CN116162785A - High nickel matte full-chain integrated leaching method, ternary positive electrode material precursor, preparation method and application thereof - Google Patents

High nickel matte full-chain integrated leaching method, ternary positive electrode material precursor, preparation method and application thereof Download PDF

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Publication number
CN116162785A
CN116162785A CN202310055115.XA CN202310055115A CN116162785A CN 116162785 A CN116162785 A CN 116162785A CN 202310055115 A CN202310055115 A CN 202310055115A CN 116162785 A CN116162785 A CN 116162785A
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China
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leaching
powder
nickel matte
roasting
high nickel
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Inventor
鲁游
张荣荣
刘勇奇
王涛
巩勤学
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202310055115.XA priority Critical patent/CN116162785A/en
Publication of CN116162785A publication Critical patent/CN116162785A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention discloses a high nickel matte full-chain integrated leaching method, a ternary positive electrode material precursor, a preparation method and application thereof, wherein the high nickel matte leaching method comprises the following steps: raw material pretreatment, namely mixing high nickel matte powder with an oxidant, and performing primary roasting and secondary roasting, wherein the primary roasting temperature is 150-250 ℃, and the secondary roasting temperature is 350-450 ℃ to obtain pretreated powder; and leaching under normal pressure and low acid, mixing the pretreated powder with water, acid and a supplemental oxidant to obtain slurry, reacting, and carrying out solid-liquid separation on the slurry for the first time after the reaction to obtain low acid leaching solution. In the pretreatment process of the high nickel matte, the two-stage roasting is adopted, the high nickel matte material after roasting is easier to leach with low acid, the leaching time is shortened by 2 to 3 times compared with the conventional normal-pressure low-acid leaching time, the production efficiency is improved, the metal simple substance is converted into oxide, no hydrogen is generated during low-acid leaching, and the method has lower requirements on equipment and is safer and environment-friendly compared with the conventional high temperature of 1000 ℃ and oxygen atmosphere.

Description

High nickel matte full-chain integrated leaching method, ternary positive electrode material precursor, preparation method and application thereof
Technical Field
The invention relates to the technical field of pyrometallurgy and hydrometallurgy, in particular to a high nickel matte full-chain integrated leaching method, a ternary positive electrode material precursor, a preparation method and application thereof.
Background
Currently, the entire power battery industry is under intense revolution. Regardless of policy guidance, market demand, or technology evolution, the high nickel content of ternary materials has become a necessary trend in the development of lithium battery materials. Under the large background of subsidy and slope returning and international competition aggravation, domestic enterprises are actively laying out the high-nickel ternary field.
The high nickel makes the energy density of the power battery obviously improved, means that the battery with the same weight can provide more charge quantity, realizes the light weight, reduces hundred kilometers of electricity consumption, and obviously improves the endurance mileage of the new energy automobile, which is important for the passenger car with limited space and sensitive endurance performance.
With the development of high nickel content of ternary materials, the demand for nickel is increased year by year, and the establishment of a full-chain integrated industrial garden is the primary choice for reducing cost and enhancing efficiency of most lithium battery anode material manufacturers at present by smelting high nickel matte to prepare ternary anode materials.
The high nickel matte is a eutectic of nickel, copper, cobalt, iron, sulfur and metal sulfide which are obtained by smelting nickel concentrate through electric and primary conversion, and a nickel copper cobalt phase mainly exists in a sulfide phase and an alloy phase, and the high nickel matte is called as low nickel matte because the nickel content is high (55-65%). The method is mainly used for producing electrolytic nickel, nickel oxide, nickel iron, nickel-containing alloy and various nickel salts, and can be directly used for steelmaking after special treatment. It is clear that the high nickel matte is only one transition, and the final purpose is to produce nickel sulfate and the like, wherein the nickel sulfate is the necessary material for producing ternary precursors, and the ternary precursors finally produce the positive electrode material of the battery. The method takes natural nickel ore as a source, and finally the nickel ore is used as a positive electrode material, and the middle part of the nickel ore is subjected to complex and long processing procedures, and each processing procedure can become a subdivision industry.
The leaching high nickel matte industry generally adopts a high-pressure acid leaching process, the high-pressure acid leaching has higher requirements on equipment working conditions, large slag quantity, large equipment volume, high manufacturing cost and low safety, while the leaching rate of the traditional high nickel matte normal-pressure low-acid leaching is only 20 to 50 percent, the leaching time is long, and a leaching mode which is efficient, rapid, safe and economic needs to be developed. In addition, when the solid-liquid separation is realized by filter pressing during leaching of high nickel matte and low acid, the filter cloth filter pressing is often blocked by gelatinous oily substances in the leaching process of high nickel matte, so that the solid-liquid separation efficiency is low, the production efficiency is restricted, large-particle floccules are formed on a production line by increasing the pH value, the filter pressing is promoted, but the pH value is increased, auxiliary materials are consumed, and meanwhile, impurity elements are easily caused to be enriched in low acid to make the leaching of high nickel matte and low acid difficult, the cost of the production line is increased, so that the filter pressing is difficult for the leaching of high nickel matte and low acid, and a low-cost filter pressing method for promoting the low acid pressure filtration and improving the production efficiency is also needed to be found.
The common ternary precursor in the market is hydroxide composed of three metal elements of nickel, cobalt and manganese, and the proportion of each element determines the performance of the ternary precursor. The new energy automobile industry is rapidly developed nowadays, and the requirement on a high-capacity lithium ion battery is vigorous, so that the requirement on the performance of a front-end ternary positive electrode material is provided, and a high-nickel ternary precursor gradually becomes the mainstream. Development of new leaching methods is a development of industry to reduce the cost of synthesizing ternary precursors.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a high nickel matte full-chain integrated leaching method, a preparation method of a ternary positive electrode material precursor and the ternary positive electrode material precursor obtained by the preparation method.
The invention is realized in the following way:
in a first aspect, the present invention provides a method of leaching high nickel matte, comprising:
raw material pretreatment, namely mixing high nickel matte powder with an oxidant, and performing primary roasting and secondary roasting, wherein the primary roasting temperature is 150-250 ℃, and the secondary roasting temperature is 350-450 ℃ to obtain pretreated powder;
and leaching under normal pressure and low acid, mixing the pretreated powder with water, acid and a supplemental oxidant to obtain slurry, reacting, and carrying out solid-liquid separation on the slurry for the first time after the reaction to obtain low acid leaching solution.
In an alternative embodiment, the feedstock pretreatment step satisfies at least one of the following (1) - (7):
(1) the granularity of the high nickel matte powder is 60-200 meshes;
(2) the oxidant is lithium manganate pole piece powder, lithium cobaltate pole piece powder or lithium nickel cobalt manganate pole piece powder;
(3) the mass ratio of the high nickel matte powder to the oxidant is 1:1-1.5;
(4) the roasting time is 50-70min;
(5) the two-stage roasting time is 250-300min;
(6) spraying water into the material until the water content in the material is 4.5-5.5wt% when the second-stage roasting is performed for 80-100 min;
(7) the primary roasting and the secondary roasting are carried out in an air atmosphere.
In an alternative embodiment, the atmospheric low acid leaching step satisfies at least one of the following (1) - (8):
(1) the pretreatment powder and water are mixed according to the ratio of 1:2.5-3.5 for pulping;
(2) the mass ratio of the pretreatment powder to the added oxidant is 1:1-1:3;
(3) the reaction temperature is 60-90 ℃;
(4) the slurry reacts for 2-3 hours under the condition that the pH value is 0.5-1.0, and then is subjected to primary solid-liquid separation;
(5) the slurry reacts for 0.5 to 2 hours under the condition that the pH value is 0.5 to 1.0, then the pH value is adjusted back to 2.0 to 2.5, and the slurry reacts for 2 to 3 hours and then is subjected to primary solid-liquid separation;
(6) in the normal pressure low acid leaching step, the slurry reacts for 0.5-2 hours under the condition that the pH value is 0.5-1.0, then the unqualified ternary precursor is added to adjust the pH value to 2.0-2.5 for reacting for 2-3 hours, and then the first solid-liquid separation is carried out;
(7) adding a filter aid into the slurry after the reaction is finished, and adjusting the temperature to 80-90 ℃;
(8) the first solid-liquid separation is performed in a membrane filter press.
In an alternative embodiment, the filter aid comprises activated carbon and powdered charcoal:
preferably, 0.9-1.1kg of filter aid is added per cubic meter of slurry;
preferably, the activated carbon is coconut shell hard activated carbon, and the mass ratio of the coconut shell hard activated carbon to the charcoal powder is 1:0.5-1.5;
more preferably, the coconut shell hard activated carbon is waste activated carbon in the extraction and oil removal process, and the waste activated carbon is dried for 2-3 hours at 80-90 ℃ before being used;
preferably, the particle size of the filter aid is from 10 to 60 mesh.
In an alternative embodiment, the first solid-liquid separation step also obtains low acid leaching slag, and the low acid leaching slag is leached by normal pressure high acid, wherein the normal pressure high acid leaching is to add acid to the low acid leaching slag to reach the acidity of 100-400g/L, adjust the temperature to 50-90 ℃ and add a reducing agent for reaction, and then carry out second solid-liquid separation to obtain high acid leaching liquor after the reaction;
preferably, the reducing agent is at least one of hydrogen peroxide, sodium sulfite and sodium thiosulfate;
preferably, the high acid leaching solution is returned to the normal pressure low acid leaching step to be mixed with the pretreated powder for pulping.
In an alternative embodiment, the low-acid leaching solution is subjected to impurity removal to obtain an impurity-removed leaching solution;
preferably, the removing impurities includes: adding iron powder into the low-acid leaching solution to remove copper primarily, adding hydrogen peroxide to remove ferrous iron, heating to 80-95 ℃, adjusting the pH value to 3.8-4.2 to remove iron and aluminum, and adding sodium sulfide to remove copper deeply; then removing calcium, magnesium and zinc in the copper-removing leaching solution by adopting an extraction method, and removing lithium in the raffinate to obtain a impurity-removing leaching solution;
more preferably, after the temperature is raised to 80-95 ℃, firstly adding unqualified ternary precursor to adjust the pH to 3.0-3.5, and then adding sodium carbonate concentrate to adjust the pH to 3.8-4.2;
more preferably, the molar ratio of the iron powder to the copper ions in the low-acid leaching solution is 1:0.9-1.1.
In a second aspect, the present invention provides a method for preparing a ternary cathode material precursor, which includes performing hydrothermal synthesis using the leachate according to any one of the foregoing embodiments as a raw material, to obtain a ternary cathode material precursor.
In an alternative embodiment, in the hydrothermal synthesis step, metal salt is added to the leaching solution, and a ternary positive electrode material precursor with a specified composition is obtained through hydrothermal synthesis by a coprecipitation method.
In a third aspect, the present invention provides a ternary cathode material precursor obtained by the preparation method according to the foregoing embodiment.
In a fourth aspect, the present invention provides a ternary cathode material prepared from the ternary cathode material precursor according to the foregoing embodiments.
The invention has the following beneficial effects:
in the pretreatment process of the high nickel matte, the two-stage roasting is adopted, the high nickel matte material after roasting is easier to leach with low acid, the leaching time is shortened by 2 to 3 times compared with the conventional normal-pressure low-acid leaching time, the production efficiency is improved, the metal simple substance is converted into oxide, no hydrogen is generated during low-acid leaching, and the method has lower requirements on equipment and is safer and environment-friendly compared with the conventional high temperature of 1000 ℃ and oxygen atmosphere.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment provides a method for leaching high ice nickel, which comprises the following steps:
raw material pretreatment, namely mixing high nickel matte powder with an oxidant, and performing primary roasting and secondary roasting, wherein the primary roasting temperature is 150-250 ℃, and the secondary roasting temperature is 350-450 ℃ to obtain pretreated powder;
and leaching under normal pressure and low acid, mixing the pretreated powder with water, acid and a supplemental oxidant to obtain slurry, reacting, and carrying out solid-liquid separation on the slurry for the first time after the reaction to obtain low acid leaching solution.
The embodiment carries out pretreatment on the high nickel matte, adopts two-stage roasting, the high nickel matte material after roasting is easier to leach with low acid, the leaching time is shortened by 2 to 3 times compared with the conventional normal pressure low acid leaching time, the production efficiency is improved, the metal simple substance is converted into oxide, no hydrogen is generated during low acid leaching, and the method has lower requirements on equipment and is safer and environment-friendly compared with the traditional 1000 ℃ high temperature and oxygen atmosphere.
In some embodiments of the application, the high nickel matte powder has a granularity of 60-200 meshes, is too large in granularity, has a small contact area with the oxidant, is unfavorable for reaction, has too small granularity, increases raw material pretreatment energy consumption, and can be agglomerated, but is unfavorable for improving the contact area with the oxidant.
In some embodiments of the present application, the oxidizing agent is lithium manganate pole piece powder, lithium cobaltate pole piece powder or lithium nickel cobalt manganate pole piece powder, where the pole piece powder may be newly prepared positive electrode material powder or positive electrode material powder recovered from a waste lithium ion battery pole piece, and according to experimental results, the lithium cobaltate pole piece powder or lithium manganate pole piece powder is preferentially adopted, and also the lithium nickel cobalt manganate pole piece powder may be used, but the lithium nickel cobalt manganate pole piece powder is not as good as the Lithium Cobalt (LCO) pole piece powder and the lithium manganate pole piece powder (LMO) oxidation effect.
In some embodiments of the present application, the mass ratio of the high nickel matte powder to the oxidizing agent is 1:1-1.5, for example, may be 1:1.1, 1:1.2, 1:1.3, 1:1.4, or 1:1.5;
in some embodiments of the present application, the period of firing time is 50-70min, for example, may be 50min, 60min or 70min, preferably 60min;
in some embodiments of the present application, the secondary firing time is 250-300min, for example, 250min, 260min, 270min, 280min, 290min, or 300min.
In some embodiments of the application, water is sprayed into the material until the moisture content in the material is 4.5-5.5wt% when the second-stage roasting is performed for 80-100min, so that on one hand, the increase of the reaction temperature can be restrained, on the other hand, the contact area between the high nickel matte powder and the lithium manganate pole piece powder LMO can be increased, and the reaction efficiency is improved. In some preferred embodiments, water is sprayed into the material to a moisture content of 5wt% in the material when the two-stage roasting is performed for 90 min.
In some embodiments of the present application, the primary roasting and the secondary roasting are both performed under an air atmosphere to promote the forward reaction, and through the secondary roasting, sulfide materials in the high nickel matte are oxidized, simple substances are oxidized into oxides, the treated materials are easier to leach with low acid, and the efficiency of converting the high nickel matte into nickel sulfate is 20% to 35% (a, if lithium cobalt oxide pole piece powder or lithium manganate pole piece powder is adopted as an oxidant in the system, the nickel content of leaching liquid and leaching slag of the system is detected, and the leaching efficiency of the high nickel matte is calculated according to the total metal content of nickel in the pretreated powder, b, the concentration of nickel copper in the high acid leaching liquid is detected in the low acid leaching system using the high acid leaching liquid to calculate the leaching efficiency).
In some embodiments of the present application, the pre-treatment powder is slurried with water in a 1:2.5-3.5 mix, for example, 1:2.5, 1:3, or 1:3.5 mix.
In some embodiments of the present application, the mass ratio of the pretreatment powder to the additional oxidant is 1:1-1:3, and the excess oxidant is beneficial to improving leaching rate and leaching efficiency.
In some embodiments of the present application, the reaction temperature is 60-90 ℃, and in some preferred embodiments, the reaction temperature is 70 ℃. When heating the slurry, in order to improve the heating efficiency and the heating uniformity, the slurry is heated by introducing steam into the slurry.
In some embodiments of the present application, the slurry is subjected to a first solid-liquid separation after reacting for 2-3 hours at a pH of 0.5-1.0;
in some embodiments of the present application, the slurry is reacted for 0.5-2 hours under the condition that the pH value is 0.5-1.0, then the pH value is adjusted back to 2.0-2.5, and the first solid-liquid separation is performed after the reaction for 2-3 hours;
in some embodiments of the present application, in the atmospheric low acid leaching step, the slurry is reacted for 0.5-2 hours under the condition that the pH is 0.5-1.0, then the unqualified ternary precursor is supplemented to adjust back to the pH to 2.0-2.5, and after reacting for 2-3 hours, the first solid-liquid separation is performed.
And sulfuric acid is added into the slurry to adjust the pH to be 0.5-1.0, under the action of acid, the reaction is continuously accelerated by combining with the increase of the temperature, the reaction rate is increased, the forward reaction is promoted, and the leaching efficiency is also greatly improved. The pH of the slurry will increase spontaneously during the reaction, so that repeated sulfuric acid addition is needed, and the sulfuric acid addition rate is controlled to be 0.2-1m 3 And/h, so that the pH of the system is controlled to be 0.5-1.0, and the leaching reaction is facilitated, but the situation that the leaching solution needs to be subjected to impurity removal in the later period is considered, and a great amount of hydrogen is generated in the process of removing copper by the iron powder with too low acid degree in the impurity removal procedure, so that the pH is adjusted back to be 2.0-2.5 in the later period of the reaction, and the resource utilization rate can be improved by adopting the unqualified ternary precursor to adjust back to the pH. The leaching efficiency of the high nickel matte after the normal pressure low acid leaching step can reach 60 to 80 percent.
In some embodiments of the present application, a filter aid is added to the slurry after the reaction is completed, and the temperature is adjusted to 80-90 ℃;
in some embodiments of the present application, the first solid-liquid separation is performed in a membrane filter press.
In some embodiments of the present application, the filter aid comprises activated carbon and powdered charcoal, 0.9-1.1kg of filter aid is added per cubic meter of slurry, the activated carbon and insoluble particles in the high nickel matte form wrapped adsorption, large particles are formed, and the filter pressing efficiency is reduced by half compared with the time without adding activated carbon.
In some preferred embodiments, the activated carbon is coconut shell hard activated carbon, the mass ratio of the coconut shell hard activated carbon to the charcoal powder is 1:0.5-1.5, the coconut shell hard activated carbon is waste activated carbon in the oil extraction and removal process, and the waste activated carbon is firstly dried for 2-3 hours at 80-90 ℃ before being used, so that a small amount of oil in the carbon powder is removed. The extraction active carbon comes from an extraction liquid degreasing process in the production process of the anode material, a large amount of nickel and cobalt are entrained, the extraction active carbon is used for leaching high nickel matte low-acid, belongs to waste recycling, and the cost is far lower than that of the conventional active carbon. Although the extracted active carbon is deoiled, the extracted active carbon cannot be completely removed, and charcoal powder can absorb oil to assist in filtration, wherein the charcoal powder can also adopt waste charcoal powder. The hardness of the coconut shell activated carbon is higher than that of common activated carbon, the slag forming plate is good when the coconut shell activated carbon is pressed and filtered by a membrane press filter, the plate is quickly removed, and the coconut shell hard activated carbon is preferred.
In some preferred embodiments, the particle size of the filter aid is 10-60 meshes, and the filter aid has better filtering effect.
In some embodiments of the present application, the first solid-liquid separation step further obtains a low acid leaching residue, and the low acid leaching residue is subjected to normal pressure high acid leaching, wherein the normal pressure high acid leaching is to add acid to the low acid leaching residue to reach acidity of 100-400g/L, adjust the temperature to 50-90 ℃ and add a reducing agent to react, and then perform a second solid-liquid separation to obtain a high acid leaching solution. At the moment, the system slag is mainly lithium cobalt oxide pole piece powder or lithium manganate pole piece powder and a small amount of high nickel matte powder, a reducing agent is added to reduce the components which cannot be leached in the steps, the leaching efficiency can be improved by adjusting the acidity, and the metal leaching rate can reach 99.6% after the high acid leaching step.
Preferably, the reducing agent is at least one of hydrogen peroxide, sodium sulfite and sodium thiosulfate;
preferably, the high acid leaching solution is returned to the normal pressure low acid leaching step to be mixed with the pretreated powder for pulping.
In some embodiments of the present application, the low acid leaching solution is decontaminated to obtain a decontaminated leaching solution;
preferably, the removing impurities includes: adding iron powder into the low-acid leaching solution to remove copper primarily, adding 8% hydrogen peroxide to remove ferrous iron, heating to 80-95 ℃, adjusting pH to 3.8-4.2 to remove iron and aluminum, and adding sodium sulfide to remove copper deeply; then removing calcium, magnesium and zinc in the copper-removing leaching solution by adopting an extraction method, and removing lithium in the raffinate to obtain a impurity-removing leaching solution;
more preferably, after the temperature is raised to 80-95 ℃, firstly adding unqualified ternary precursor to adjust the pH to 3.0-3.5, and then adding sodium carbonate concentrate to adjust the pH to 3.8-4.2; the pH value can be adjusted by adding the unqualified ternary precursor, so that the utilization rate of raw materials can be improved, but if the pH value is adjusted to 3.8-4.2 by directly adopting the unqualified ternary precursor, the unqualified ternary precursor is not fully reacted and is entrained in slag, so that the utilization rate of the raw materials is reduced.
More preferably, the molar ratio of copper ions in the iron powder to the low acid leaching solution is 1:0.9-1.1, preferably 1:1, so that the preliminary copper removal effect is ensured without excessively increasing iron-containing impurities.
In a second aspect, the present invention provides a method for preparing a ternary cathode material precursor, which includes performing hydrothermal synthesis using the leachate according to any one of the foregoing embodiments as a raw material, to obtain a ternary cathode material precursor.
In some embodiments of the present application, in the hydrothermal synthesis step, metal salt is added to the leachate, and a ternary positive electrode material precursor with a specified composition is obtained through hydrothermal synthesis by a coprecipitation method, and when each element in the leachate cannot meet the requirement of a target ternary positive electrode material precursor, the missing metal element needs to be added.
In a third aspect, the present invention provides a ternary cathode material precursor obtained by the preparation method according to the foregoing embodiment.
In a fourth aspect, the present invention provides a ternary cathode material prepared from the ternary cathode material precursor according to the foregoing embodiments.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The method for preparing the ternary precursor by leaching the high nickel matte in the embodiment comprises the following specific steps:
(1) Taking nickel content of 58.29%, co content of 1.22%, cu content of 15.21%, S content of 21.242%, ca content of 0.012% as raw materials, mg content of 0.016%, fe content of 0.91% and Zn content of 0.0018% as raw materials, crushing the nickel with high nickel matte, crushing the crushed nickel matte into powder materials of 60-200 meshes by a conical ball mill, and grinding the powder materials according to the nickel matte powder materials: lithium manganate pole piece powder mass ratio = 1:1, mixing, carrying out primary roasting by a rotary kiln, wherein the roasting temperature is set at 200 ℃, the roasting time is set at 60 minutes, carrying out secondary roasting on the material after the primary roasting, wherein the roasting temperature is set at 400 ℃, spraying primary water when the material is roasted to 90 minutes in the middle, controlling the water content to be 5% of the total weight of the material, the roasting time is set at 180 minutes, the protective atmosphere is air, and cooling to obtain high nickel matte pretreatment powder;
(2) The pretreated high nickel matte pretreatment powder is prepared according to the mass ratio of 1:2, adding concentrated water as base water by matching with positive electrode material powder, and mixing according to a solid-liquid ratio of 1:3 pulping, namely, adding sulfuric acid into a normal pressure steel lining acid-resistant brick reaction tank with slightly different leaching rates, repeatedly adjusting back the pH to 0.5-1.0, adding an unqualified ternary precursor, adjusting back the pH to 2.0-2.5, adding 50 kg of filter aid, and heating to 80 ℃ to obtain low-acid leaching slurry;
(3) Filtering the reaction liquid by a membrane filter press with the filtering efficiency of 20m 3 And/h, separating out the low-acid leachingThe method comprises the steps of deslagging and low-acid leaching, wherein the low-acid leaching is carried out in a normal pressure high-acid leaching process, the high-acid leaching returns to the normal pressure low-acid leaching step to be mixed with the pretreatment powder for pulping, the low-acid leaching is subjected to a chemical impurity removal process, iron powder is added for one-time copper removal, 8% of hydrogen peroxide is oxidized into ferrous iron, the temperature is controlled to be 80-95 ℃, unqualified precursors are added to adjust the pH value to 3.0-3.5, sodium carbonate solution is added to adjust the pH value to 3.8-4.2 for removing iron and aluminum, and after solid-liquid separation, the obtained wet liquid is further subjected to calcium, magnesium and zinc removal by extraction, and raffinate is subjected to lithium removal, so that qualified wet liquid is obtained;
(4) Mixing 1/3 of sodium borohydride with the mass concentration of 0.5wt%, 1/3 of ammonia water with the mass concentration of 6wt%, water and sodium hydroxide, adding the mixture into a reaction kettle to serve as base solution, adding cobalt sulfate and manganese sulfate into the prepared qualified wet-process liquid to prepare a nickel cobalt manganese mixed solution with the molar ratio of nickel to cobalt to manganese of 6:2:2 and the total concentration of nickel to cobalt to manganese of 100g/L, mixing the nickel cobalt manganese mixed solution with the rest of ammonia water and sodium borohydride, adding the mixture into the reaction kettle, and introducing nitrogen to serve as protective gas;
(5) Regulating the pH value in the reaction kettle to 10.1, controlling the temperature to 50-60 ℃ and the stirring speed to 250r/min, performing nucleation reaction (the reaction only generates nucleation and does not grow through controlling the residence time by a nucleation generator) in the reaction kettle to obtain slurry, designing a procedure for configuring kettle serial overflow, overflowing the prepared slurry to a growth kettle, and enabling the verification of the ternary precursor to grow under the condition that no new nuclei are generated; and (3) overflowing the slurry of the growth kettle to a synthesis kettle (a reaction kettle used in the synthesis process), and performing precipitation, washing, separation and drying to obtain the 6-series ternary precursor.
Example 2
The method for leaching the high nickel matte in the embodiment comprises the following specific steps:
(1) Taking nickel content of 58.29%, co content of 1.22%, cu content of 15.21%, S content of 21.242%, ca content of 0.012% as raw materials, mg content of 0.016%, fe content of 0.91% and Zn content of 0.0018% as raw materials, crushing the nickel with high nickel matte, crushing the crushed nickel matte into powder materials of 60-200 meshes by a conical ball mill, and grinding the powder materials according to the nickel matte powder materials: lithium cobaltate pole piece powder mass ratio = 1:1.5, mixing, carrying out primary roasting by a rotary kiln, wherein the roasting temperature is set at 150 ℃, the roasting time is set at 70min, carrying out secondary roasting on the material after the primary roasting, wherein the roasting temperature is set at 350 ℃, spraying primary water when the material is roasted to 80min in the middle, controlling the water content to be 5% of the total weight of the material, the roasting time is set at 220min, the protective atmosphere is air, and cooling to obtain high nickel matte pretreatment powder;
(2) The pretreated high nickel matte pretreatment powder is prepared according to the mass ratio of 1:1, adding concentrated water as base water according to a solid-to-liquid ratio of 1:3 pulping, namely, adding sulfuric acid into a normal pressure steel lining acid-resistant brick reaction tank with slightly different leaching rates, repeatedly adjusting back the pH to 0.5-1.0, adding an unqualified ternary precursor, adjusting back the pH to 2.0-2.5, adding 50 kg of filter aid, and heating to 60 ℃ to obtain low-acid leaching slurry;
(3) Filtering the reaction liquid through a membrane filter press to separate low-acid leaching slag and low-acid leaching liquid, carrying out normal-pressure high-acid leaching on the low-acid leaching slag, returning the high-acid leaching liquid to the normal-pressure low-acid leaching step, mixing with the pretreated powder for pulping, carrying out chemical impurity removal on the low-acid leaching liquid, adding iron powder for one time to remove copper, adding 8% hydrogen peroxide ferrous oxide, controlling the temperature to 80-95 ℃ and adding unqualified precursors to adjust the pH value to 3.0-3.5, adding sodium carbonate solution to adjust the pH value to 3.8-4.2 to remove iron and aluminum, and carrying out solid-liquid separation, wherein the obtained wet solution is further subjected to calcium magnesium and zinc removal by extraction, and lithium removal of raffinate to obtain qualified wet solution.
Example 3
The method for leaching the high nickel matte in the embodiment comprises the following specific steps:
(1) Taking nickel content of 58.29%, co content of 1.22%, cu content of 15.21%, S content of 21.242%, ca content of 0.012% as raw materials, mg content of 0.016%, fe content of 0.91% and Zn content of 0.0018% as raw materials, crushing the nickel with high nickel matte, crushing the crushed nickel matte into powder materials of 60-200 meshes by a conical ball mill, and grinding the powder materials according to the nickel matte powder materials: lithium manganate pole piece powder mass ratio = 1:1, mixing, carrying out primary roasting by a rotary kiln, wherein the roasting temperature is set at 250 ℃, the roasting time is set at 70min, carrying out secondary roasting on the material after the primary roasting, wherein the roasting temperature is set at 450 ℃, spraying primary water when the middle roasting is carried out for 100min, controlling the water content to be 5% of the total weight of the material, the roasting time is set at 150min, the protective atmosphere is air, and cooling to obtain high nickel matte pretreatment powder;
(2) The pretreated high nickel matte pretreatment powder is prepared according to the mass ratio of 1:3, matching with positive electrode material powder, adding concentrated water as base water, and according to a solid-to-liquid ratio of 1:3 pulping, namely, adding sulfuric acid into a normal pressure steel lining acid-resistant brick reaction tank with slightly different leaching rates, repeatedly adjusting back the pH to 0.5-1.0, adding an unqualified ternary precursor, adjusting back the pH to 2.0-2.5, adding 50 kg of filter aid, and heating to 90 ℃ to obtain low-acid leaching slurry;
(3) Filtering the reaction liquid through a membrane filter press to separate low-acid leaching slag and low-acid leaching liquid, carrying out normal-pressure high-acid leaching on the low-acid leaching slag, returning the high-acid leaching liquid to the normal-pressure low-acid leaching step, mixing with the pretreated powder for pulping, carrying out chemical impurity removal on the low-acid leaching liquid, adding iron powder for one time to remove copper, adding 8% hydrogen peroxide ferrous oxide, controlling the temperature to 80-95 ℃ and adding unqualified precursors to adjust the pH value to 3.0-3.5, adding sodium carbonate solution to adjust the pH value to 3.8-4.2 to remove iron and aluminum, and carrying out solid-liquid separation, wherein the obtained wet solution is further subjected to calcium magnesium and zinc removal by extraction, and lithium removal of raffinate to obtain qualified wet solution.
Comparative example 1:
1) Taking nickel content of 58.29%, co content of 1.22%, cu content of 15.21%, S content of 21.242%, ca content of 0.012% as raw materials, mg content of 0.016%, fe content of 0.91% and Zn content of 0.0018% as raw materials, crushing the nickel with high nickel matte, crushing the crushed nickel matte into powder materials of 60-200 meshes by a conical ball mill, and grinding the powder materials according to the nickel matte powder materials: lithium manganate pole piece powder (or lithium cobaltate pole piece powder) mass ratio=1: 1, mixing, carrying out primary roasting by a rotary kiln, wherein the roasting temperature is set at 200 ℃, the roasting time is set at 60 minutes, carrying out secondary roasting on the material after the primary roasting, wherein the roasting temperature is set at 400 ℃, spraying primary water when the material is roasted to 90 minutes in the middle, controlling the water content to be 5% of the total weight of the material, the roasting time is set at 180 minutes, the protective atmosphere is air, and cooling to obtain high nickel matte pretreatment powder;
(2) The pretreated high nickel matte pretreatment powder is prepared according to the following weight ratio of 1:2, adding concentrated water as base water by matching with positive electrode material powder, and mixing according to a solid-liquid ratio of 1:3 pulping, namely, adding sulfuric acid into a normal-pressure steel lining acid-resistant brick reaction tank with slightly different leaching rates, repeatedly adjusting back the pH to 0.5-1.0, adding unqualified ternary precursor, adjusting back the pH to 2.0-2.5, adding no extracted waste activated carbon, and heating to 80 ℃ to obtain low-acid leaching slurry;
(3) Filtering the reaction liquid by a membrane filter press with the filtering efficiency of 5 to 10m 3 And (3) separating low-acid leaching slag and low-acid leaching liquid, performing normal-pressure high-acid leaching on the low-acid leaching slag, performing chemical impurity removal on the low-acid leaching liquid, adding iron powder to remove copper once, controlling the temperature to be 80-95 ℃ by adding unqualified precursors to adjust the pH value to 3.0-3.5, adding sodium carbonate solution to adjust the pH value to 3.8-4.2 to remove iron and aluminum, performing solid-liquid separation, and further removing calcium, magnesium and zinc from the obtained wet liquid by extraction, and removing lithium from raffinate to obtain qualified wet liquid.
Comparative example 2
The only difference from example 1 is that calcination is carried out at 1000℃for 4 hours, followed by low acid leaching.
Comparative example 3
The only difference from example 1 is that no water was added in the two-stage calcination step.
Comparative example 4
The only difference from example 1 is that the oxidant is replaced by 8% hydrogen peroxide from the lithium manganate pole piece powder.
Comparative example 5
The only difference from example 1 is that the filter aid is wood activated carbon.
The high nickel matte leaching was monitored for each step in the examples and comparative examples, and the results are shown in the following table.
Figure BDA0004060279500000141
1. In the invention, the oxidant adopted by the high nickel matte low-acid normal pressure leaching is the positive electrode material LCO or NCO recovered from the waste lithium ion battery, so that the auxiliary material cost during the high nickel matte leaching is saved, the valuable metal in the waste lithium battery is recovered, the pressure of nickel sulfate raw material supply is relieved, two benefits are realized, and the win-win effect of economic benefit and social benefit is realized.
2. The method has the advantages that for the treatment procedure of the extracted coconut shell activated carbon, the extracted waste activated carbon is adopted, nickel cobalt metal carried in the extracted activated carbon in the extraction and recovery process can be recovered, the filter pressing efficiency after leaching of the high nickel matte low-acid can be improved, slag plates are better, the number of filter cloth is less, the efficiency of filter pressing and plate disassembling is higher, and the industrial problem of low solid-liquid separation efficiency of slurry after leaching of the high nickel matte low-acid is solved by adopting the extracted coconut shell activated carbon for leaching of the high nickel matte low-acid;
3. the pretreatment process of the high nickel matte adopts two-stage roasting, the lithium cobaltate powder or the lithium manganate powder is used as the oxidant, the roasted high nickel matte material is easier to leach with low acid, the leaching time is shortened by 2 to 3 times compared with the conventional normal-pressure low-acid leaching time, the production efficiency is improved, the metal simple substance is converted into the oxide, no hydrogen is generated during low-acid leaching, and compared with the conventional 1000 ℃ high temperature, the oxygen atmosphere has lower requirements on equipment and is safer and environment-friendly;
4. when the low-acid normal-pressure leaching is carried out, because the acidity is low, hydrogen sulfide generated by the high-grade nickel matte is little, and the hydrogen sulfide can react with the lithium LCO cobalt oxide positive electrode powder preferentially and be oxidized into sulfate radical;
5. when the high acid is leached at normal pressure, as the amount of the oxidant such as lithium cobalt oxide powder in the low acid leaching slag is far higher than the ratio of the high nickel matte, sulfide in the high nickel matte can react with the oxidant preferentially, so that the generation of hydrogen sulfide is avoided;
6. when the low-acid leaching slurry is subjected to pressure filtration, the pressure filtration of the membrane filter press is affected due to the fact that a small amount of oil is contained in the slurry, and the waste charcoal powder is low in price and is used for assisting in filtration, so that the cost is low;
7. compared with the prior art of leaching high nickel matte by traditional low-acid, the method provided by the invention uses the positive electrode material powder recovered from the waste lithium ion battery as the oxidant to replace high-concentration oxygen or hydrogen peroxide, so that the safety risk caused by oxygen or hydrogen peroxide is eliminated, and the method is safer, more environment-friendly and economical.
8. Compared with the traditional high-pressure leaching technology for high-nickel matte, the method disclosed by the invention is normal-pressure leaching, the leaching efficiency is close to that of high-pressure leaching, the equipment requirement is simple, the safety coefficient is higher, the recovery rate of nickel and cobalt in the anode material and the extracted waste active carbon is improved while the high-nickel matte is leached, and the economic cost is lower.
9. The qualified wet method liquid obtained by the method is added with a cobalt source and a manganese source, the proportion is adjusted, a ternary precursor (nickel cobalt manganese hydroxide) is synthesized by a hydrothermal synthesis method, the unqualified precursor returns to the front end and is used for the low-acid leaching process and the impurity removal process to adjust back the pH value, the reaction is not foamed, the concentration of the feed liquid is improved, the risk of bubbling with sodium carbonate to cause a groove due to too low acid is avoided, and the green circulation from the unqualified intermediate product to the battery anode material of the waste lithium ion battery and the metal in high nickel matte is realized.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method of leaching high ice nickel, comprising:
raw material pretreatment, namely mixing high nickel matte powder with an oxidant, and performing primary roasting and secondary roasting, wherein the primary roasting temperature is 150-250 ℃, and the secondary roasting temperature is 350-450 ℃ to obtain pretreated powder;
and leaching under normal pressure and low acid, mixing the pretreated powder with water, acid and a supplemental oxidant to obtain slurry, reacting, and carrying out solid-liquid separation on the slurry for the first time after the reaction to obtain low acid leaching solution.
2. The high nickel matte leaching process according to claim 1, wherein said raw material pretreatment step satisfies at least one of the following items (1) to (7):
(1) the granularity of the high nickel matte powder is 60-200 meshes;
(2) the oxidant is lithium manganate pole piece powder, lithium cobaltate pole piece powder or lithium nickel cobalt manganate pole piece powder;
(3) the mass ratio of the high nickel matte powder to the oxidant is 1:1-1.5;
(4) the roasting time is 50-70min;
(5) the two-stage roasting time is 250-300min;
(6) spraying water into the material until the water content in the material is 4.5-5.5wt% when the second-stage roasting is performed for 80-100 min;
(7) the primary roasting and the secondary roasting are carried out in an air atmosphere.
3. The high nickel matte leaching process according to claim 1, wherein said atmospheric low acid leaching step satisfies at least one of the following items (1) - (8):
(1) the pretreatment powder and water are mixed according to the ratio of 1:2.5-3.5 for pulping;
(2) the mass ratio of the pretreatment powder to the added oxidant is 1:1-1:3;
(3) the reaction temperature is 60-90 ℃;
(4) the slurry reacts for 2-3 hours under the condition that the pH value is 0.5-1.0, and then is subjected to primary solid-liquid separation;
(5) the slurry reacts for 0.5 to 2 hours under the condition that the pH value is 0.5 to 1.0, then the pH value is adjusted back to 2.0 to 2.5, and the slurry reacts for 2 to 3 hours and then is subjected to primary solid-liquid separation;
(6) in the normal pressure low acid leaching step, the slurry reacts for 0.5-2 hours under the condition that the pH value is 0.5-1.0, then the unqualified ternary precursor is added to adjust the pH value to 2.0-2.5 for reacting for 2-3 hours, and then the first solid-liquid separation is carried out;
(7) adding a filter aid into the slurry after the reaction is finished, and adjusting the temperature to 80-90 ℃;
(8) the first solid-liquid separation is performed in a membrane filter press.
4. The high nickel matte extraction process of claim 3 wherein the filter aid comprises activated carbon and powdered charcoal:
preferably, 0.9-1.1kg of filter aid is added per cubic meter of slurry;
preferably, the activated carbon is coconut shell hard activated carbon, and the mass ratio of the coconut shell hard activated carbon to the charcoal powder is 1:0.5-1.5;
more preferably, the coconut shell hard activated carbon is waste activated carbon in the extraction and oil removal process, and the waste activated carbon is dried for 2-3 hours at 80-90 ℃ before being used;
preferably, the particle size of the filter aid is from 10 to 60 mesh.
5. The method for leaching the high nickel matte according to claim 1, wherein the first solid-liquid separation step also obtains low acid leaching residues, the low acid leaching residues are leached by normal pressure high acid, the normal pressure high acid leaching is to add acid to the low acid leaching residues until the acidity is 100-400g/L, the temperature is adjusted to 50-90 ℃ and a reducing agent is added for reaction, and the second solid-liquid separation is carried out after the reaction to obtain high acid leaching liquid;
preferably, the reducing agent is at least one of hydrogen peroxide, sodium sulfite and sodium thiosulfate;
preferably, the high acid leaching solution is returned to the normal pressure low acid leaching step to be mixed with the pretreated powder for pulping.
6. The method for leaching high nickel matte according to claim 1, wherein the low acid leaching solution is subjected to impurity removal to obtain an impurity-removed leaching solution;
preferably, the removing impurities includes: adding iron powder into the low-acid leaching solution to remove copper primarily, adding hydrogen peroxide to remove ferrous iron, heating to 80-95 ℃, adjusting the pH value to 3.8-4.2 to remove iron and aluminum, and adding sodium sulfide to remove copper deeply; then removing calcium, magnesium and zinc in the copper-removing leaching solution by adopting an extraction method, and removing lithium in the raffinate to obtain a impurity-removing leaching solution;
more preferably, after the temperature is raised to 80-95 ℃, firstly adding unqualified ternary precursor to adjust the pH to 3.0-3.5, and then adding sodium carbonate concentrate to adjust the pH to 3.8-4.2;
more preferably, the molar ratio of the iron powder to the copper ions in the low-acid leaching solution is 1:0.9-1.1.
7. A method for preparing a ternary cathode material precursor, which is characterized by comprising the step of performing hydrothermal synthesis by taking the leaching solution as a raw material according to any one of claims 1-6 to obtain the ternary cathode material precursor.
8. The method for producing a ternary positive electrode material precursor according to claim 7, wherein in the hydrothermal synthesis step, a metal salt is added to the leachate, and a ternary positive electrode material precursor having a predetermined composition is obtained by hydrothermal synthesis using a coprecipitation method.
9. A ternary cathode material precursor obtained by the method of claim 7 or 8.
10. A ternary cathode material prepared from the ternary cathode material precursor of any one of claims 7-9.
CN202310055115.XA 2023-02-03 2023-02-03 High nickel matte full-chain integrated leaching method, ternary positive electrode material precursor, preparation method and application thereof Pending CN116162785A (en)

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