CN112209450A - Five-element precursor material and preparation method and application thereof - Google Patents

Five-element precursor material and preparation method and application thereof Download PDF

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CN112209450A
CN112209450A CN202011062739.7A CN202011062739A CN112209450A CN 112209450 A CN112209450 A CN 112209450A CN 202011062739 A CN202011062739 A CN 202011062739A CN 112209450 A CN112209450 A CN 112209450A
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solution
salt
equal
auxiliary metal
quinary
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张勇杰
万江涛
任海朋
张宁
李子郯
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Svolt Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention relates to a quinary precursor material and a preparation method and application thereof, wherein the preparation method comprises the steps of preparing a solution containing auxiliary metal salt and a complexing additive, mixing the auxiliary metal in the auxiliary metal salt, a precipitator solution and a mixed salt solution of nickel salt, cobalt salt and manganese salt, adjusting the pH value, and carrying out heating reaction to obtain the quinary precursor material; the auxiliary metal salt is compounded in the preparation process to obtain a first solution, which can effectively inhibit local segregation phenomenon, and for the auxiliary metal element with larger precipitation coefficient, a specific complexing additive is added to effectively reduce the precipitation coefficient and improve the consistency of the precipitation coefficient of each element, so that a five-element precursor material with uniform distribution of five elements, high sphericity, good dispersibility and concentrated particle size distribution is obtained; and the temperature of subsequent sintering is reduced, and the obtained quinary anode material has higher specific capacity.

Description

Five-element precursor material and preparation method and application thereof
Technical Field
The invention belongs to the field of battery materials, and relates to a five-element precursor material, and a preparation method and application thereof.
Background
The lithium ion battery plays an important role in daily life, the development of the new energy automobile industry puts new requirements on the lithium ion battery, and the improvement of the energy density and the cycle stability of the lithium ion battery is urgent. The nickel-cobalt-manganese ternary material is a common cathode material at present, and the preparation process generally comprises the following steps: (1) preparing a precursor; (2) and sintering the precursor. The ternary material has higher theoretical specific capacity, but the cycling stability and the safety of the ternary material are still to be improved. The quinary material is prepared by adding auxiliary elements such as W, Al, B, Ca, Zr, Ti, Mg, Mo, Ga, Ge and the like in the coprecipitation process on the basis of a nickel-cobalt-manganese ternary material, so that the specific capacity of the material is improved on the basis of keeping the cycling stability and the rate capability of the material;
the preparation method of the prior ternary precursor is mainly a coprecipitation method, a salt solution of soluble nickel, cobalt and manganese and a precipitator are reacted under the participation of a complexing agent to obtain precursor precipitate, and the precipitator mainly comprises the following steps: soluble carbonate or hydroxide, etc. and the complexing agent mainly includes ammonia water, ammonium bicarbonate, etc.
Due to the technical problem of precursor coprecipitation, the preparation method of the quinary material on the market at present generally comprises the following steps: firstly, preparing a common nickel-cobalt-manganese ternary material precursor by a coprecipitation method, and then adding other element compounds in the sintering process to prepare a five-element material; the method can cause that (1) elements such as W, Al, B, Ca, Zr, Ti, Mg, Mo, Ga, Ge and the like are unevenly distributed in a precursor, so that the material performance is poor, (2) the sintering temperature is higher, the energy consumption is higher, and (3) nano-grade auxiliary material mixing is required during sintering, so that the process is complex and the cost is higher. As for the coprecipitation technology of multiple elements, the precipitation coefficients of some elements such as tungsten, molybdenum, magnesium and the like are slightly lower than those of the ternary NCM, the precipitation coefficients of other elements such as aluminum, titanium, germanium and the like are much higher than those of the NCM, and the range of the precipitation coefficients of five elements after being combined is greatly expanded, so that the difficulty of coprecipitation of five elements is greatly increased, and the reaction difficulty is higher than that of coprecipitation of ternary or quaternary materials.
CN109987647A discloses a doped high-nickel ternary precursor and a preparation method thereof. The chemical formula of the doped high-nickel ternary precursor is as follows: nixCoyMnzMn(OH)2Wherein x + y + z is 1, x is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than 0 and less than 0.2, and n is more than 0 and less than 0.01; m is at least one selected from Zr, Ce, V, Cr, Sr, Mo, Sc, La, P, Nb, Y and Ga. The preparation method of the doped high-nickel ternary precursor comprises the following steps: firstly, preparing an undoped high-nickel ternary precursor, then adding M, and continuing to react to prepare a doped high-nickel ternary precursor; CN106910873A discloses a method for doping Sr and H3BO3LiNi of (2)0.5Co0.2Mn0.3O2The preparation method of the cathode material comprises the following steps: step one, a battery-grade ternary precursor Ni0.5Co0.2Mn0.3(OH)2And battery grade lithium carbonate Li2CO3In the theoretical stoichiometric ratio m (Li)+)/m(Ni2++Co2++Mn2+) 1.04: 1, mixing the materials according to Sr and H3BO3The doping ratio of (A) is analytically pure Sr (OH)2·8H2O and analytically pure boric acid H3BO3(ii) a Adding the prepared raw materials into a three-dimensional mixer, and adding mixing balls for mixing; step three, placing the uniformly mixed materials in a box-type atmosphere furnace, heating to 300 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 1 h; then heating to 600 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 1 h; then heating to 950 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4 hours; cooling to room temperature after sintering to prepare the doped Sr and H3BO3Lithium ion battery LiNi0.5Co0.2Mn0.3O2A ternary positive electrode material; the five-membered anode material obtained by the method has uneven distribution of doping elements, thereby affecting the material performance.
Therefore, the development of the preparation method of the quinary precursor material, which can effectively improve the distribution uniformity of the quinary element in the quinary precursor material and further improve the specific capacity of the quinary material, is still significant.
Disclosure of Invention
The invention aims to provide a quinary precursor material and a preparation method and application thereof, wherein the preparation method comprises the steps of preparing a solution containing an auxiliary metal salt and a complexing additive, mixing the solution with a precipitator solution and a mixed salt solution containing a nickel salt, a cobalt salt and a manganese salt, adjusting the pH value, and carrying out a heating reaction to obtain the quinary precursor material; the auxiliary metal salt is prepared into the first solution by a compounding method in the preparation process, the first solution can effectively inhibit local segregation phenomenon existing after the auxiliary metal salt is respectively prepared and added into a reaction system, and for the auxiliary metal element with larger precipitation coefficient, the specific complexing additive is added to effectively reduce the precipitation coefficient and improve the consistency of the precipitation coefficient of each element, thereby being beneficial to obtaining a quinary precursor material with uniform distribution of five elements, high sphericity, good dispersibility and concentrated particle size distribution; the five-element anode material obtained by the method has higher specific capacity.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a pentabasic precursor material, the method comprising the steps of:
(1) preparing a first solution comprising an auxiliary metal salt and a complexing additive; the auxiliary metal in the auxiliary metal salt comprises a metal with a precipitation coefficient greater than that of Ni, Co and Mn;
(2) preparing a second solution containing nickel salt, cobalt salt and manganese salt;
(3) and mixing the first solution, the precipitant solution and the second solution, adjusting the pH value, and heating for reaction to obtain the five-element precursor material.
The preparation method of the traditional five-element precursor material generally adopts the steps of firstly preparing a nickel-cobalt-manganese ternary precursor and then adding auxiliary metal elements in the sintering process; the method has the defects of uneven dispersion of auxiliary metal elements in the ternary precursor, poorer material performance, high sintering temperature, large energy consumption, complex working procedures and higher cost because nanoscale auxiliary material mixing is required in the sintering process; the existing multi-element coprecipitation technology has the problems of large precipitation coefficient range of five elements and large coprecipitation difficulty.
In order to solve the technical problems, the preparation method of the five-element precursor material adopts compounding to obtain a solution containing two auxiliary metal salts and a complexing additive, mixes the solution with a mixed salt solution of a precipitator solution, a nickel salt, a cobalt salt and a manganese salt, adjusts the pH value, and then carries out heating reaction to obtain the five-element precursor material; in the preparation method, the auxiliary metal salt solution is prepared in a compounding manner, compared with the respective independent preparation, the local segregation phenomenon can be effectively avoided, in addition, in order to adjust the precipitation coefficients of the five metals, for the auxiliary metals (including aluminum, titanium, germanium and the like) with larger precipitation coefficients, specific complexing additives are added into the auxiliary metal salt solution, the precipitation coefficients of the auxiliary metals can be effectively reduced, the range of the precipitation coefficients of the five metals in the solution is further narrowed, and the five-element precursor material with uniform distribution of the five elements, high sphericity, good dispersibility and concentrated particle size distribution can be obtained; the five-element anode material obtained by the method has higher specific capacity.
Experimental research shows that in the process of preparing the five-element anode material by subsequent sintering, the sintering temperature required by the five-element precursor material obtained by the method is obviously reduced, and the required temperature is reduced by more than 50 ℃ compared with the prior art (namely, the ternary precursor is prepared and then mixed with auxiliary metal for sintering).
The quinary anode material obtained from the quinary precursor material has a better quinary synergistic effect, and the specific capacity of the quinary anode material is improved by 5-10 mAh/g compared with that of a quinary anode material obtained in the prior art on the basis of keeping the cycle performance and the rate performance. For example, the auxiliary elements are aluminum and tungsten, the five-element anode material obtained by the method has 0.1C discharge gram capacity of 195-201 mAh/g and 1C discharge gram capacity of 178-184 mAh/g, while the common material obtained by the traditional method (firstly carrying out coprecipitation to obtain an NCM precursor and adding doping metal during sintering) has 0.1C discharge gram capacity of only about 192mAh/g and 1C discharge gram capacity of only about 175 mAh/g; if the auxiliary elements are aluminum and boron, the 0.1C discharge gram capacity of the quinary anode material obtained by the method can reach 205-210 mAh/g, the 1C discharge gram capacity can reach 185-192 mAh/g, while the 0.1C discharge gram capacity of the common material obtained by the traditional method can only reach about 201mAh/g, and the 1C discharge gram capacity can only reach 175-182 mAh/g.
The quinary precursor material prepared by the method of the invention does not need to introduce nano-grade auxiliary materials in the sintering process, and the cost is obviously reduced.
The auxiliary metal in the auxiliary metal salt is selected from any two of W, Al, B, Ca, Zr, Ti, Mg, Mo, Ga and Ge;
preferably, the auxiliary metal in the auxiliary metal salt is selected from any one of Al, Ti, Ge, Zr, Ga and any one of W, Mo, Mg, B, Ca.
Preferably, the complexing additive is selected from at least one of an amino acid, a polypeptide, and sulfamic acid.
Preferably, the amino acid is selected from amino acids having a basic isoelectric point; preferably lysine and/or arginine.
The invention adopts the amino acid with basic isoelectric point as the complexing additive, has better chelating effect under the alkaline condition, and is convenient to reduce the precipitation coefficient range of the auxiliary metal and the nickel-cobalt-manganese through the complexing ability of the complexing additive and the precipitation coefficient of the metal under the conditions of the isoelectric point of the amino acid and the configuration concentration, thereby improving the coprecipitation effect and obtaining the quinary precursor material with uniform distribution of five elements, high sphericity, good dispersibility and concentrated particle size distribution.
And the addition of the complexing additive can reduce the precipitation coefficient of auxiliary metals (such as Al, Ti, Ge and the like) with larger precipitation coefficient, reduce the difference between the precipitation coefficients of the auxiliary metals and the precipitation coefficients of nickel, cobalt and manganese, further reduce the difficulty of coprecipitation and improve the element dispersion uniformity of a coprecipitation product.
Preferably, the concentration of the complexing additive in the first solution is 0.02-2 mol/L; for example, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.3mol/L, 1.5mol/L, 1.7mol/L, or 1.9mol/L, etc., preferably 0.05 to 1.5 mol/L.
The concentration of the complexing additive is controlled in the range, so that the difference of the precipitation coefficients of the auxiliary metal with larger precipitation coefficient and the nickel, the cobalt and the manganese in a reaction system is favorably reduced, the coprecipitation difficulty is further reduced, the coprecipitation effect is improved, and the five-element precursor material with uniform distribution of five elements and high sphericity is favorably obtained.
Preferably, the nickel salt comprises nickel sulfate.
Preferably, the cobalt salt comprises cobalt sulfate.
Preferably, the manganese salt comprises manganese sulfate.
Preferably, the auxiliary metal salt is selected from soluble salts of the auxiliary metal, such as aluminium sulphate, sodium metaaluminate, sodium borate or magnesium sulphate and the like.
Preferably, the solvents of the first solution, the second solution and the precipitant solution are all selected from water.
Preferably, the concentration of the auxiliary metal salt in the first solution is 1-100 g/L, such as 5g/L, 10g/L, 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L or 90 g/L.
Preferably, the sum of the concentrations of the nickel salt, the cobalt salt and the manganese salt in the second solution is 80-400 g/L, such as 100g/L, 150g/L, 200g/L, 250g/L, 300g/L or 350 g/L.
Preferably, the concentration of the hydroxide (such as soluble hydroxide like sodium hydroxide and potassium hydroxide) in the precipitant solution is 100-300 g/L, such as 150g/L, 200g/L or 250 g/L.
Preferably, the concentration of ammonia in the precipitant solution is 0.3-1.2 mol/L, such as 0.5mol/L, 0.7mol/L, 0.9mol/L, or 1.1 mol/L. Preferably 0.5 to 0.8 mol/L.
Preferably, the pH is adjusted to 10-12, such as 10.5, 11 or 11.5.
The precipitator solution comprises sodium hydroxide and ammonia, the concentration of the ammonia is controlled within the range, after the precipitator solution is mixed with the first solution and the second solution, the pH value is adjusted to 10-12, and the specific ammonia concentration is controlled at the same time, so that the precipitation coefficient of auxiliary metals (such as tungsten, molybdenum, magnesium and the like) with lower precipitation coefficient is favorably improved, the difference between the precipitation coefficient and nickel, cobalt and manganese is further reduced, the range of the precipitation coefficient of the metals in the reaction solution is narrowed, the coprecipitation difficulty is further reduced, and the five-element precursor material with uniform distribution of five elements, high sphericity, good dispersibility and concentrated particle size distribution is obtained.
For the auxiliary metal with the precipitation coefficient lower than that of nickel, cobalt and manganese, the research of the invention finds that the pH value is increased within the range, the stirring speed is increased, the precipitation coefficient can be effectively increased, the difference of the metal precipitation coefficients in the reaction solution is further reduced, the uniform coprecipitation effect is further realized, and the electrochemical performance of the material is improved.
Preferably, the temperature of the heating reaction is 65 to 80 ℃, such as 68 ℃, 70 ℃, 72 ℃, 75 ℃ or 78 ℃.
Preferably, stirring is carried out in the heating reaction process, and the stirring speed is preferably 500-1000 rpm; for example 600rpm, 700rpm, 800rpm or 900rpm, etc.
For the auxiliary metal with lower precipitation coefficient, the research of the invention finds that the precipitation coefficient can be effectively improved under the stirring speed, the effect of reducing the precipitation coefficient range of the metal in the reaction solution is achieved, the coprecipitation effect is further improved, and the five-element precursor material with uniform distribution of five elements, high sphericity, good dispersibility and concentrated particle size distribution is obtained.
Preferably, the heating reaction time is 5-150 h, such as 10h, 30h, 50h, 70h, 90h, 110h or 130h, etc., preferably 50-120 h.
Preferably, the solid content of the slurry obtained by the heating reaction is 50-1000 g/L, such as 100g/L, 200g/L, 300g/L, 400g/L, 500g/L, 600g/L, 700g/L, 800g/L or 900 g/L.
Preferably, aging is further included after the heating reaction is finished.
Preferably, the aging process is accompanied by stirring, preferably at a stirring speed of 200-300 rpm, such as 220rpm, 240rpm, 260rpm, 280rpm, or the like.
Preferably, the aging time is 0.5 to 5h, such as 1h, 2h, 3h, 4h, or the like.
Preferably, the aging process further comprises the steps of demagnetization, solid-liquid separation, washing, drying and screening.
Preferably, the washing is water washing.
As a preferable technical scheme of the invention, the preparation method of the five-element precursor material comprises the following steps:
(a) preparing a first solution comprising an auxiliary metal salt and a complexing additive; wherein the concentration of the complexing additive is 0.02-2 mol/L, and the concentration of the auxiliary metal salt is 1-100 g/L;
(b) preparing a second solution containing nickel salt, cobalt salt and manganese salt; wherein the sum of the concentrations of the nickel salt, the cobalt salt and the manganese salt is 80-400 g/L;
(c) preparing a precipitant solution, wherein the concentration of sodium hydroxide is 100-300 g/L, and the concentration of ammonia is 0.3-1.2 mol/L;
(d) mixing the first solution, the precipitant solution and the second solution, adjusting the pH value to 10-12, and heating and reacting for 5-150 h under the conditions that the stirring speed is 500-1000 rpm and the temperature is 65-80 ℃; obtaining slurry with solid content of 50-1000 g/L;
(e) aging the slurry obtained in the step (d) in an aging kettle at a stirring speed of 200-300 rpm for 0.5-5 h;
(f) and (e) demagnetizing the aging product obtained in the step (e), carrying out solid-liquid separation, washing with water, and drying to obtain the five-element precursor material.
In a second aspect, the invention provides a five-element precursor material prepared by the method of the first aspect, wherein the molecular general formula of the five-element precursor is NiaCobMncXdYe(OH)2Wherein a is between 50% and 90%, such as 55%, 60%, 65%, 70%, 75%, 80% or 85%, etc., 0%<b.ltoreq.10%, e.g. 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc., c.ltoreq.3% or more and c.ltoreq.30%, examplesE.g., 5%, 10%, 15%, 20%, or 25%, etc., 0.1% d.ltoreq.3%, e.g., 0.5%, 1%, 1.5%, 2%, or 2.5%, etc., 0.1% e.ltoreq.3%, e.g., 0.5%, 1%, 1.5%, 2%, or 2.5%, etc., a + b + c + d + e is 1, X, Y is two different auxiliary metals.
Preferably, the particle size D50 of the quinary precursor material is 3-12 μm, such as 5 μm, 8 μm or 10 μm.
In a third aspect, the invention provides a preparation method of a quinary positive electrode material, which comprises the following steps: and mixing the quinary precursor material and lithium salt, and sintering to obtain the quinary anode material.
Preferably, the sintering method comprises a first sintering and a second sintering in sequence.
Preferably, the temperature of the first sintering is 450-600 ℃, such as 480 ℃, 500 ℃, 520 ℃, 550 ℃ or 580 ℃, and the time is 4-6 h, such as 4.5h, 5h or 5.5 h.
Preferably, the temperature of the second sintering is 700-850 ℃, such as 750 ℃ or 800 ℃, and the time is 15-25 h, such as 18h, 20h, 22h or 24 h.
The preparation method of the quinary anode material adopts the quinary precursor material as described in the first aspect, the sintering temperature is low, nano-scale auxiliary materials are not required to be added, the energy consumption and the cost are obviously reduced, five elements in the quinary anode material are uniformly distributed, and the specific capacity of the quinary anode material is 5-10 gAh/g higher than that of a common material (namely the quinary anode material prepared by firstly preparing the ternary nickel-cobalt-manganese precursor and then mixing the ternary nickel-cobalt-manganese precursor with the nano-scale auxiliary metal salt) on the basis of keeping the cycle performance and the rate performance.
In a fourth aspect, the invention provides a five-element cathode material, which is prepared by the method in the third aspect.
Five elements in the quinary anode material are uniformly distributed, and the specific capacity of the quinary anode material is 5-10 gAh/g higher than that of a common material (namely the quinary anode material prepared by preparing a ternary nickel-cobalt-manganese precursor and mixing a nanoscale auxiliary metal salt) on the basis of keeping the cycle performance and the rate performance.
Preferably, the molecular general formula of the five-membered cathode material is Li (Ni)aCobMncXdYe)O2Wherein a is more than or equal to 0.5 and less than or equal to 0.9 and 0<b is not more than 0.1, c is not less than 0.03 and not more than 0.3, d is not less than 0.0001 and not more than 0.03, e is not less than 0.0001 and not more than 0.03, a + b + c + d + e is 1, X, Y is auxiliary metal, X, Y is two different auxiliary metals.
Preferably, the quinary positive electrode material is used for a lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method of the five-element precursor material, the auxiliary metal salt is added in the form of the compound solution, so that the local segregation phenomenon existing in the respective preparation and addition is avoided, the uniformity of element distribution is improved, the coprecipitation effect is improved, and the coprecipitation difficulty is reduced;
(2) according to the preparation method of the five-element precursor material, the specific complexing additive is added into the auxiliary metal salt solution for the auxiliary metal with a larger precipitation coefficient, so that the precipitation coefficient is reduced, the range of the metal precipitation coefficient in the reaction solution is further narrowed, and the five-element precursor material with uniform distribution of five elements, high sphericity, good dispersibility and concentrated particle size distribution is favorably obtained;
(3) the five-element precursor material has lower sintering temperature in the preparation process of preparing the five-element anode material, does not need to add nano-grade auxiliary materials, and reduces energy consumption and cost under the name of name;
(4) the quinary anode material obtained by sintering the quinary precursor material has the specific capacity 5-10 gAh/g higher than that of a common material on the basis of keeping the cycle performance and the rate capability.
Drawings
FIG. 1 is an electron micrograph of a five-membered precursor material obtained in example 1 of the present invention;
FIG. 2 is a graph of the distribution of elements Mn, Co, Ni, Al and W within the box areas of FIG. 1;
FIG. 3 is a graph of the elemental distribution of Mn within the box region of FIG. 1;
FIG. 4 is a graph of the elemental distribution of Co within the box region of FIG. 1;
FIG. 5 is a diagram of the distribution of elements of Ni within the box area of FIG. 1;
FIG. 6 is a graph of elemental distribution of Al within the box region of FIG. 1;
fig. 7 is a diagram of the distribution of elements of W within the box area of fig. 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the quinary precursor material comprises the following steps:
(1) preparing a first solution: preparing an auxiliary metal salt solution with the molar ratio of aluminum to tungsten elements being 2:1, wherein the concentration is 40g/L, soluble salt raw materials are sodium metaaluminate and sodium tungstate respectively, a proper amount of lysine is added as a complexing additive, the concentration is 0.05mol/L, and the precipitation coefficient of aluminum is reduced;
(2) preparing a second solution: preparing a solution with the molar ratio of nickel, cobalt and manganese elements of 76.1:7.1:16.8 by using pure water, and adjusting the concentration to 400g/L, wherein nickel salt, cobalt salt and manganese salt are respectively selected from nickel sulfate, cobalt sulfate and manganese sulfate;
(3) preparing a precipitant solution, wherein the concentration of sodium hydroxide is 200g/L, the concentration of ammonia is 0.6mol/L, and the raw materials are sodium hydroxide and ammonia water;
(4) simultaneously adding the first solution, the second solution and the precipitant solution into a reaction kettle, controlling the rotation speed to be 600rpm and the temperature to be 70 ℃, adjusting the flow rates of the three solutions, controlling the pH of the system to be 11.1, reacting for 100 hours, aging for 2 hours after the reaction is finished, and stirring the stirring speed of the aging kettle to be 300 rpm; in the reaction process, a laser particle sizer can be used for detecting particle size distribution, and meanwhile, the solid content of the monitoring system overflows within a standard range;
(5) demagnetizing the aged feed liquid, performing solid-liquid separation, and washing with 1 time of pure water at 80 ℃; and drying the washed solid material to obtain the five-element precursor.
The five-membered precursor prepared in this example has the chemical formula [ Ni ]0.75Co0.07Mn0.165Al0.01W0.005](OH)2Particle diameter D50＝3μm。
The preparation method of the quinary anode material comprises the following steps:
fully mixing lithium hydroxide with the quinary precursor material, wherein the lithium hydroxide is 0.06 wt% more than the theoretical amount, calcining for 6 hours at 500 ℃ in air atmosphere, crushing and secondary sintering at 700 ℃ for 18 hours to generate the quinary anode material Li [ Ni ]0.75Co0.07Mn0.165Al0.01W0.005]O2。
An electron microscope image of the five-element precursor material obtained in the embodiment is shown in fig. 1, and it can be seen that the five-element precursor material has high sphericity, uniform dispersion and concentrated particle size distribution; wherein the elemental distribution plots are shown in FIGS. 2-7; it can be seen that the elements in the five-membered precursor material are uniformly distributed.
Example 2
The preparation method of the five-element precursor material comprises the following steps:
(1) preparing a first solution: preparing an auxiliary metal salt solution with the molar ratio of aluminum to boron being 5:4, wherein the concentration is 40g/L, soluble salt raw materials are sodium metaaluminate and sodium borate respectively, a proper amount of sulfamic acid is added to be used as a complexing additive, and the concentration is 0.1mol/L to reduce the precipitation coefficient of aluminum;
(2) preparing a second solution: preparing a solution with the molar ratio of nickel, cobalt and manganese elements being 79.4:8.1:12.5, and adjusting the concentration to 300g/L, wherein the raw materials of soluble nickel, cobalt and manganese are nickel sulfate, cobalt sulfate and manganese sulfate respectively;
(3) preparing a precipitant solution: the concentration of sodium hydroxide is 200g/L, the concentration of ammonia is 0.6mol/L, wherein the raw materials are sodium hydroxide and ammonia water;
(4) adding the three solutions into a reaction kettle at the same time, controlling the rotating speed to be 500rpm and the temperature to be 75 ℃, adjusting the flow of the three solutions, controlling the pH of the system to be 11, controlling the reaction time to be 80 hours, aging for 2 hours after the reaction is finished, and controlling the stirring speed of the aging kettle to be 200 rpm;
in the reaction process, a laser particle sizer can be used for detecting particle size distribution, and meanwhile, the solid content of the monitoring system overflows within a standard range;
(5) demagnetizing the aged feed liquid, performing solid-liquid separation, and washing with 1 time of pure water at 80 ℃; drying the washed solid material to obtain a five-element precursor material;
the five-membered precursor prepared in this example has the chemical formula [ Ni ]0.78Co0.08Mn0.122Al0.01B0.008](OH)2. Particle diameter D50＝5μm。
The preparation method of the quinary anode material comprises the following steps:
fully mixing lithium hydroxide with the quinary precursor material, wherein the lithium hydroxide is 0.06 wt% more than the theoretical amount, calcining for 5 hours at 500 ℃ in air atmosphere, crushing and secondary sintering at 750 ℃ for 20 hours to generate the quinary anode material Li [ Ni ]0.78Co0.08Mn0.122Al0.01B0.008]O2。
Example 3
This example is different from example 1 in that sodium metaaluminate and sodium tungstate in the auxiliary metal salt solution were replaced with titanium sulfate and sodium molybdate, respectively, the concentration of the auxiliary metal salt was replaced with 80g/L, the concentration of the complexing additive was replaced with 1mol/L, and other parameters and conditions were exactly the same as in example 1.
Example 4
This example differs from example 1 in that an equimolar amount of complexing additive was replaced with arginine and the other parameters and conditions were exactly the same as in example 1.
Example 5
This example differs from example 1 in that the temperature of the heating reaction was replaced by 60 ℃ and the other parameters and conditions were exactly the same as in example 1.
Example 6
This example differs from example 1 in that the temperature of the heating reaction was replaced by 85 ℃ and the other parameters and conditions were exactly the same as in example 1.
Example 7
This example differs from example 1 in that the concentration of complexing additive is 2mol/L, and the other parameters and conditions are exactly the same as in example 1.
Example 8
This example differs from example 1 in that the concentration of complexing additive is 1.5mol/L, and the other parameters and conditions are exactly the same as in example 1.
Comparative example 1
The comparative example differs from example 1 only in that the method for producing the five-membered positive electrode material comprises: and mixing the second solution with a precipitant solution, heating for reaction to obtain a nickel-cobalt-manganese ternary precursor, mixing the nickel-cobalt-manganese ternary precursor with an auxiliary metal salt, ball-milling and sintering, wherein the sintering method comprises the steps of calcining for 10 hours at the temperature of 600 ℃ in an air atmosphere, crushing and sintering for 20 hours at the temperature of 800 ℃ to obtain the quinary anode material.
Comparative example 2
This comparative example differs from example 1 only in that no complexing additive was added to the first solution and the other parameters and conditions were exactly the same as in example 1.
Comparative example 3
This comparative example differs from example 2 only in that no complexing additive was added to the first solution and the other parameters and conditions were exactly the same as in example 2.
Comparative example 4
This comparative example differs from example 3 only in that no complexing additive was added to the first solution and the other parameters and conditions were exactly the same as in example 3.
And (3) performance testing:
mixing the five-membered positive electrode materials obtained in the examples and the comparative examples with SP (carbon black conductive agent) and PVDF (polyvinylidene fluoride), pulping and stirring for several hours by using NMP (N-methyl pyrrolidone) as a solvent to prepare a lithium ion half battery, and performing charge and discharge tests at 3.0-4.3V by using a blue tester to obtain the discharge gram capacity of the half battery at 0.1C and 1.0C and the capacity retention rate of 50 cycles;
the above test results are shown in table 1;
TABLE 1
Figure BDA0002712856590000141
Figure BDA0002712856590000151
As can be seen from the table 1, on the basis of keeping the cycle performance and the rate performance, the specific capacity of the quinary anode material prepared by the method is improved by 5-10 mAh/g compared with that of the material in the comparative example;
compared with the examples 1 and 4, the preparation method disclosed by the invention has the advantages that the amino acid is used as the complexing additive, so that the precipitation coefficient of metal with a larger precipitation coefficient can be effectively reduced, the uniformity of elements in a coprecipitation product is improved, and the electrochemical performance of the material is improved.
Compared with the examples 1 and 5-6, the reaction process of the preparation method disclosed by the invention is carried out at 65-80 ℃, so that the range of the precipitation coefficient of metal ions in a reaction solution is favorably narrowed, the coprecipitation effect is further improved, and the specific capacity of the material is improved.
Compared with the examples 1 and 7-8, the concentration of the complexing additive in the preparation method is in the range of 0.02-2 mol/L, and the complexing additive can effectively reduce the precipitation coefficient of the auxiliary metal with larger precipitation coefficient, so that the range of the precipitation coefficient in the reaction solution is reduced; and further preferably, the concentration of the complexing additive is 0.05-1.5 mol/L.
It can be seen from the comparison of example 1 and comparative example 1 that the quinary precursor material prepared by the method of the present invention requires lower sintering temperature in the process of preparing the quinary anode material, the sintering temperature is reduced by more than 50 ℃, the energy consumption is greatly reduced, and the preparation methods of comparative examples 1 and 2 have the problems of uneven element distribution and insufficient specific capacity.
Comparing example 1 with comparative example 2, example 2 with comparative example 3, and example 3 with comparative example 4, respectively, it can be seen that, without adding the complexing additive, the auxiliary metal with a large precipitation coefficient in the reaction solution cannot be uniformly precipitated with nickel, cobalt, and manganese, and five elements in the obtained product are not uniformly distributed, so that the specific capacity of the obtained product is poor.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A method for preparing a pentabasic precursor material, comprising the steps of:
(1) preparing a first solution comprising an auxiliary metal salt and a complexing additive; the auxiliary metal in the auxiliary metal salt comprises a metal with a precipitation coefficient greater than that of Ni, Co and Mn;
(2) preparing a second solution containing nickel salt, cobalt salt and manganese salt;
(3) and mixing the first solution, the precipitant solution and the second solution, adjusting the pH value, and heating for reaction to obtain the five-element precursor material.
2. The production method according to claim 1, wherein the auxiliary metal in the auxiliary metal salt is selected from any two of Al, Ti, Ge, Zr, and Ga;
preferably, the auxiliary metal in the auxiliary metal salt is selected from any one of metals having a precipitation coefficient greater than Ni, Co and Mn, and any one of W, Mo, Mg and B; preferably, the complexing additive is selected from at least one of an amino acid, a polypeptide, and sulfamic acid;
preferably, the amino acid is selected from amino acids having a basic isoelectric point; preferably lysine and/or arginine.
3. The method according to claim 1 or 2, wherein the concentration of the complexing additive in the first solution is 0.02 to 2 mol/L; preferably 0.05-1.5 mol/L;
preferably, the concentration of the auxiliary metal salt in the first solution is 1-100 g/L.
4. The method according to any one of claims 1 to 3, wherein the sum of the concentrations of the nickel salt, the cobalt salt and the manganese salt in the second solution is 80 to 400 g/L.
5. The method according to any one of claims 1 to 4, wherein the concentration of the hydroxide in the precipitant solution is 100 to 300 g/L;
preferably, the concentration of ammonia in the precipitant solution is 0.3-1.2 mol/L;
preferably, the pH value is adjusted to 10-12;
preferably, the temperature of the heating reaction is 65-80 ℃;
preferably, stirring is carried out in the heating reaction process, and the stirring speed is preferably 500-1000 rpm;
preferably, the heating reaction time is 5-150 h;
preferably, the solid content of the slurry obtained by the heating reaction is 50-1000 g/L.
6. The production method according to any one of claims 1 to 5, further comprising aging after the completion of the heating reaction;
preferably, the aging process is accompanied by stirring, and the stirring speed is preferably 200-300 rpm;
preferably, the aging time is 0.5-5 h;
preferably, the aging process further comprises the steps of demagnetization, solid-liquid separation, washing, drying and screening;
preferably, the washing is water washing.
7. The method of any one of claims 1 to 6, wherein the method comprises the steps of:
(a) preparing a first solution comprising an auxiliary metal salt and a complexing additive; wherein the concentration of the complexing additive is 0.02-2 mol/L, and the concentration of the auxiliary metal salt is 1-100 g/L;
(b) preparing a second solution containing nickel salt, cobalt salt and manganese salt; wherein the sum of the concentrations of the nickel salt, the cobalt salt and the manganese salt is 80-400 g/L;
(c) preparing a precipitant solution, wherein the concentration of sodium hydroxide is 100-300 g/L, and the concentration of ammonia is 0.3-1.2 mol/L;
(d) mixing the first solution, the precipitant solution and the second solution, adjusting the pH value to 10-12, and heating and reacting for 5-150 h under the conditions that the stirring speed is 500-1000 rpm and the temperature is 65-80 ℃; obtaining slurry with solid content of 50-1000 g/L;
(e) aging the slurry obtained in the step (d) in an aging kettle at a stirring speed of 200-300 rpm for 0.5-5 h;
(f) and (e) demagnetizing the aging product obtained in the step (e), carrying out solid-liquid separation, washing with water, and drying to obtain the five-element precursor material.
8. The five-membered precursor material prepared by the method according to any one of claims 1 to 7, wherein the five-membered precursor has a molecular formula of NiaCobMncXdYe(OH)2Wherein a is more than or equal to 50 percent and less than or equal to 90 percent, and 0 percent<b is less than or equal to 10 percent, c is less than or equal to 30 percent and more than or equal to 3 percent, d is less than or equal to 3 percent and more than or equal to 0.1 percent, e is less than or equal to 3 percent and a + b + c + d + e is 1, X, Y are two different auxiliary metals;
preferably, the particle size D50 of the quinary precursor material is 3-12 μm.
9. A method for preparing a five-membered positive electrode material, the method comprising: mixing the quinary precursor material of claim 8 with a lithium salt, and sintering to obtain the quinary positive electrode material;
preferably, the sintering method comprises a first sintering and a second sintering in sequence;
preferably, the temperature of the first sintering is 450-600 ℃, and the time is 4-6 h;
preferably, the temperature of the second sintering is 700-850 ℃, and the time is 15-25 h.
10. A five-membered positive electrode material, characterized in that it is prepared by the method of claim 9;
preferably, the molecular general formula of the five-membered cathode material is Li (Ni)aCobMncXdYe)O2Wherein a is more than or equal to 0.5 and less than or equal to 0.9 and 0<b is less than or equal to 0.1, c is less than or equal to 0.03 and less than or equal to 0.3, d is less than or equal to 0.0001 and less than or equal to 0.03, e is less than or equal to 0.0001 and less than or equal to 0.03, a + b + c + d + e is 1, X, Y is an auxiliary metal, and X, Y is two different auxiliary metals;
preferably, the quinary positive electrode material is used for a lithium ion battery.
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Citations (3)

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Publication number Priority date Publication date Assignee Title
CN103500825A (en) * 2013-09-26 2014-01-08 东莞新能源科技有限公司 Positive electrode material of multi-element layered lithium ion battery and preparation method thereof
CN109461928A (en) * 2018-09-19 2019-03-12 北京当升材料科技股份有限公司 A kind of high-energy density polynary positive pole material and preparation method thereof
CN109768275A (en) * 2019-01-03 2019-05-17 湖南中伟新能源科技有限公司 A kind of preparation method for mixing titanium lithium ion anode material presoma

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103500825A (en) * 2013-09-26 2014-01-08 东莞新能源科技有限公司 Positive electrode material of multi-element layered lithium ion battery and preparation method thereof
CN109461928A (en) * 2018-09-19 2019-03-12 北京当升材料科技股份有限公司 A kind of high-energy density polynary positive pole material and preparation method thereof
CN109768275A (en) * 2019-01-03 2019-05-17 湖南中伟新能源科技有限公司 A kind of preparation method for mixing titanium lithium ion anode material presoma

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