Method for preparing ternary precursor solution from deep sea cobalt manganese oxide sulfuric acid leachate, ternary precursor, ternary positive electrode material and lithium ion battery

Abstract

The invention provides a method for preparing a ternary precursor solution from deep sea cobalt manganese oxide sulfuric acid leachate, a ternary precursor, a ternary positive electrode material and a lithium ion battery, and relates to the technical field of new energy. According to the method for preparing the ternary precursor solution from the deep sea cobalt-manganese oxide sulfuric acid leaching solution, the ternary precursor solution is prepared through a full extraction process that a first synergistic extraction system is used for removing impurities, a second synergistic extraction system is used for selectively recovering copper, and a third synergistic extraction system is used for co-extracting nickel, cobalt and manganese; according to the method, the ternary precursor is directly prepared from the deep-sea cobalt-manganese oxide sulfuric acid leaching solution, single nickel, cobalt and manganese metal salt does not need to be prepared through separation, the technological process is simplified, the production cost is reduced, and the ternary precursor solution conforming to battery production is obtained.

Description

Technical Field

[0001] The present application relates to the field of new energy technology, and in particular to a method for preparing a ternary precursor solution from a deep-sea cobalt-manganese oxide sulfuric acid leaching solution, a ternary precursor, a ternary positive electrode material, and a lithium-ion battery. Background Art

[0002] Land metal mineral resources are non-renewable. With the development and progress of society, the demand for metal mineral resources is increasing year by year. The easy-to-process and rich ores on land are becoming less and less, and their mining costs are getting higher and higher. Deep-sea cobalt-manganese oxides include polymetallic nodules and cobalt-rich crusts, which are rich in key metal resources such as cobalt, nickel, copper, and manganese. Their resources are extremely rich. They are an important replacement resource for land metals and a potential important source and security guarantee for my country's metal resources. However, deep-sea cobalt-manganese oxides are far away from land, deep in water, low in grade, complex in composition and mineral structure, high in mining and transportation costs, and there is no mature land mineral production process that can be directly copied and applied; therefore, how to achieve efficient and economic extraction of deep-sea cobalt-manganese oxides is the main driving force for the commercial development of deep-sea resources.

[0003] The ternary cathode material of lithium-ion power battery is generally synthesized by the co-precipitation of nickel, cobalt and manganese hydroxide (ternary precursor) and lithium salt. The ternary precursor is mainly nickel, cobalt and manganese soluble salts co-precipitated in a certain proportion to form a composite hydroxide Ni x Co y Mn (1-x-y) (OH)2 or oxide is an important raw material for battery positive electrode materials. At present, the preparation of ternary precursors mainly uses pure nickel, cobalt and manganese reagents as raw materials and prepares them into ternary precursors according to a certain ratio.

[0004] Deep-sea cobalt-manganese oxides are low-grade complex oxide ores, with the main valuable elements being cobalt, nickel, copper, and manganese, and the manganese content is much higher than that of laterite nickel ore, making it difficult to extract and separate using existing terrestrial mineral processes; its main metallurgical processes include reduction ammonia leaching, atmospheric pressure reduction sulfuric acid leaching, reduction smelting-leaching, matte smelting-leaching, etc. At present, the recycling of deep-sea cobalt-manganese oxide resources is mainly used to produce products such as electrolytic copper, electrolytic nickel, cobalt oxide, manganese concentrate or ferromanganese alloy. In the process of sulfuric acid leaching, in addition to the valuable metals cobalt, nickel, copper, and manganese leaching into the liquid phase, some iron, calcium, aluminum, zinc, magnesium, and rare elements also enter the solution. In particular, the manganese concentration in the solution is relatively high, and the obtained leachate has a complex composition and many elements of similar properties, which makes separation and purification difficult, resulting in a long process, complex process, and high production cost when producing single products of copper, nickel, cobalt, and manganese.

[0005] In addition, there is also a chemical precipitation-extraction combined process to recover nickel, cobalt and manganese. Although the chemical precipitation-extraction combined process is simpler than the preparation of a single nickel, cobalt and manganese product, the process flow is still relatively long, the chemical precipitation impurity removal rate is low, the operation is complicated, and the production cost is high. For example, the Chinese patent application for a method for preparing lithium battery positive electrode material precursors from seabed polymetallic nodules (patent application number CN201811084156.7) and a method for extracting valuable metals from seabed polymetallic nodules and co-producing lithium battery lithium battery positive electrode material precursors and titanium-doped positive electrode materials (patent application number CN201910059034.0) discloses a chemical precipitation-step-by-step extraction and impurity removal-extraction combined process, which has a long process flow and is relatively complicated to operate.

[0006] Therefore, combining the characteristics of deep-sea cobalt manganese oxide minerals and the requirements for the composition of the ternary precursor, the present invention aims to achieve full extraction from the deep-sea cobalt manganese polymetallic oxide leachate to prepare the ternary precursor solution in a short process without using chemical precipitation, thereby simplifying the process, reducing production costs, and increasing the value of deep-sea resources, which is crucial to the commercial development and application of deep-sea cobalt manganese oxide. Summary of the invention

[0007] The purpose of the present application is to provide a method for preparing a ternary precursor solution from a deep-sea cobalt manganese oxide sulfuric acid leaching solution, a ternary precursor, a ternary positive electrode material, and a lithium-ion battery, aiming to solve the problem of complex process flow and high cost in the existing deep-sea cobalt manganese oxide preparation of ternary precursors.

[0008] To achieve the above objectives, the present application provides a method for preparing a ternary precursor solution from a deep-sea cobalt-manganese oxide sulfuric acid leaching solution, comprising:

[0009] Extracting the deep-sea cobalt-manganese oxide sulfuric acid leaching solution with a first synergistic extraction system to remove iron, zinc, aluminum and calcium, thereby obtaining a loaded first organic phase and a first raffinate containing copper, nickel, cobalt and manganese;

[0010] Extracting copper from the first raffinate using a second co-extraction system to obtain a second organic phase loaded with copper and a second raffinate de-coppered;

[0011] co-extracting nickel, cobalt and manganese from the second raffinate using a third synergistic extraction system to obtain a loaded third organic phase and a third raffinate;

[0012] The loaded third organic phase is stripped with sulfuric acid to obtain the organic phase of the third synergistic extraction system and a ternary precursor solution containing nickel, cobalt and manganese sulfate.

[0013] In some embodiments, the first synergistic extraction system comprises: a first extractant, a first synergistic extraction agent, and a first diluent;

[0014] The first extractant is selected from P204; the first synergistic extractant is selected from one or two of trioctylphosphine oxide and trialkylphosphine oxide; the first diluent is sulfonated kerosene, solvent oil D70, solvent oil D80, solvent oil D100 or toluene.

[0015] In some embodiments, at least one of the following conditions is met:

[0016] A. the volume percentage concentration of the first extractant in the first synergistic extraction system is 5 to 10%;

[0017] B. the volume percentage concentration of the first synergistic agent in the first synergistic extraction system is 1 to 5%;

[0018] C. The phase ratio of the first synergistic extraction system is O / A=1:1-8;

[0019] D. The sulfuric acid concentration of the extraction solution of the first synergistic extraction system is 0.3-0.8 g / L;

[0020] E. The acidity of the extraction solution of the first synergistic extraction system is adjusted by using sodium carbonate.

[0021] In some embodiments, the second synergistic extraction system comprises: a second extractant, a second synergistic extraction agent, and a second diluent;

[0022] The second extractant is selected from the compound of hydroxyaldehyde oxime and hydroxyketoxime BK992; the second synergistic extractant is isooctyl alcohol; the second diluent is sulfonated kerosene, solvent oil D70, solvent oil D80, solvent oil D100 or toluene.

[0023] In some embodiments, at least one of the following conditions is met:

[0024] A. the volume percentage concentration of the second extractant in the second synergistic extraction system is 5 to 10%;

[0025] B. The volume percentage concentration of the second synergistic extraction agent in the second synergistic extraction system is 0.5-3%;

[0026] C. The phase ratio of the second synergistic extraction system is O / A=1:1-8;

[0027] D. The sulfuric acid concentration of the extraction solution of the second synergistic extraction system is 0.05-0.5 g / L;

[0028] E. The acidity of the extraction solution of the second synergistic extraction system is adjusted by using sodium carbonate.

[0029] In some embodiments, the third synergistic extraction system comprises: a third extractant, a third synergistic extraction agent, and a third diluent;

[0030] The third extractant is isomeric carboxylic acid SRS100 synthesized from high-branched fatty acid and neutral oil; the third synergistic extractant is isooctyl alcohol; and the third diluent is sulfonated kerosene, solvent oil D70, solvent oil D80, solvent oil D100 or toluene.

[0031] In some embodiments, at least one of the following conditions is met:

[0032] A. The volume percentage concentration of the third extractant in the third synergistic extraction system is 1 to 5%;

[0033] B. The volume percentage concentration of the third synergistic extraction agent in the third synergistic extraction system is 1 to 3%;

[0034] C. The phase ratio of the third synergistic extraction system is O / A=1:1-10;

[0035] D. the pH of the extraction solution of the third synergistic extraction system is 6.5-7.0;

[0036] E. The acidity of the extraction solution of the third synergistic extraction system is adjusted by using aqueous ammonia.

[0037] The present application also provides a ternary precursor, which is prepared by the method for preparing a ternary precursor solution from the above-mentioned deep-sea cobalt manganese oxide sulfuric acid leaching solution.

[0038] The present application also provides a ternary positive electrode material, which is prepared from the above-mentioned ternary precursor.

[0039] The present application also provides a lithium-ion battery, comprising the above-mentioned ternary positive electrode material.

[0040] Compared with the prior art, the beneficial effects of this application include:

[0041] The method for preparing a ternary precursor solution from a deep-sea cobalt manganese oxide sulfuric acid leaching solution provided in the present application adopts a full extraction process in which a first synergistic extraction system is used to remove impurities, a second synergistic extraction system is used to selectively recover copper, and a third synergistic extraction system is used to co-extract nickel, cobalt and manganese to prepare the ternary precursor solution. The method directly prepares the ternary precursor from the deep-sea cobalt manganese oxide sulfuric acid leaching solution without the need to separate and prepare single nickel, cobalt and manganese metal salts, thereby simplifying the process flow, reducing production costs, and obtaining a ternary precursor solution that meets the requirements of battery production. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present application and therefore should not be regarded as limiting the scope of the present application.

[0043] Figure 1A schematic flow chart of a method for preparing a ternary precursor solution from a deep-sea cobalt-manganese oxide sulfuric acid leaching solution of the present application. DETAILED DESCRIPTION

[0044] As used herein:

[0045] "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0046] The conjunction "consisting of excludes any unspecified element, step, or component. If used in a claim, this phrase renders the claim closed-ended so that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the subject matter, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0047] When an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described in this article, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range.

[0048] In these examples, parts and percentages are by mass unless otherwise indicated.

[0049] "Parts by mass" refers to the basic unit of measurement for expressing the mass ratio of multiple components. 1 part can represent any unit mass, such as 1g or 2.689g. If we say that the mass of component A is a parts and the mass of component B is b parts, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, indicating a multiple factor). It should not be misunderstood that, unlike the mass parts, the sum of the mass of all components is not limited to 100 parts.

[0050] "And / or" is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0051] This application provides a method for preparing a ternary precursor solution from a deep-sea cobalt-manganese oxide sulfuric acid leaching solution. Figure 1 ,include:

[0052] S100: The deep-sea cobalt-manganese oxide sulfuric acid leaching solution is extracted with a first synergistic extraction system to remove iron, zinc, aluminum and calcium, thereby obtaining a loaded first organic phase and a first raffinate containing copper, nickel, cobalt and manganese.

[0053] S200: extracting copper from the first raffinate using a second synergistic extraction system to obtain a second organic phase loaded with copper and a second raffinate decoppered.

[0054] S300: co-extracting nickel, cobalt and manganese from the second raffinate using a third synergistic extraction system to obtain a loaded third organic phase and a third raffinate.

[0055] S400: stripping the loaded third organic phase with sulfuric acid to obtain an organic phase of a third synergistic extraction system and a ternary precursor solution containing nickel, cobalt and manganese sulfate.

[0056] In step S100, the deep-sea cobalt manganese oxide includes polymetallic nodules and cobalt-rich crusts. The deep-sea cobalt manganese oxide sulfuric acid leaching solution refers to the sulfuric acid leaching solution after the polymetallic nodules and cobalt-rich crusts are crushed. The deep-sea cobalt manganese oxide sulfuric acid leaching solution usually contains Fe 2+ , Mn 2+ 、Co 2+ 、Ni 2+ , Cu 2+ 、Zn 2+ 、Al 3+ , Ca 2+ wait.

[0057] In some embodiments, the first synergistic extraction system comprises: a first extractant, a first synergistic extraction agent and a first diluent; the first extractant is selected from P204; the first synergistic extraction agent is selected from one or two of trioctylphosphine oxide and trialkylphosphine oxide; the first diluent is sulfonated kerosene, solvent oil D70, solvent oil D80, solvent oil D100 or toluene.

[0058] The extraction agent P204 alone can be used to extract and remove iron, but the removal effect on other impurities such as zinc, aluminum, and calcium is poor. The present application adopts a synergistic extraction system of P204 to extract and remove iron, zinc, aluminum, and calcium, which can extract iron, zinc, aluminum, and calcium in one step, thereby improving the impurity removal effect.

[0059] In some embodiments, the volume percentage concentration of the first extractant in the first synergistic extraction system is 5-10%, for example, it can be 5%, 6%, 7%, 8%, 9% or 10%; the volume percentage concentration of the first synergistic extraction agent in the first synergistic extraction system is 1-5%, for example, it can be 1%, 2%, 3%, 4% or 5%; in addition to the first extractant and the first synergistic extraction agent, the balance of the first synergistic extraction system is the first diluent; the phase ratio O / A of the first synergistic extraction system is 1:1-8, for example, it can be 1:1, or 1:2, or 1:3, or 1:4, or 1:5, or 1:6, or 1:7, or 1:8.

[0060] In some embodiments, the sulfuric acid concentration of the extraction solution of the first synergistic extraction system, i.e., the deep-sea cobalt manganese oxide sulfuric acid leaching solution, is 0.3-0.8 g / L, for example, it can be 0.3 g / L, 0.4 g / L, 0.5 g / L, 0.6 g / L, 0.7 g / L or 0.8 g / L; the acidity of the extraction solution of the first synergistic extraction system is adjusted by sodium carbonate.

[0061] In step S200, the second synergistic extraction system includes: a second extractant, a second synergistic extraction agent and a second diluent; the second extractant is selected from a compound of hydroxyaldehyde oxime and hydroxyketoxime BK992; the second synergistic extraction agent is isooctyl alcohol; the second diluent is sulfonated kerosene, solvent oil D70, solvent oil D80, solvent oil D100 or toluene.

[0062] In some embodiments, the volume percentage concentration of the second extractant in the second synergistic extraction system is 5-10%, for example, 5%, 6%, 7%, 8%, 9% or 10%; the volume percentage concentration of the second synergistic extraction agent in the second synergistic extraction system is 0.5-3%, for example, 0.5%, 1%, 2% or 3%; in addition to the second extractant and the second synergistic extraction agent, the balance of the second synergistic extraction system is the second diluent; the phase ratio O / A of the second synergistic extraction system is 1:1-8, for example, 1:1, or 1:2, or 1:3, or 1:4, or 1:5, or 1:6, or 1:7, or 1:8.

[0063] In some embodiments, the sulfuric acid concentration of the extraction solution of the second synergistic extraction system, i.e., the first raffinate, is 0.05-0.5 g / L, for example, 0.05 g / L, 0.1 g / L, 0.2 g / L, 0.3 g / L, 0.4 g / L or 0.5 g / L; the acidity of the extraction solution of the second synergistic extraction system is adjusted using sodium carbonate.

[0064] Wherein, the second organic phase is loaded with copper, and the second organic phase can be stripped with sulfuric acid, and the concentration of sulfuric acid is 150-180 g / L, for example, it can be 150 g / L, 160 g / L, 170 g / L or 180 g / L, and the ratio O / A is 1:1-8, for example, it can be 1:1, or 1:2, or 1:3, or 1:4, or 1:5, or 1:6, or 1:7, or 1:8, to obtain the organic phase of the second synergistic extraction system and the aqueous phase containing copper sulfate.

[0065] In step S300, the third synergistic extraction system comprises: a third extractant, a third synergistic extractant and a third diluent; the third extractant is an isomeric carboxylic acid SRS100 synthesized from high-branched fatty acids and neutral oil, wherein the extractant SRS100 is produced by Shell Chemical Company, and the total carbon number of the high-branched fatty acids is 15; the third synergistic extractant is isooctyl alcohol; and the third diluent is sulfonated kerosene.

[0066] In some embodiments, the volume percentage concentration of the third extractant in the third synergistic extraction system is 1-5%, for example, 1%, 2%, 3%, 4% or 5%; the volume percentage concentration of the third synergistic extraction agent in the third synergistic extraction system is 1-3%, for example, 1%, 2% or 3%; in addition to the third extractant and the third synergistic extraction agent, the balance of the third synergistic extraction system is the third diluent; the phase ratio O / A of the third synergistic extraction system is 1:1-10, for example, 1:1, or 1:2, or 1:3, or 1:4, or 1:5, or 1:6, or 1:7, or 1:8, or 1:9, or 1:10.

[0067] In some embodiments, the pH of the extraction solution of the third synergistic extraction system, ie, the second raffinate, is 6.5-7.0; and the acidity of the extraction solution of the third synergistic extraction system is adjusted by ammonia water.

[0068] In step S400, the concentration of sulfuric acid used in sulfuric acid stripping is 50-100 g / L, for example, 50 g / L, 60 g / L, 70 g / L, 80 g / L, 90 g / L or 100 g / L, compared with O / A=1:1-8, for example, 1:1, or 1:2, or 1:3, or 1:4, or 1:5, or 1:6, or 1:7, or 1:8.

[0069] In step S400, the total concentration of nickel, cobalt and manganese ions in the ternary precursor solution is 120-180 g / L, and the total concentration of metal impurities is not higher than 30 mg / L.

[0070] After step S400, the method may further include adjusting the molar ratio of nickel, cobalt and manganese in the ternary precursor solution containing nickel, cobalt and manganese sulfate with nickel sulfate, cobalt sulfate or manganese sulfate according to the aqueous phase composition to obtain a nickel, cobalt and manganese sulfate solution of the ternary precursor molar ratio, wherein the nickel sulfate, cobalt sulfate or manganese sulfate is analytically pure.

[0071] The method for preparing a ternary precursor solution from a deep-sea cobalt manganese oxide sulfuric acid leaching solution provided in the present application adopts a full extraction process in which a first synergistic extraction system is used to remove impurities, a second synergistic extraction system is used to selectively recover copper, and a third synergistic extraction system is used to co-extract nickel, cobalt and manganese to prepare the ternary precursor solution. The method directly prepares the ternary precursor from the deep-sea cobalt manganese oxide sulfuric acid leaching solution without the need to separate and prepare single nickel, cobalt and manganese metal salts or to use a chemical precipitation method to remove impurities, thereby simplifying the process flow, reducing production costs, and obtaining a ternary precursor solution that meets the requirements of battery production.

[0072] The present application also provides a ternary precursor, which is prepared by the method for preparing a ternary precursor from the above-mentioned deep-sea cobalt manganese oxide sulfuric acid leaching solution.

[0073] The present application also provides a ternary positive electrode material, which is prepared from the above-mentioned ternary precursor.

[0074] Specifically, the ternary cathode material can be prepared by mixing a lithium source with the above-mentioned ternary precursor and then sintering to obtain the ternary cathode material.

[0075] The molar ratio of Li in the lithium source to the total molar ratio of Ni, Co and Mn in the ternary precursor is 1 to 1.1:1; and the sintering temperature can be 700°C to 1000°C.

[0076] The present application also provides a lithium-ion battery, comprising the above-mentioned ternary positive electrode material.

[0077] The embodiments of the present application will be described in detail below in conjunction with specific examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If specific conditions are not specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0078] Example 1

[0079] Take 1L of deep-sea cobalt-manganese oxide sulfuric acid leaching solution (the solution composition is shown in Table 1, the same as in the following examples), use 6% P204 + 2% trioctylphosphine oxide + sulfonated kerosene, under the conditions of O / A = 1:1 and sulfuric acid concentration of 0.5g / L, to obtain a sulfate solution containing copper, nickel, cobalt and manganese; then use 6% BK992 + 2% isooctyl alcohol + sulfonated kerosene, under the conditions of O / A = 1:2 and sulfuric acid concentration of 0.1g / L. L conditions to extract copper to obtain copper extraction residual solution; the copper extraction residual solution is then co-extracted with 2% SRS100+2% 2-octanol+sulfonated kerosene under the conditions of O / A=1:8 and pH=7; the nickel-cobalt-manganese loaded organic phase is back-extracted with 80g / L sulfuric acid under the conditions of O / A=1:4 to obtain a nickel-cobalt-manganese sulfate ternary precursor solution with a total nickel-cobalt-manganese concentration of 126g / L and a total metal impurity concentration of 14mg / L.

[0080] Table 1 Composition of sulfuric acid leaching solution of deep-sea cobalt-manganese oxide

[0081] Element Ni Co Cu Mn Fe Al Zn Mg Ca <![CDATA[H + ]]> Concentration g / L 5.21 0.93 4.14 6.15 3.99 1.82 0.45 1.72 0.81 0.51

[0082] Example 2

[0083] 1L of deep-sea cobalt-manganese oxide sulfuric acid leaching solution was taken, and extracted with 8% P204+5% trialkylphosphine oxide+sulfonated kerosene at a relative ratio of O / A=1:3 and a sulfuric acid concentration of 0.8g / L to obtain a sulfate solution containing copper, nickel, cobalt and manganese; 8% BK992+0.5% isooctyl alcohol+sulfonated kerosene was then used to extract copper at a relative ratio of O / A=1:4 and a sulfuric acid concentration of 0.2g / L to obtain a copper extraction residual solution; 4% SRS100+1.5% sec-octanol+sulfonated kerosene was used to co-extract nickel, cobalt and manganese from the copper extraction residual solution at a relative ratio of O / A=1:10 and pH=6.5; the nickel-cobalt-manganese loaded organic phase was stripped with 80g / L sulfuric acid at a relative ratio of O / A=1:4 to obtain a nickel-cobalt-manganese sulfate ternary precursor solution with a total nickel-cobalt-manganese concentration of 121g / L and a total metal impurity concentration of 19mg / L.

[0084] Example 3

[0085] 1L of deep-sea cobalt-manganese oxide sulfuric acid leaching solution was taken, and extracted with 7% P204+3% trialkylphosphine oxide+sulfonated kerosene at a relative ratio of O / A=1:1 and a sulfuric acid concentration of 0.7g / L to obtain a sulfate solution containing copper, nickel, cobalt and manganese; 10% BK992+1% isooctyl alcohol+sulfonated kerosene was then used to extract copper at a relative ratio of O / A=1:8 and a sulfuric acid concentration of 0.5g / L to obtain a copper extraction residual solution; 5% SRS100+1% isooctyl alcohol+sulfonated kerosene was used to co-extract nickel, cobalt and manganese from the copper extraction residual solution at a relative ratio of O / A=1:5 and pH=6.7; the nickel-cobalt-manganese loaded organic phase was stripped with 70g / L sulfuric acid at a relative ratio of O / A=1:8 to obtain a nickel-cobalt-manganese sulfate ternary precursor solution with a total nickel-cobalt-manganese concentration of 152g / L and a total metal impurity concentration of 25mg / L.

[0086] Example 4

[0087] 1L of deep-sea cobalt-manganese oxide sulfuric acid leaching solution was taken, and extracted with 10% P204+1% trialkylphosphine oxide+sulfonated kerosene at a relative ratio of O / A=1:4 and a sulfuric acid concentration of 0.8g / L to obtain a sulfate solution containing copper, nickel, cobalt and manganese; 10% BK992+3% isooctyl alcohol+sulfonated kerosene was then used to extract copper at a relative ratio of O / A=1:5 and a sulfuric acid concentration of 0.5g / L to obtain a copper extraction residual solution; 5% SRS100+3% isooctyl alcohol+sulfonated kerosene was used to co-extract nickel, cobalt and manganese from the copper extraction residual solution at a relative ratio of O / A=1:7 and pH=6.6; the nickel-cobalt-manganese loaded organic phase was stripped with 80g / L sulfuric acid at a relative ratio of O / A=1:6 to obtain a nickel-cobalt-manganese sulfate ternary precursor solution with a total nickel-cobalt-manganese concentration of 165g / L and a total metal impurity concentration of 20mg / L.

[0088] Example 5

[0089] 1L of deep-sea cobalt-manganese oxide sulfuric acid leaching solution was taken and extracted with 10% P204 + sulfonated kerosene at a ratio of O / A = 1:4 and a sulfuric acid concentration of 0.8g / L to obtain a sulfate solution containing copper, nickel, cobalt and manganese, and the concentrations of iron, zinc, aluminum and calcium were reduced to 0.7g / L, 0.02g / L, 0.86g / L and 0.15g / L respectively; then 12.6% BK992 + sulfonated kerosene was used at a ratio of O / A = 1:5 and a sulfuric acid concentration of 0.5g / L. The copper extraction rate was 93.91% under the conditions, and the copper concentration in the raffinate was 0.14 g / L; the copper extraction raffinate was then treated with 5% SRS100 + sulfonated kerosene to co-extract nickel, cobalt and manganese under the conditions of relative O / A=1:7 and pH=6.6; the nickel, cobalt and manganese loaded organic phase was stripped with 80 g / L sulfuric acid under the conditions of relative O / A=1:6 to obtain a nickel, cobalt and manganese sulfate ternary precursor solution with a total nickel, cobalt and manganese concentration of 145 g / L and a total metal impurity concentration of 152 mg / L.

[0090] The impurity content of the nickel-cobalt-manganese sulfate ternary precursor solution obtained by using the P204+BK992+SRS100 extraction system alone is far more than 30 mg / L.

[0091] Example 6

[0092] 1L of deep-sea cobalt-manganese oxide sulfuric acid leaching solution was taken, and extracted with 10% P204+1% sec-octanol+sulfonated kerosene at a relative ratio of O / A=1:4 and a sulfuric acid concentration of 0.8g / L to obtain a sulfate solution containing copper, nickel, cobalt and manganese; 10% BK992+3% sec-octanol+sulfonated kerosene was then used to extract copper at a relative ratio of O / A=1:5 and a sulfuric acid concentration of 0.5g / L to obtain a copper extraction residual solution; 5% SRS100+3% sec-octanol+sulfonated kerosene was used to co-extract nickel, cobalt and manganese from the copper extraction residual solution at a relative ratio of O / A=1:7 and pH=6.6; the nickel-cobalt-manganese loaded organic phase was stripped with 80g / L sulfuric acid at a relative ratio of O / A=1:6 to obtain a nickel-cobalt-manganese sulfate ternary precursor solution with a total nickel-cobalt-manganese concentration of 152g / L and a total metal impurity concentration of 104mg / L.

[0093] When full extraction is performed using 2-octanol as a co-extractant, the impurity content in the obtained nickel-cobalt-manganese sulfate ternary precursor solution far exceeds 30 mg / L.

[0094] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

[0095] In addition, those skilled in the art will appreciate that, although some embodiments herein include certain features included in other embodiments but not other features, the combination of features of different embodiments is meant to be within the scope of the present application and form different embodiments. For example, in the above claims, any one of the claimed embodiments may be used in any combination. The information disclosed in this background technology section is intended only to deepen the understanding of the overall background technology of the present application and should not be regarded as an admission or in any form of implication that the information constitutes prior art known to those skilled in the art.

Claims

1. A method for preparing a ternary precursor solution from a deep-sea cobalt-manganese oxide sulfuric acid leaching solution, characterized in that: include: Extracting the deep-sea cobalt-manganese oxide sulfuric acid leaching solution with a first synergistic extraction system to remove iron, zinc, aluminum and calcium, thereby obtaining a loaded first organic phase and a first raffinate containing copper, nickel, cobalt and manganese; Extracting copper from the first raffinate using a second co-extraction system to obtain a second organic phase loaded with copper and a second raffinate de-coppered; co-extracting nickel, cobalt and manganese from the second raffinate using a third synergistic extraction system to obtain a loaded third organic phase and a third raffinate; The loaded third organic phase is stripped with sulfuric acid to obtain the organic phase of the third synergistic extraction system and a ternary precursor solution containing nickel, cobalt and manganese sulfate.

2. The method for preparing a ternary precursor solution from a deep-sea cobalt-manganese oxide sulfuric acid leaching solution according to claim 1, characterized in that: The first synergistic extraction system comprises: a first extractant, a first synergistic extraction agent and a first diluent; The first extractant is selected from P204; the first synergistic extractant is selected from one or two of trioctylphosphine oxide and trialkylphosphine oxide; the first diluent is sulfonated kerosene, solvent oil D70, solvent oil D80, solvent oil D100 or toluene.

3. The method for preparing a ternary precursor solution from a deep-sea cobalt-manganese oxide sulfuric acid leaching solution according to claim 2, characterized in that: At least one of the following conditions is met: A. the volume percentage concentration of the first extractant in the first synergistic extraction system is 5 to 10%; B. the volume percentage concentration of the first synergistic agent in the first synergistic extraction system is 1 to 5%; C. The phase ratio of the first synergistic extraction system is O / A=1:1-8; D. The sulfuric acid concentration of the extraction solution of the first synergistic extraction system is 0.3-0.8 g / L; E. The acidity of the extraction solution of the first synergistic extraction system is adjusted by using sodium carbonate.

4. The method for preparing a ternary precursor solution from a deep-sea cobalt-manganese oxide sulfuric acid leaching solution according to claim 1, characterized in that: The second synergistic extraction system comprises: a second extractant, a second synergistic extraction agent and a second diluent; The second extractant is selected from the compound of hydroxyaldehyde oxime and hydroxyketoxime BK992; the second synergistic extractant is isooctyl alcohol; the second diluent is sulfonated kerosene, solvent oil D70, solvent oil D80, solvent oil D100 or toluene.

5. The method for preparing a ternary precursor solution from a deep-sea cobalt-manganese oxide sulfuric acid leaching solution according to claim 4, characterized in that: At least one of the following conditions is met: A. the volume percentage concentration of the second extractant in the second synergistic extraction system is 5 to 10%; B. The volume percentage concentration of the second synergistic extraction agent in the second synergistic extraction system is 0.5-3%; C. The phase ratio of the second synergistic extraction system is O / A=1:1-8; D. The sulfuric acid concentration of the extraction solution of the second synergistic extraction system is 0.05-0.5 g / L; E. The acidity of the extraction solution of the second synergistic extraction system is adjusted by using sodium carbonate.

6. The method for preparing a ternary precursor solution from a deep-sea cobalt-manganese oxide sulfuric acid leaching solution according to claim 1, characterized in that: The third synergistic extraction system comprises: a third extractant, a third synergistic extraction agent and a third diluent; The third extractant is isomeric carboxylic acid SRS100 synthesized from high-branched fatty acid and neutral oil; the third synergistic extractant is isooctyl alcohol; and the third diluent is sulfonated kerosene, solvent oil D70, solvent oil D80, solvent oil D100 or toluene.

7. The method for preparing a ternary precursor solution from a deep-sea cobalt-manganese oxide sulfuric acid leaching solution according to claim 6, characterized in that: At least one of the following conditions is met: A. The volume percentage concentration of the third extractant in the third synergistic extraction system is 1 to 5%; B. The volume percentage concentration of the third synergistic extraction agent in the third synergistic extraction system is 1 to 3%; C. The phase ratio of the third synergistic extraction system is O / A=1:1-10; D. the pH of the extraction solution of the third synergistic extraction system is 6.5-7.0; E. The acidity of the extraction solution of the third synergistic extraction system is adjusted by using aqueous ammonia.

8. A ternary precursor, characterized in that: The solution is prepared by the method for preparing a ternary precursor solution from a sulfuric acid leaching solution of deep-sea cobalt manganese oxide as described in any one of claims 1 to 7.

9. A ternary positive electrode material, characterized in that: The ternary positive electrode material is prepared from the ternary precursor described in claim 8.

10. A lithium ion battery, characterized in that: Including the ternary positive electrode material as described in claim 9.

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