated sulfuric acid for 15min, and filtering, wherein the pH value is kept to be less than or equal to 2 in the soaking process to obtain primary filtrate and residual materials;
2) adding the residual material obtained in the step 1) into 3 times of water by weight, slowly adding 1.5mol/L concentrated sulfuric acid, heating to 160 ℃ at the speed of 20 ℃/min, stopping adding the concentrated sulfuric acid, carrying out constant-temperature treatment for 45min, filtering to obtain filter residue, and adding the filter residue into the primary filtrate obtained in the step 1) to obtain a purified solution;
3) adding modified biomass particles into the purified liquid obtained in the step 2), slowly stirring at a rotating speed of 15r/min for 2 hours, and filtering and separating to obtain secondary filtrate and precipitated particles;
4) carrying out combustion treatment on the precipitate particles obtained in the step 3), dissolving the precipitate particles in 0.5mol/L sulfuric acid after complete combustion treatment, adjusting the pH value to 1.5 by using sodium hydroxide or potassium hydroxide, and filtering to obtain a precipitate;
5) adding the precipitate obtained in the step 4) into the secondary filtrate obtained in the step 3), stirring until the precipitate is completely dissolved, adding a biomass filler, stirring at a low speed of 15r/min for 2 hours, filtering the biomass filler, performing combustion treatment on the biomass filler until the biomass filler is completely combusted, then performing ball milling, and obtaining a ternary precursor after the ball milling is finished;
wherein the modified biomass particles used in the step 3) are prepared from the following raw materials in a mass ratio of 8: 12: 5: 3, the coast cedar bark, the west Sichuan spruce bark, the small dried pine bark and the red poplar bark waste wood are prepared, and the modification treatment steps are as follows: immersing waste wood in a modifying solution, and carrying out ultrasonic oscillation for 30min, wherein the modifying solution contains 2.5wt% of formaldehyde, 0.5wt% of sulfuric acid, 0.01mol/L of nickel ions, 0.05mol/L of cobalt ions and 0.015mol/L of manganese ions;
step 5) preparing the biomass filler from a raw material consisting of the following components in a mass ratio of 2: 1: 2, the waste maple bark, the waste sugar maple bark and the waste silver fir bark are ground into powder, and the average particle size of the powder is 2 mm.
Example 3
A preparation method of a high-purity ternary precursor comprises the following preparation steps:
1) taking waste batteries as raw materials, performing operations of disassembling, sorting and crushing on the waste batteries to obtain slag, soaking the slag in 2mol/L concentrated sulfuric acid for 10min, and filtering, wherein the pH value is kept to be less than or equal to 2 in the soaking process to obtain primary filtrate and residual materials;
2) adding the residual material obtained in the step 1) into 3 times of water by weight, slowly adding 1.5mol/L concentrated sulfuric acid, heating to 150 ℃ at a speed of 15 ℃/min, stopping adding the concentrated sulfuric acid, carrying out constant-temperature treatment for 60min, filtering to obtain filter residue, and adding the filter residue into the primary filtrate obtained in the step 1) to obtain a purified solution;
3) adding modified biomass particles into the purified liquid obtained in the step 2), slowly stirring at a rotating speed of 20r/min for 1.5h, and filtering and separating to obtain secondary filtrate and precipitated particles;
4) carrying out combustion treatment on the precipitate particles obtained in the step 3), dissolving the precipitate particles in 0.5mol/L sulfuric acid after complete combustion treatment, adjusting the pH value to 1.5 by using sodium hydroxide or potassium hydroxide, and filtering to obtain a precipitate;
5) adding the precipitate obtained in the step 4) into the secondary filtrate obtained in the step 3), stirring until the precipitate is completely dissolved, adding a biomass filler, stirring at a low speed of 15r/min for 1h, filtering the biomass filler, performing combustion treatment on the biomass filler until the biomass filler is completely combusted, then performing ball milling, and obtaining a ternary precursor after the ball milling is finished;
wherein the modified biomass particles used in the step 3) are prepared from the following raw materials in a mass ratio of 8: 12: 5: 3, the coast cedar bark, the west Sichuan spruce bark, the small dried pine bark and the red poplar bark waste wood are prepared, and the modification treatment steps are as follows: immersing waste wood in a modifying solution, and carrying out ultrasonic oscillation for 25min, wherein the modifying solution contains 2.2 wt% of formaldehyde, 0.3 wt% of sulfuric acid, 0.0075mol/L of nickel ions, 0.025mol/L of cobalt ions and 0.0115mol/L of manganese ions;
step 5) preparing the biomass filler from a raw material consisting of the following components in a mass ratio of 2: 1: 2, the waste maple bark, the waste sugar maple bark and the waste silver fir bark are ground into powder, and the average particle size of the powder is 1 mm.
Example 4
A preparation method of a high-purity ternary precursor comprises the following preparation steps:
1) taking waste batteries as raw materials, performing operations of disassembling, sorting and crushing on the waste batteries to obtain slag, soaking the slag in 2mol/L concentrated sulfuric acid for 15min, and filtering, wherein the pH value is kept to be less than or equal to 2 in the soaking process to obtain primary filtrate and residual materials;
2) adding the residual material obtained in the step 1) into 2.5 times of water by weight, slowly adding 1.5mol/L concentrated sulfuric acid, heating to 160 ℃ at the speed of 20 ℃/min, stopping adding the concentrated sulfuric acid, carrying out constant-temperature treatment for 50min, filtering to obtain filter residue, and adding the filter residue into the primary filtrate obtained in the step 1) to obtain a purified solution;
3) adding modified biomass particles into the purified liquid obtained in the step 2), slowly stirring at a rotating speed of 20r/min for 2 hours, and filtering and separating to obtain secondary filtrate and precipitated particles;
4) carrying out combustion treatment on the precipitate particles obtained in the step 3), dissolving the precipitate particles in 0.3mol/L sulfuric acid after complete combustion treatment, adjusting the pH value to 1.0 by using sodium hydroxide or potassium hydroxide, and filtering to obtain a precipitate;
5) adding the precipitate obtained in the step 4) into the secondary filtrate obtained in the step 3), stirring until the precipitate is completely dissolved, adding a biomass filler, stirring at a low speed of 15r/min for 2 hours, filtering the biomass filler, performing combustion treatment on the biomass filler until the biomass filler is completely combusted, then performing ball milling, and obtaining a ternary precursor after the ball milling is finished;
wherein the modified biomass particles used in the step 3) are prepared from the following raw materials in a mass ratio of 8: 12: 5: 3, the coast cedar bark, the west Sichuan spruce bark, the small dried pine bark and the red poplar bark waste wood are prepared, and the modification treatment steps are as follows: immersing waste wood in a modifying solution, and carrying out ultrasonic oscillation for 25min, wherein the modifying solution contains 2.5wt% of formaldehyde, 0.2 wt% of sulfuric acid, 0.005mol/L of nickel ions, 0.05mol/L of cobalt ions and 0.008mol/L of manganese ions;
step 5) preparing the biomass filler from a raw material consisting of the following components in a mass ratio of 2: 1: 2, the waste maple bark, the waste sugar maple bark and the waste silver fir bark are ground into powder, and the average particle size of the powder is 2 mm.
Example 5
A preparation method of a high-purity ternary precursor comprises the following preparation steps:
1) taking waste batteries as raw materials, performing operations of disassembling, sorting and crushing on the waste batteries to obtain slag, soaking the slag in 2mol/L concentrated sulfuric acid for 10min, and filtering, wherein the pH value is kept to be less than or equal to 2 in the soaking process to obtain primary filtrate and residual materials;
2) adding the residual material obtained in the step 1) into 3 times of water by weight, slowly adding 1.5mol/L concentrated sulfuric acid, heating to 150 ℃ at a speed of 15 ℃/min, stopping adding the concentrated sulfuric acid, carrying out constant-temperature treatment for 55min, filtering to obtain filter residue, and adding the filter residue into the primary filtrate obtained in the step 1) to obtain a purified solution;
3) adding modified biomass particles into the purified liquid obtained in the step 2), slowly stirring at a rotating speed of 15r/min for 2 hours, and filtering and separating to obtain secondary filtrate and precipitated particles;
4) carrying out combustion treatment on the precipitate particles obtained in the step 3), dissolving the precipitate particles in 0.5mol/L sulfuric acid after complete combustion treatment, adjusting the pH value to 1.0 by using sodium hydroxide or potassium hydroxide, and filtering to obtain a precipitate;
5) adding the precipitate obtained in the step 4) into the secondary filtrate obtained in the step 3), stirring until the precipitate is completely dissolved, adding a biomass filler, stirring at a low speed of 15r/min for 2 hours, filtering the biomass filler, performing combustion treatment on the biomass filler until the biomass filler is completely combusted, then performing ball milling, and obtaining a ternary precursor after the ball milling is finished;
wherein the modified biomass particles used in the step 3) are prepared from the following raw materials in a mass ratio of 8: 12: 5: 3, the coast cedar bark, the west Sichuan spruce bark, the small dried pine bark and the red poplar bark waste wood are prepared, and the modification treatment steps are as follows: immersing waste wood in a modifying solution, and carrying out ultrasonic oscillation for 20min, wherein the modifying solution contains 2.5wt% of formaldehyde, 0.5wt% of sulfuric acid, 0.01mol/L of nickel ions, 0.05mol/L of cobalt ions and 0.01mol/L of manganese ions;
step 5) preparing the biomass filler from a raw material consisting of the following components in a mass ratio of 2: 1: 2, the waste maple bark, the waste sugar maple bark and the waste silver fir bark are ground into powder, and the average particle size of the powder is 1.5 mm.
The impurity components, water content and particle size of the ternary precursor prepared in examples 1 to 5 were measured. The results are shown in the following table.
Figure BDA0001803845200000081
As is apparent from the above table, the ternary precursor prepared by the method of the present invention has very low impurity content, and the concentrations of some elements such as chromium, cadmium and lead are too low to be measured by a thermoelectric atomic absorption instrument and an atomic absorption method. Therefore, the ternary precursor prepared by the method has the characteristic of high purity.

Claims (3)

1. The preparation method of the high-purity ternary precursor is characterized by comprising the following preparation steps of:
1) taking waste batteries containing nickel, cobalt and manganese as raw materials, performing operations of disassembling, sorting and crushing on the waste batteries to obtain slag, soaking the slag in concentrated sulfuric acid for 10-15 min, and filtering to obtain primary filtrate rich in manganese and residual materials containing nickel, cobalt and iron;
2) adding the residual materials obtained in the step 1) into 2-3 times of water by weight, slowly adding concentrated sulfuric acid, heating to 150-160 ℃, stopping adding the concentrated sulfuric acid, carrying out constant-temperature treatment for 45-60 min, filtering out filter residues containing nickel and cobalt, and adding the filter residues into the primary filtrate obtained in the step 1) to obtain a purified liquid containing nickel, cobalt and manganese;
3) adding modified biomass particles into the purified liquid obtained in the step 2), stirring at a low speed for 1-2 h, and filtering and separating to obtain secondary filtrate containing nickel and manganese and precipitated particles containing cobalt and iron;
the modified biomass particles are prepared from the following components in a mass ratio of 8: 12: 5: 3, preparing waste wood consisting of coast cedar wood bark, western Sichuan spruce wood bark, small dried pine wood bark and red poplar wood bark, wherein the waste wood is subjected to modification treatment, and the modification treatment comprises the following steps: immersing waste wood in the modifying liquid, and ultrasonically oscillating for 20-30 min;
the modifying solution contains 1.5-2.5 wt% of formaldehyde, 0.2-0.5 wt% of sulfuric acid, 0.005-0.01 mol/L of nickel ions, 0.01-0.05 mol/L of cobalt ions and 0.008-0.015 mol/L of manganese ions;
4) carrying out combustion treatment on the precipitate particles obtained in the step 3), dissolving the precipitate particles in 0.25-0.5 mol/L sulfuric acid after complete combustion treatment, adjusting the pH value to 1.0-1.5 by using sodium hydroxide or potassium hydroxide, and filtering to obtain a precipitate containing cobalt;
5) adding the precipitate obtained in the step 4) into the secondary filtrate obtained in the step 3), stirring until the precipitate is completely dissolved, adding a biomass filler, stirring at a low speed for 1-2 hours, filtering out the biomass filler, performing combustion treatment on the biomass filler until the biomass filler is completely combusted, then performing ball milling, and obtaining a nickel-cobalt-manganese ternary precursor after the ball milling is finished;
the biomass filler is prepared by grinding waste maple bark, waste maple bark and waste silver fir bark;
the mass ratio of the waste maple bark, the waste maple bark and the waste silver fir bark used for preparing the biomass filler is 2: 1: 2.
2. the preparation method of the high-purity ternary precursor according to claim 1, wherein the concentration of the concentrated sulfuric acid in the step 1) is 1.5-2 mol/L, and the pH value in the dipping process is controlled to be less than or equal to 2.
3. The preparation method of the high-purity ternary precursor according to claim 1, wherein the concentrated sulfuric acid in the step 2) is 1-1.5 mol/L, and the temperature rise rate is controlled to be 15-20 ℃/min in the temperature rise process.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102082305A (en) * 2010-12-21 2011-06-01 无锡市霄鹰环境科技有限公司 Ionic lead-acid cell repair protection solution
CN106450305A (en) * 2016-11-15 2017-02-22 哈尔滨工程大学 Preparation method of lithium ion battery cathode material CoP/C
US9834827B2 (en) * 2012-04-04 2017-12-05 Worcester Polytechnic Institute Method and apparatus for recycling lithium-ion batteries

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10522884B2 (en) * 2012-04-04 2019-12-31 Worcester Polytechnic Institute Method and apparatus for recycling lithium-ion batteries
CN104685674B (en) * 2012-09-28 2019-03-26 卡博特公司 Active material composite comprising high surface area carbonaceous material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102082305A (en) * 2010-12-21 2011-06-01 无锡市霄鹰环境科技有限公司 Ionic lead-acid cell repair protection solution
US9834827B2 (en) * 2012-04-04 2017-12-05 Worcester Polytechnic Institute Method and apparatus for recycling lithium-ion batteries
CN106450305A (en) * 2016-11-15 2017-02-22 哈尔滨工程大学 Preparation method of lithium ion battery cathode material CoP/C

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
废旧锂离子电池回收利用研究进展;朱虹等;《盐湖研究》;20180915;第26卷(第3期);第70-74页 *

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