CN110718679A - High-performance primary large-particle ternary cathode composite material, and preparation method and application thereof - Google Patents

High-performance primary large-particle ternary cathode composite material, and preparation method and application thereof Download PDF

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CN110718679A
CN110718679A CN201810771076.2A CN201810771076A CN110718679A CN 110718679 A CN110718679 A CN 110718679A CN 201810771076 A CN201810771076 A CN 201810771076A CN 110718679 A CN110718679 A CN 110718679A
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ternary cathode
sulfur
sintering
ternary
cathode material
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CN110718679B (en
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李旭
罗亮
吴小珍
杨顺毅
黄友元
杨才德
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Shenzhen Battery Nanotechnology Co Ltd
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    • H—ELECTRICITY
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    • H01M10/05—Accumulators with non-aqueous electrolyte
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
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    • 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
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Abstract

The invention discloses a high-performance primary large-particle ternary cathode composite material, and a preparation method and application thereof. The composite material comprises a ternary cathode material with the primary particle size of 5-8 mu m, and a sulfur coating layer and a composite modified layer which are sequentially coated on the surface of the ternary cathode material from inside to outside; the composite modified layer is formed by compounding a high-molecular conductive polymer and a surfactant. The method comprises the following steps: 1) preparing lithium from a precursor of the ternary cathode material, and sintering for the first time to obtain the ternary cathode material with secondary particles formed by agglomeration of primary particles; 2) mixing with a fluxing agent, performing wet ball milling to change the particle size to be nano-scale, and performing secondary sintering; 3) coating sulfur and a composite modifier formed by compounding a high-molecular conductive polymer and a surfactant to obtain the ternary cathode composite material. The invention can effectively realize the preparation of the primary large-particle high-nickel ternary cathode material with high discharge specific capacity, high conductivity and high thermal stability, has simple process and is easy to realize large-scale production.

Description

High-performance primary large-particle ternary cathode composite material, and preparation method and application thereof
Technical Field
The invention relates to the field of new energy materials, relates to a ternary cathode composite material, a preparation method and application thereof, and particularly relates to a high-performance primary large-particle high-nickel ternary cathode composite material, and a preparation method and application thereof.
Background
High nickel ternary positive electrode material (LiNi)xM1-xO2，0.8≤x<1.0, M is one or more of Co, Mn and Al) is attracted by attention due to higher energy density, but the M is easy to react with electrolyte to generate a large amount of gas in a charging state, and meanwhile, certain problems exist in thermal stability, safety and cycling stability under high voltage, so that the high-nickel ternary LiNi is severely restrictedxM1-xO2Development of positive electrode materials. While the high nickel ternary LiNi with primary large particle structurexM1-xO2The positive electrode material has high thermal stability, is not easy to break in the rolling process of the pole piece, has high cycling stability, has the advantages of high compaction, high tap density and small specific surface area, and can effectively improve the volume energy density of the material.
CN 107665980A discloses a preparation method of a ternary battery material, which comprises 1) stirring and mixing lithium carbonate and a lithium cobaltate/lithium nickel cobalt aluminate precursor uniformly, and rapidly pushing the mixture into a first temperature zone of a two-section sintering furnace for heat preservation and decomposition; 2) after decomposition, pushing the mixture into a second temperature area of a two-section sintering furnace for sintering; 3) and after the mixture is sintered, cooling and crushing to obtain the nickel-cobalt-manganese/nickel-cobalt-aluminum ternary material. The method can improve the obstruction of inert atmosphere such as carbon dioxide, water vapor and the like generated when the precursor and the lithium carbonate are heated and decomposed to oxygen-enriched sintering atmosphere when the ternary material is sintered, so that divalent nickel ions in the ternary material can be fully oxidized and sintered, and finally the problems of cation mixed discharge, high alkalinity, easy moisture absorption and the like caused by difficult oxidation of the high-nickel type anode material are solved, and a product with obviously improved electrochemical performance is obtained. However, the product has small primary particle size, low capacity and poor conductivity, and the electrical performance of the material is seriously influenced.
How to reduce the mixed discharge of lithium and nickel in the process of increasing the size of primary particles, improve the specific discharge capacity of a sample, improve the conductivity and electrochemical stability of a material, and effectively apply the material to large-scale production still has a plurality of difficulties to be overcome.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a high-performance primary large-particle ternary cathode composite material, a preparation method and application thereof, in order to effectively solve the technical problems and better prepare a high-conductivity primary large-particle high-nickel ternary cathode material.
The high performance of the invention refers to: it has high capacity and good conductivity, capacity of more than 195mAh/g, and conductivity of 0.1S cm-1The above.
The invention provides a ternary cathode composite material, which comprises a ternary cathode material with a primary particle size of 5-8 mu m, a sulfur coating layer and a composite modified layer, wherein the sulfur coating layer and the composite modified layer are sequentially coated on the surface of the ternary cathode material from inside to outside;
the composite modified layer is formed by compounding a high-molecular conductive polymer and a surfactant.
In the composite material of the invention, the particle size of the ternary cathode material is 5-8 μm, such as 5 μm, 5.2 μm, 5.5 μm, 5.8 μm, 6 μm, 6.5 μm, 6.6 μm, 7 μm, 7.5 μm or 8 μm.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In the invention, because the hydrophilic end of the surfactant is combined with the high molecular conductive polymer in the composite modified layer, the composite material coated with the composite modified layer shows hydrophobicity.
Preferably, the high molecular conductive polymer is poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate, preferably poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate (PEDOT-PSS).
Preferably, the surfactant is any one or a combination of at least two of sodium alkyl benzene sulfonate, super-hydrophobic polyethylene, super-hydrophobic polyvinylidene fluoride or super-hydrophobic polyester fiber.
Preferably, the ternary cathode material is a high nickel ternary cathode material, preferably LiNixM1-xO2Wherein x is more than or equal to 0.8<1.0, M is any one or the combination of at least two of Co, Mn or Al. Such as 0.8, 0.85, 0.9, or 0.95, etc.
In a preferred embodiment of the composite material of the present invention, the thickness of the sulfur-coated layer is 0.1nm to 100nm, for example, 0.1nm, 0.5nm, 1nm, 2nm, 3nm, 5nm, 8nm, 10nm, 12nm, 15nm, 17nm, 20nm, 25nm, 28nm, 33nm, 36nm, 40nm, 45nm, 50nm, 55nm, 57nm, 60nm, 65nm, 68nm, 72nm, 76nm, 80nm, 85nm, 90nm, 95nm or 100nm, etc., preferably 0.1nm to 50nm, and more preferably 1nm to 20 nm.
Preferably, the thickness of the composite modified layer is 0.1nm to 100nm, for example, 0.1nm, 1nm, 2nm, 3nm, 4nm, 5nm, 8nm, 10nm, 12nm, 15nm, 17nm, 20nm, 25nm, 28nm, 33nm, 36nm, 40nm, 45nm, 50nm, 55nm, 57nm, 60nm, 65nm, 68nm, 72nm, 76nm, 80nm, 85nm, 90nm, 95nm, 100nm, or the like, preferably 1nm to 50nm, and more preferably 1nm to 20 nm.
In a second aspect, the present invention provides a method for preparing a ternary positive electrode composite material according to the first aspect, the method comprising the steps of:
(1) mixing a ternary cathode material precursor with a lithium source, and performing primary sintering to obtain a ternary cathode material with secondary particles formed by agglomeration of primary particles;
(2) mixing the ternary cathode material obtained in the step (1) with a fluxing agent, and performing wet ball milling to change the particle size of the ternary cathode material with secondary particles formed by agglomeration of primary particles to a nanometer level;
(3) secondary sintering is carried out to obtain a ternary cathode material with the primary particle size of 5-8 mu m;
(4) coating sulfur;
(5) coating a composite modified substance compounded by a high-molecular conductive polymer and a surfactant to form a composite modified layer, and obtaining the ternary cathode composite material.
In the method of the present invention, the primary particle size in step (1) and step (2) is on the nanometer scale.
In the method of the present invention, the primary particles in step (3) are single crystals and do not substantially agglomerate into secondary particles.
In the method, the wet ball milling in the step (2) is wet high-energy ball milling, secondary particles of the ternary cathode material are ball milled to a nanometer level through the wet high-energy ball milling and are sintered at a high temperature, and the ternary cathode material with the primary particle size of 5-8 microns can be prepared through the method. And then continuously coating sulfur and a composite modified layer, thereby successfully preparing the primary large-particle ternary cathode material with super hydrophobicity, low residual alkali, high conductivity and high capacity.
The primary sintering and the secondary sintering are both secondary high-temperature sintering.
As a preferred technical scheme of the method, the precursor of the ternary cathode material in the step (1) is NixM1-x(OH)2X is more than or equal to 0.8 and less than or equal to 0.9. Such as 0.8, 0.82,. 0.85, 0.87, or 0.9, etc.
Preferably, the lithium source of step (1) comprises lithium hydroxide and/or lithium carbonate.
Preferably, the ratio of lithium in step (1) is 1.0-1.15, such as 1.0, 1.05, 1.1 or 1.15, and preferably 1.05-1.15.
Preferably, the temperature of the primary sintering in the step (1) is 300 to 1000 ℃, for example, 300 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 850 ℃, 900 ℃ or 1000 ℃, and the like, preferably 500 to 1000 ℃, and more preferably 600 to 900 ℃.
Preferably, the time for the primary sintering in the step (1) is 3h to 12h, for example, 3h, 4h, 5h, 6h, 8h, 9h, 10h or 12h, etc., preferably 5h to 12h, and more preferably 7h to 12 h.
Preferably, the fluxing agent in the step (2) is H3BO3LiF, NaCl or ZrO2Any one or a combination of at least two of them, preferably H3BO3And/or ZrO2。
In the step (2), the amount of the flux added to the ternary positive electrode material obtained in the step (1) is preferably 500 to 5000ppm, more preferably 500 to 3000ppm, still more preferably 1000 to 3000ppm, and particularly preferably 1500 to 2500 ppm.
In the method, the fluxing agent has the function of reducing the melting point of the sample, and if the addition amount of the fluxing agent is less than 500ppm, the primary particles are smaller; if the amount of the flux added is greater than 5000ppm, the exertion of the sample volume is affected.
Preferably, the temperature of the secondary sintering in the step (3) is 300 to 1000 ℃, for example 300 ℃, 400 ℃, 500 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 850 ℃, 900 ℃ or 1000 ℃, etc., preferably 500 to 1000 ℃, and more preferably 600 to 800 ℃.
Preferably, the time for the secondary sintering in the step (3) is 3 to 12 hours, such as 3, 5, 6, 7, 8, 9, 10, or 12 hours, preferably 5 to 12 hours, and more preferably 7 to 10 hours.
As a preferable technical scheme of the method, the method for coating the sulfur in the step (4) comprises the following steps:
and (4) mixing the ternary cathode material obtained in the step (3) with nano sulfur, ball-milling, and sintering for three times to obtain the sulfur-coated ternary cathode composite material.
The particle size of the nano sulfur is preferably 10nm to 100nm, for example, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, or 100nm, preferably 10nm to 50nm, and more preferably 10nm to 30 nm.
In the method of coating sulfur, the coating amount of nano sulfur with respect to the ternary positive electrode material obtained in step (3) is preferably 200ppm to 3000ppm, more preferably 500ppm to 2000ppm, and still more preferably 500ppm to 1500 ppm. If the sulfur coating amount is less than 200ppm, the capacity cannot be improved; if the sulfur coating amount is more than 3000ppm, migration of lithium ions is restricted, increasing the internal resistance of the battery.
Preferably, in the method for coating sulfur, the rotation speed of the ball mill is 100r/min to 2000r/min, such as 100r/min, 200r/min, 300r/min, 450r/min, 600r/min, 800r/min, 1000r/min, 1200r/min, 1350r/min, 1500r/min, 1600r/min, 1800r/min or 2000r/min, etc., preferably 100r/min to 1000r/min, and more preferably 200r/min to 500 r/min.
Preferably, the ball milling time is 0.5h to 24h, for example, 0.5h, 1h, 2h, 3.5h, 5h, 6h, 8h, 10h, 12h, 15h, 18h, 20h or 24h, etc., preferably 0.5h to 12h, and more preferably 2h to 12 h.
According to the preferable technical scheme, the surface of the sample is coated with sulfur by a melting method, and the method can be used for better improving the specific discharge capacity of the sample.
Preferably, the temperature of the third sintering is 150 ℃ to 500 ℃, for example 150 ℃, 170 ℃, 200 ℃, 225 ℃, 245 ℃, 260 ℃, 280 ℃, 300 ℃, 350 ℃, 375 ℃, 400 ℃, 450 ℃ or 500 ℃, preferably 150 ℃ to 300 ℃, and more preferably 200 ℃ to 300 ℃.
The time for the third sintering is preferably 2 to 12 hours, for example 2, 3, 5, 6, 8, 10, 11 or 12 hours, preferably 2 to 10 hours, and more preferably 5 to 10 hours.
As a preferred technical scheme of the method, the method for coating the composite modifier in the step (5) comprises the following steps:
and (4) adding the sulfur-coated ternary cathode composite material obtained in the step (4) into a water solution of a high-molecular conductive polymer dispersed with a surfactant, stirring and drying to obtain the sulfur-coated ternary cathode composite material, namely the ternary cathode composite material, of the high-molecular conductive polymer/the surfactant.
Preferably, the high molecular conductive polymer is poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate.
The amount of the polymer conductive polymer added is preferably 0.1 to 20% by mass, for example, 0.1%, 0.5%, 1%, 2%, 3%, 5%, 8%, 10%, 12%, 14%, 16%, 18%, 20% or the like, preferably 0.1 to 15%, and more preferably 0.5 to 5% by mass of the sulfur-coated ternary positive electrode composite material obtained in step (4).
Preferably, the surfactant is sodium alkyl benzene sulfonate.
In the method of coating the composite modified product, the amount of the surfactant added to the sulfur-coated ternary positive electrode composite material obtained in step (4) is preferably 200ppm to 5000ppm, for example, 200ppm, 450ppm, 650ppm, 1000ppm, 1500ppm, 1750ppm, 2000ppm, 2300ppm, 2600ppm, 3000ppm, 3500ppm, 4000ppm, 5000ppm or the like, preferably 500ppm to 5000ppm, more preferably 1000ppm to 3000ppm, and particularly preferably 1000ppm to 2000 ppm.
Preferably, in the method for coating the composite modified substance, the stirring is high-speed stirring, and the rotating speed is 100r/min to 3000r/min, such as 100r/min, 200r/min, 400r/min, 500r/min, 800r/min, 1000r/min, 1250r/min, 1500r/min, 1750r/min, 2000r/min, 2300r/min, 2600r/min or 3000r/min, etc., preferably 200r/min to 2000r/min, and more preferably 500r/min to 1500 r/min.
Preferably, in the method for coating the composite modified product, the drying is any one or a combination of at least two of spray drying, oil bath evaporation drying, freeze drying and vacuum drying, preferably any one or a combination of at least two of spray drying, freeze drying and vacuum drying, and more preferably any one or a combination of two of spray drying and vacuum drying.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) precursor Ni of ternary positive electrode materialxM1-x(OH)2Mixing with a lithium source, wherein the proportion of lithium is 1.05-1.15, and carrying out primary sintering at the temperature of 600-900 ℃ in a certain timeThe time is 7-12 h, so that the ternary cathode material with secondary particles formed by the agglomeration of primary particles is obtained, and x is more than or equal to 0.8 and less than or equal to 0.9;
(2) mixing the ternary cathode material obtained in the step (1) with a fluxing agent, and performing wet ball milling to change the particle size of the ternary cathode material with secondary particles formed by agglomeration of primary particles to a nanometer level;
wherein the fluxing agent is H3BO3And/or ZrO2The addition amount is 1500ppm to 2500 ppm;
(3) secondary sintering is carried out, the sintering temperature is 600-800 ℃, the sintering time is 7-10 h, and the ternary cathode material with the primary particle size of 5-8 mu m is obtained;
(4) mixing the ternary cathode material obtained in the step (3) with nano sulfur, ball-milling, and sintering for three times, wherein the sintering temperature is 200-300 ℃, and the sintering time is 5-10 hours, so as to obtain a sulfur-coated primary large-particle ternary cathode composite material;
wherein the sulfur coating amount is 500ppm to 1500 ppm;
(5) adding the sulfur-coated ternary positive electrode composite material obtained in the step (4) into an aqueous solution of poly (3, 4-ethylenedioxythiophene) dispersed with sodium alkyl benzene sulfonate, namely polystyrene sulfonate, stirring and drying to obtain a primary large-particle ternary positive electrode composite material, namely a ternary positive electrode composite material, coated with sulfur and a high-molecular conductive polymer/surfactant;
wherein the addition amount of the sodium alkyl benzene sulfonate is 1000ppm to 2000 ppm.
According to the preferred technical scheme, the high-nickel ternary positive electrode material is ball-milled to be nanoscale through wet high-energy ball milling, the high-nickel ternary positive electrode material and a fluxing agent are mixed more uniformly, then sulfur is coated on the surface of a sample through a melting method, the discharge specific capacity of the sample is improved, and finally the PEDOT-PSS/hydrophobic sodium alkyl benzene sulfonate is coated through the wet method, so that the high-conductivity and super-hydrophobic primary large-particle high-nickel ternary positive electrode material can be obtained.
In a third aspect, the present invention provides a lithium ion battery comprising the ternary positive electrode composite material of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the method can simply and effectively realize the preparation of the primary large-particle high-nickel ternary cathode material with high discharge specific capacity, high conductivity and high thermal stability.
(1) The secondary particles formed by aggregating the primary particles are ball-milled and crushed to a nanometer level by using a high-energy ball-milling method, a fluxing agent is used in a matching manner, and the secondary particles are sintered at a high temperature again, so that the crystal lattice structure is better in consistency, the primary large particles are more uniform in size, and the transmission of electrons is facilitated.
(2) The sulfur is coated on the primary large-particle ternary positive electrode material, particularly the sulfur is coated by using a melting method, so that the mixed discharge of lithium and nickel can be reduced, the specific discharge capacity and the electrochemical stability of the material are greatly improved, and the residual alkali on the surface of the material is reduced.
(3) The high-molecular conductive polymer (such as PEDOT-PSS) and the surfactant (such as hydrophobic sodium alkyl benzene sulfonate) are used for coating, so that the electronic conductivity of the material can be greatly improved, the side reaction between the material and electrolyte can be effectively inhibited, and the generation of gas can be reduced; the surfactant can reduce the reaction of ambient moisture with surface free lithium and the side reaction of trace amounts of water with the electrolyte.
(4) The method has simple process and is easy to realize large-scale production.
Drawings
FIG. 1 is an SEM image of a material prepared in example 1;
FIG. 2 is an SEM image of the material prepared in example 2.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1:
a preparation method of a primary large-particle high-nickel ternary cathode material comprises the following steps:
(1) 100g of Ni were weighed0.88Co0.09Al0.03(OH)2Precursor, Ni0.88Co0.09Al0.03(OH)2Mixing the precursor and LiOH according to the mol ratio of 1:1.03, and carrying out primary firing at 700 DEG CObtaining a material A after 5 hours;
(2) addition of H3BO3Let H stand for3BO3Adding 1000ppm of the material A, performing wet high-energy ball milling, wherein the dispersing agent is ethanol, performing ball milling on the mixed material to a nanometer level, and performing secondary sintering at 850 ℃ for 10 hours to obtain a primary large-particle high-nickel ternary cathode material B, wherein the primary particle size of the primary large-particle high-nickel ternary cathode material B is about 5 microns;
(3) adding nano sulfur to enable the addition amount of the nano sulfur to be 500ppm relative to the material B, mixing and ball-milling for 2 hours at 200r/min, and sintering and coating at 200 ℃ to obtain a material C;
(4) adding hydrophobic sodium alkyl benzene sulfonate into aqueous solution containing PEDOT-PSS (accounting for 1% of the mass of the material C), and adding the material C into the aqueous solution dispersed with the hydrophobic sodium alkyl benzene sulfonate
And in the aqueous solution of PEDOT-PSS, the addition amount of the hydrophobic sodium alkyl benzene sulfonate relative to the material C is 1000ppm, stirring at a high speed, and freeze-drying for 48 hours to obtain the primary large-particle high-nickel ternary cathode material with high conductivity and high specific discharge capacity.
Fig. 1 is an SEM spectrum prepared in example 1, and it can be seen from the graph that the size of the primary particles of the sample is about 5 μm, the primary large particles are single crystals, the surfaces of the particles are round and smooth, and have no edges and corners, and thus the sample can be effectively prevented from penetrating through the separator during the battery preparation process to cause short circuit.
Example 2:
a preparation method of a primary large-particle high-nickel ternary cathode material comprises the following steps:
(1) 100g of Ni were weighed0.88Co0.09Al0.03(OH)2Precursor, Ni0.88Co0.09Al0.03(OH)2Mixing the precursor and LiOH according to a molar ratio of 1:1.05, and sintering at 700 ℃ for 5 hours at one time to obtain a material A;
(2) 1500ppm of ZrO were added to feed A2Performing wet high-energy ball milling, wherein a dispersing agent is ethanol, ball milling the mixed materials to be nano-scale, and performing secondary sintering at 850 ℃ for 10 hours to obtain a primary large-particle high-nickel ternary cathode material B, wherein the primary particle size of the primary large-particle high-nickel ternary cathode material B is about 6 microns;
(3) adding 1000ppm of nano sulfur into the material B, mixing and ball-milling for 1h at 200r/min, and sintering and coating at 200 ℃ to obtain a material C;
(4) and adding 1000ppm of hydrophobic sodium alkyl benzene sulfonate into a PEDOT-PSS aqueous solution containing 1% of the mass of the positive electrode material, then adding the material C into the PEDOT-PSS aqueous solution in which the hydrophobic sodium alkyl benzene sulfonate is dispersed, stirring at a high speed, and freeze-drying for 48 hours to obtain the primary large-particle high-nickel ternary positive electrode material with high conductivity and high specific discharge capacity.
FIG. 2 is an SEM spectrum of the material prepared in this example 2, and it can be seen that the sample has a primary particle size of about 5 μm, and is well dispersed without agglomeration.
The ternary cathode material of the embodiment has high capacity, high conductivity and cycle performance similar to those of the embodiment 1, the capacity is more than 195mAh/g, and the conductivity is 0.1S-cm by adopting the same conditions for testing as the embodiment 1-1The above.
Example 3:
a preparation method of a primary large-particle high-nickel ternary cathode material comprises the following steps:
(1) 200g of Ni are weighed0.8M0.2(OH)2Precursor, Ni0.8M0.2(OH)2Mixing the precursor and LiOH according to a molar ratio of 1:1.12, and sintering at 750 ℃ for 3 hours at one time to obtain a material A;
(2) addition of H3BO3Let H stand for3BO3Adding 2500ppm of the material A, performing wet high-energy ball milling, wherein the dispersing agent is ethanol, performing ball milling on the mixed material to a nanometer level, and performing secondary sintering at 950 ℃ for 5 hours to obtain a primary large-particle high-nickel ternary cathode material B, wherein the primary particle size of the primary large-particle high-nickel ternary cathode material B is about 7 microns;
(3) adding nano sulfur to enable the addition amount of the nano sulfur relative to the material B to be 2000ppm, mixing and ball-milling for 1h at 300r/min, and sintering and coating at 300 ℃ to obtain a material C;
(4) adding hydrophobic sodium alkyl benzene sulfonate into 2000ppm PEDOT-PSS (3% of the material C in mass) aqueous solution, then adding material C into the PEDOT-PSS aqueous solution dispersed with the hydrophobic sodium alkyl benzene sulfonate, wherein the addition amount of the hydrophobic sodium alkyl benzene sulfonate relative to the material C is 2000ppm, stirring at a high speed, and spray drying to obtain the primary large-particle high-nickel ternary cathode material with high conductivity and high specific discharge capacity.
The ternary cathode material of the embodiment has high capacity, high conductivity and cycle performance similar to those of the embodiment 1, the capacity is more than 195mAh/g, and the conductivity is 0.1S-cm by adopting the same conditions for testing as the embodiment 1-1The above.
Example 4:
a preparation method of a primary large-particle high-nickel ternary cathode material comprises the following steps:
(1) 100g of Ni were weighed0.85Mn0.15(OH)2Precursor, Ni0.85Mn0.15(OH)2Mixing the precursor and LiOH according to a molar ratio of 1:1, and sintering at 500 ℃ for 12h at one time to obtain a material A;
(2) adding LiF to enable the addition amount of the LiF to be 3500ppm relative to the material A, performing wet high-energy ball milling, wherein the dispersing agent is ethanol, performing ball milling on the mixed material to a nanometer level, and performing secondary sintering at 800 ℃ for 8 hours to obtain a primary large-particle high-nickel ternary cathode material B, wherein the primary particle size of the primary large-particle high-nickel ternary cathode material B is about 5 microns;
(3) adding nano sulfur to enable the addition amount of the nano sulfur relative to the material B to be 1500ppm, mixing and ball-milling for 1h at 400r/min, and sintering and coating at 500 ℃ to obtain a material C;
(4) adding hydrophobic sodium alkyl benzene sulfonate into aqueous solution containing PEDOT-PSS (accounting for 15% of the mass of the material C), and adding the material C into the aqueous solution dispersed with the hydrophobic sodium alkyl benzene sulfonate
And in the aqueous solution of PEDOT-PSS, 3500ppm of addition amount of hydrophobic sodium alkyl benzene sulfonate relative to material C, stirring at high speed, and drying in vacuum to obtain the primary large-particle high-nickel ternary cathode material with high conductivity and high specific discharge capacity.
The ternary positive electrode material of the present example has high capacity, high conductivity and cycle performance similar to those of example 1, tested under the same conditions as example 1, and the capacity is 195mAh/g or more, and the conductivity is 0.1S-cm-1The above.
Example 5:
a preparation method of a primary large-particle high-nickel ternary cathode material comprises the following steps:
(1) 100g of Ni were weighed0.88Co0.12(OH)2Precursor, Ni0.88Co0.12(OH)2Mixing the precursor and LiOH according to a molar ratio of 1:1.08, and sintering at 650 ℃ for 7 hours at one time to obtain a material A;
(2) adding NaCl to enable the addition amount of the NaCl relative to the material A to be 5000ppm, carrying out wet high-energy ball milling, wherein the dispersing agent is ethanol, carrying out ball milling on the mixed material to be in a nanometer level, and carrying out secondary sintering at 1000 ℃ for 4 hours to obtain a primary large-particle high-nickel ternary cathode material B, wherein the primary particle size of the primary large-particle high-nickel ternary cathode material B is about 6 microns;
(3) adding nano sulfur to ensure that the addition amount of the nano sulfur relative to the material B is 2500ppm, mixing and ball-milling for 2 hours at 350r/min, and sintering and coating at 400 ℃ to obtain a material C;
(4) adding hydrophobic sodium alkyl benzene sulfonate into aqueous solution containing PEDOT-PSS (accounting for 8% of the mass of the material C), and adding the material C into the aqueous solution dispersed with the hydrophobic sodium alkyl benzene sulfonate
And in the aqueous solution of PEDOT-PSS, the addition amount of the hydrophobic sodium alkyl benzene sulfonate relative to the material C is 5000ppm, stirring at a high speed, and evaporating and drying in an oil bath to obtain the primary large-particle high-nickel ternary cathode material with high conductivity and high specific discharge capacity.
The ternary cathode material of the embodiment has high capacity, high conductivity and cycle performance similar to those of the embodiment 1, the capacity is more than 195mAh/g, and the conductivity is 0.1S-cm by adopting the same conditions for testing as the embodiment 1-1The above.
Comparative example 1
The procedure and conditions were the same as in example 1 except that steps (3) and (4) were not performed.
Comparative example 2
The procedure and conditions were the same as in example 1 except that step (4) was not conducted.
Comparative example 3
The procedure and conditions were the same as in example 1 except that the sulfur coating in step (3) was not conducted, but step (4) was directly conducted.
The positive electrode materials of example 1 and comparative examples 1 to 3 were tested by the following methods:
the invention adopts a Malvern laser particle size tester MS 2000 to test the particle size range of the material and the average particle size of the raw material particles.
The surface appearance, particle size and the like of the sample were observed by a scanning electron microscope of Hitachi S4800.
The residual alkali of the sample was measured using an automatic potentiometric titrator from Mettler corporation.
Electrochemical cycling performance was tested using the following method: mixing a positive electrode material, a conductive agent and a binder according to the mass percentage of 94: 1: 5, dissolving the materials in a solvent, mixing, controlling the solid content to be 50%, coating the mixture on an aluminum foil current collector, and drying in vacuum to obtain a positive pole piece; then, a lithium sheet, 1mol/L LiPF6/EC + DMC + EMC (v/v ═ 1:1:1) electrolyte, Celgard2400 separator, and a conventional 2016 button cell was used for the negative electrode. The charge and discharge test of the button cell is carried out on a LAND cell test system of Wuhanjinnuo electronic Limited company, the first discharge and the first effect are measured under the condition of normal temperature and constant current charge and discharge of 0.1C, and the charge and discharge voltage is limited to 3.0-4.3V under the condition of 0.5C/1C measurement circulation.
TABLE 1 data sheet of samples of examples and comparative examples
Figure BDA0001730271610000141
Table 1 is a data table of samples of example 1 and comparative example, and it can be seen from the table that comparative example 1 has high residual alkali, low conductivity, and poor specific discharge capacity and cycle under the condition of no coating; after sulfur coating, the residual alkali of the sample of comparative example 2 is reduced, the first-release effect and the first-effect are both improved, but the conductivity is poor because sulfur is a poor conductor of electrons; comparative example 3 in the case of no sulfur coating, the super-hydrophobic conductive polymer composite material is directly coated, the electronic conductivity is greatly improved, the residual alkali is reduced, the first effect and the first release are improved, but compared with example 1, the performances of the three comparative examples are lower.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The ternary cathode composite material is characterized by comprising a ternary cathode material with the primary particle size of 5-8 microns, and a sulfur coating layer and a composite modified layer which are sequentially coated on the surface of the ternary cathode material from inside to outside;
the composite modified layer is formed by compounding a high-molecular conductive polymer and a surfactant.
2. The composite material of claim 1, wherein the composite modification layer of the outermost layer of the composite material renders the composite material hydrophobic;
preferably, the high molecular conductive polymer is poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate, preferably poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate;
preferably, the surfactant is any one or a combination of at least two of sodium alkyl benzene sulfonate, super-hydrophobic polyethylene, super-hydrophobic polyvinylidene fluoride or super-hydrophobic polyester fiber;
preferably, the ternary cathode material is a high nickel ternary cathode material, preferably LiNixM1-xO2Wherein x is more than or equal to 0.8<1.0, M is any one or the combination of at least two of Co, Mn or Al.
3. Composite material according to any of claims 1-3, characterized in that the thickness of the sulfur coating is 0.1 to 100nm, preferably 0.1 to 50nm, more preferably 1 to 30 nm;
preferably, the thickness of the composite modified layer is 0.1nm to 100nm, preferably 1nm to 50nm, and more preferably 5nm to 30 nm.
4. A method of preparing a ternary positive electrode composite according to any of claims 1 to 3, characterized in that it comprises the following steps:
(1) mixing a ternary cathode material precursor with a lithium source, and performing primary sintering to obtain a ternary cathode material with secondary particles formed by agglomeration of primary particles;
(2) mixing the ternary cathode material obtained in the step (1) with a fluxing agent, and performing wet ball milling to change the particle size of the ternary cathode material with secondary particles formed by agglomeration of primary particles to a nanometer level;
(3) secondary sintering is carried out to obtain a ternary cathode material with the primary particle size of 5-8 mu m;
(4) coating sulfur;
(5) coating a composite modified substance compounded by a high-molecular conductive polymer and a surfactant to form a composite modified layer, and obtaining the ternary cathode composite material.
5. The method according to claim 4, wherein the ternary positive electrode material precursor in the step (1) is NixM1-x(OH)2，0.8≤x<1；
Preferably, the lithium source of step (1) comprises lithium hydroxide and/or lithium carbonate;
preferably, the ratio of lithium in the step (1) is 1.0-1.15, preferably 1.05-1.15, and the ratio of lithium refers to the molar ratio of lithium ions to the precursor;
preferably, the temperature of the primary sintering in the step (1) is 300-1000 ℃, preferably 500-1000 ℃, and further preferably 600-900 ℃;
preferably, the time for the primary sintering in the step (1) is 3 to 12 hours, preferably 5 to 12 hours, and more preferably 7 to 12 hours.
6. The method of claim 4 or 5, wherein the step (2) is performed in the same manner as the method of claim 4 or 5The fluxing agent is H3BO3LiF, NaCl or ZrO2Any one or a combination of at least two of them, preferably H3BO3And/or ZrO2；
In the step (2), the addition amount of the flux to the ternary positive electrode material obtained in the step (1) is preferably 500ppm to 5000ppm, more preferably 500ppm to 3000ppm, even more preferably 1000ppm to 3000ppm, and particularly preferably 1500ppm to 2500 ppm;
preferably, the temperature of the secondary sintering in the step (3) is 300-1000 ℃, preferably 500-1000 ℃, and more preferably 600-800 ℃;
preferably, the time for the secondary sintering in the step (3) is 3 to 12 hours, preferably 5 to 12 hours, and more preferably 7 to 10 hours.
7. The method according to any one of claims 4 to 6, wherein the step (4) of coating sulfur is performed by:
mixing the ternary cathode material obtained in the step (3) with nano sulfur, ball-milling, and sintering for three times to obtain a sulfur-coated ternary cathode composite material;
preferably, the particle size of the nano sulfur is 10nm to 100nm, more preferably 10nm to 50nm, and still more preferably 10nm to 30 nm;
preferably, in the sulfur coating method, the coating amount of the nano sulfur relative to the ternary cathode material obtained in the step (3) is 200ppm to 3000ppm, preferably 500ppm to 2000ppm, and more preferably 500ppm to 1500 ppm;
preferably, in the sulfur coating method, the rotation speed of the ball mill is 100r/min to 2000r/min, preferably 100r/min to 1000r/min, and more preferably 200r/min to 500 r/min;
preferably, in the sulfur coating method, the mixing and ball milling time is 0.5 to 24 hours, preferably 0.5 to 12 hours, and further preferably 2 to 12 hours;
preferably, the temperature of the third sintering is 150-500 ℃, preferably 150-300 ℃, and further preferably 200-300 ℃;
preferably, the time for the third sintering is 2 to 12 hours, preferably 2 to 10 hours, and more preferably 5 to 10 hours.
8. The method according to any one of claims 4 to 7, wherein the step (5) of coating the composite modifier comprises the following steps:
adding the sulfur-coated ternary positive electrode composite material obtained in the step (4) into a water solution of a high-molecular conductive polymer dispersed with a surfactant, stirring and drying to obtain a sulfur-coated ternary positive electrode composite material, namely a ternary positive electrode composite material, of the high-molecular conductive polymer/the surfactant;
preferably, the high molecular conductive polymer is poly 3, 4-ethylenedioxythiophene, polystyrene sulfonate;
preferably, the addition amount of the high molecular conductive polymer is 0.1-20% of the mass of the sulfur-coated ternary cathode composite material obtained in the step (4), preferably 0.1-15%, and more preferably 0.5-5%;
preferably, the surfactant is any one or a combination of at least two of sodium alkyl benzene sulfonate, super-hydrophobic polyethylene, super-hydrophobic polyvinylidene fluoride or super-hydrophobic polyester fiber;
preferably, in the method for coating the composite modified product, the addition amount of the surfactant relative to the sulfur-coated ternary positive electrode composite material obtained in the step (4) is 200ppm to 5000ppm, preferably 500ppm to 5000ppm, more preferably 1000ppm to 3000ppm, and particularly preferably 1000ppm to 2000 ppm;
preferably, in the method for coating the composite modifier, the stirring speed is 100r/min to 3000r/min, preferably 200r/min to 2000r/min, and more preferably 500r/min to 1500 r/min;
preferably, in the method for coating the composite modified product, the drying is any one or a combination of at least two of spray drying, oil bath evaporation drying, freeze drying and vacuum drying, preferably any one or a combination of at least two of spray drying, freeze drying and vacuum drying, and more preferably any one or a combination of two of spray drying and vacuum drying.
9. Method according to any of claims 4-8, characterized in that the method comprises the steps of:
(1) precursor Ni of ternary positive electrode materialxM1-x(OH)2Mixing the lithium source with the lithium in the proportion of 1.05-1.15, and performing primary sintering at the sintering temperature of 600-900 ℃ for 7-12 h to obtain a ternary cathode material with secondary particles formed by agglomeration of primary particles, wherein x is more than or equal to 0.8 and less than or equal to 0.9;
(2) mixing the ternary cathode material obtained in the step (1) with a fluxing agent, and performing wet ball milling to change the particle size of the ternary cathode material with secondary particles formed by agglomeration of primary particles to a nanometer level;
wherein the fluxing agent is H3BO3And/or ZrO2The addition amount of the fluxing agent relative to the ternary cathode material obtained in the step (1) is 1500 ppm-2500 ppm;
(3) secondary sintering is carried out, the sintering temperature is 600-800 ℃, the sintering time is 7-10 h, and the ternary cathode material with the primary particle size of 5-8 mu m is obtained;
(4) mixing the ternary cathode material obtained in the step (3) with nano sulfur, ball-milling, and sintering for three times, wherein the sintering temperature is 200-300 ℃, and the sintering time is 5-10 hours, so as to obtain a sulfur-coated ternary cathode composite material;
wherein the coating amount of the nano sulfur relative to the ternary cathode material obtained in the step (3) is 500 ppm-1500 ppm;
(5) adding the sulfur-coated ternary positive electrode composite material obtained in the step (4) into an aqueous solution of poly (3, 4-ethylenedioxythiophene) dispersed with sodium alkyl benzene sulfonate, namely polystyrene sulfonate, stirring and drying to obtain a sulfur-coated and high-molecular conductive polymer/surfactant-coated ternary positive electrode composite material, namely a ternary positive electrode composite material;
wherein the addition amount of the sodium alkyl benzene sulfonate relative to the sulfur-coated ternary cathode composite material obtained in the step (4) is 1000ppm to 2000 ppm.
10. A lithium ion battery comprising the ternary positive electrode composite of any of claims 1-3.
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