CN112952049A - Method for repairing surface structure of high-nickel anode material, high-nickel anode material obtained by method and lithium ion battery - Google Patents
Method for repairing surface structure of high-nickel anode material, high-nickel anode material obtained by method and lithium ion battery Download PDFInfo
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Abstract
The invention provides a method for repairing a surface structure of a high-nickel anode material, the high-nickel anode material obtained by the method and a lithium ion battery. The method comprises the following steps: 1) mixing a high-nickel positive electrode material, a first lithium source and a metal oxide, and sintering to obtain a sintered product; 2) and mixing the sintered product with an acid solution, reacting, evaporating to dryness, and sintering to obtain the high-nickel anode material with the repaired surface structure. Firstly, respectively carrying out a synthesis reaction on a first lithium source and a metal oxide with nickel oxide and residual lithium on the surface of a material to remove part of impurity phases on the surface of the material and form a protective layer on the surface of the material; and then weak acid is utilized to further remove impurities on the surface of the material, and a lithium ion conductor coating layer is formed on the surface of the material, so that the discharge capacity and the first effect of the battery are improved, and the cycle performance and the safety performance are improved.
Description
Technical Field
The invention belongs to the technical field of energy storage, relates to a method for repairing a surface structure of a positive electrode material, and particularly relates to a method for repairing a surface structure of a high-nickel positive electrode material, a high-nickel positive electrode material obtained by the method, and a lithium ion battery.
Background
With the continuous development of new energy industry, the requirements of people on power batteries are higher and higher, and the content of nickel in ternary materials is increased, but the stability problem of the anode material, the matching problem of electrolyte, the battery failure caused by high-current charging temperature rise and the like are more and more concerned by people, so that the single crystal material is generated by transportation, the stability of the anode material is enhanced, the voltage of the whole system can be increased to a new height, and a solution is provided for the requirement of higher energy density. At present, the wide application in the market is mainly the medium-low nickel single crystal positive electrode material, including NCM523 and NCM 622. The surface residual lithium and impure phase of the medium-low nickel single crystal anode material are very little, the general physical and chemical properties are stable, but the energy density is low, and the requirements of pure electric vehicles on long endurance can not be met. The high-nickel single-crystal anode material has high energy density and can meet the requirement of an electric automobile on long endurance, but the single-crystal anode material with higher NCM811 and nickel content is less in application at present, and the main reason is that the surface of the high-nickel single-crystal anode material is more in residual lithium and other impurity phases, which seriously influences the physical and chemical properties of the high-nickel single-crystal material. In order to meet the market demand on the single crystal anode material with higher energy density, how to repair the surface structure of the high-nickel single crystal anode material, and therefore, the high-nickel single crystal anode material with excellent performance is of great significance.
CN108011098A discloses a ternary cathode material and a preparation method thereof, wherein the method mixes a ternary material precursor Ni according to a certain proportionxCoyMnz(OH)2、LiOH、MoO2Then presintering at a first designated temperature for a first designated time to obtain a presintering mixture, wherein x + y + z is 1; removing the unburnt substances in the pre-burning mixtureSintering powder, calcining the residual pre-sintering mixture at a second specified temperature for a second specified time, and cooling to obtain a Mo-doped ternary material; the ternary material doped with Mo is mixed with Li2CO3And Al2O3And calcining the mixture for a third specified time at a third specified temperature in proportion, and cooling to obtain the ternary cathode material.
CN110010877A discloses a surface-coated high-nickel ternary material, a preparation method and application thereof, wherein a binary coating layer consisting of sodium silicate and transition metal oxide is generated on the surface of the high-nickel ternary material. The scheme comprises the following steps: 1) preparing a coating solution A: preparing a sodium silicate aqueous solution with the mass percentage concentration of 3-10 wt%, wherein the molecular formula of the sodium silicate is Na2O·nSiO2N is 1 to 3; 2) preparing a coating solution B: preparing a transition metal compound solution with the mass percent concentration of 10-30 wt%; 3) fully dispersing the high-nickel ternary material in the coating liquid A, and stirring to obtain a suspension, wherein the process is finished at the temperature of 10-60 ℃ for 1-5 hours, and the stirring speed is 200-1000 rpm; 4) then, dripping the coating liquid B into the suspension obtained in the step 3), and finishing dripping within 0.5-2 hours to obtain a mixed solution, wherein the mixing process is kept at the temperature of 10-60 ℃, and the stirring speed is 200-800 rpm; 5) heating the mixed solution obtained in the step 4) in a 70-100 ℃ water bath, evaporating until the residual solution amount is 15-50% of the initial amount, filtering while hot, drying the filter cake in an air-blast drying oven for 2-6 hours, and fully grinding to obtain powder for later use; 6) the obtained powder is processed at high temperature in air atmosphere, the atmosphere in the cavity is normal pressure air, the gas flow rate of the cavity is 100-.
However, the above solution has limited improvement on the performance of high nickel ternary material, and is still difficult to meet the market demand.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, the present invention aims to provide a method for repairing the surface structure of a high nickel cathode material, a high nickel cathode material obtained by the same, and a lithium ion battery. The method provided by the invention not only improves the discharge capacity and first effect of the battery, but also improves the cycle performance and safety performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for repairing a surface structure of a high nickel cathode material, the method comprising the steps of:
(1) mixing a high-nickel positive electrode material, a first lithium source and a metal oxide, and sintering to obtain a sintered product;
(2) and (2) mixing the sintered product obtained in the step (1) with an acid solution, reacting, evaporating to dryness, and sintering to obtain the high-nickel cathode material with the repaired surface structure.
The method provided by the invention comprises the steps of firstly, respectively oxidizing nickel (Ni) on the surface of a material by a first lithium source and a metal oxidexO) and residual lithium are subjected to a synthesis reaction, part of impurity phases on the surface of the material are removed, and a protective layer is formed on the surface of the material; and then weak acid is utilized to further remove impurities on the surface of the material, and a lithium ion conductor coating layer is formed on the surface of the material, so that the discharge capacity and the first effect of the battery are improved, and the cycle performance and the safety performance are improved.
In the present invention, the step (2) is a drying operation for removing water from the material without damaging the coating layer on the surface of the material.
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.
As a preferable technical scheme of the invention, the chemical formula of the high-nickel cathode material in the step (1) is LiNi1-x- yCoxMnyO2Where 0 < x.ltoreq.0.10, e.g.x is 0.01, 0.02, 0.04, 0.06, 0.08 or 0.1 etc., 0. ltoreq.y.ltoreq.0.15, e.g.y is 0, 0.2, 0.4, 0.6, 0.8, 0.9, 1.0, 1.1, 1.3 or 1.5 etc.
Preferably, the first lithium source in step (1) comprises any one or a combination of at least two of lithium hydroxide, lithium acetate or lithium nitrate, preferablyLithium hydroxide is selected. Lithium hydroxide can be mixed with Ni on the surface of the high-nickel cathode material in the sintering processxO and the like react to form a layered lithium metal oxide.
Preferably, the metal oxide in step (1) comprises any one of alumina, titania, zirconia, yttria, cobalt oxide, molybdenum oxide or niobium oxide or a combination of at least two thereof. The metal oxide can be lithiated with residual lithium on the surface of the high-nickel cathode material to synthesize the lithium metal oxide.
In a preferred embodiment of the present invention, the first lithium source is added in an amount of 500-2000ppm based on the mass of the high nickel positive electrode material in step (1). For example, 500ppm, 750ppm, 1000ppm, 1250ppm, 1500ppm, 1750ppm or 2000ppm, etc., but is not limited to the numerical values recited, and other numerical values not recited in the numerical value range are also applicable. In the invention, if the first lithium source is added too much, the residual alkali on the surface of the material is higher; if too little first lithium source is added, the extent of sufficient reaction with the metal oxide will be affected.
Preferably, the amount of the metal oxide added in step (1) is 500-2000ppm, such as 500ppm, 750ppm, 1000ppm, 1250ppm, 1500ppm, 1750ppm or 2000ppm, based on the mass of the high nickel cathode material, but is not limited to the recited values, and other values not recited in the range of the values are also applicable. In the invention, if the metal oxide is added too much, the surface coating layer is too thick, and the discharge capacity of the material is influenced; if too little metal oxide is added, the extent of reaction with surface residual lithium is affected.
Preferably, the sintering temperature in step (1) is 500-800 ℃, such as 500 ℃, 600 ℃, 700 ℃ or 800 ℃, but not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the sintering time in step (1) is 5-10h, such as 5h, 6h, 7h, 8h, 9h or 10h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the sintering of step (1) is performed in an atmosphere furnace.
Preferably, the sintering of step (1) is performed in an oxygen atmosphere.
As a preferred embodiment of the present invention, the concentration of the acid solution in the step (2) is 0.05 to 0.1mol/L, for example, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L or 0.1mol/L, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable. Here, if the acid solution concentration is too high, surface structure destruction may be caused; if the acid solution concentration is too low, it may result in insufficient reaction with surface residual alkali.
Preferably, the acid of step (2) comprises H2MoO4，H2WO4，H3BO3Or H3PO4Any one or a combination of at least two of them. The acid of the kind can react with LiOH and Li on the surface of the high-nickel cathode material2CO3Reaction not only reduces the alkalinity of the material and improves the processing performance of the material, but also Li formed by the reaction2MoO3，Li2WO4，LiBO2，Li3PO4The lithium ion conductor is attached to the surface of the material, so that the product performance can be improved.
Preferably, in the step (2), the solid-liquid mass ratio of the sintered product to the acid solution is 1.0 to 1.5, for example, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
The reaction in step (2) is accompanied by stirring.
Preferably, the stirring speed is 500-2000r/min, such as 500r/min, 800r/min, 1000r/min, 1200r/min, 1500r/min, 1750r/min or 2000r/min, but not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the reaction time in step (2) is 30-60min, such as 30min, 40min, 50 min, 60min, etc., but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature for evaporating in step (2) is 80-120 deg.C, such as 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C or 120 deg.C, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, said evaporating to dryness in step (2) is heated with an oil bath or water bath.
Preferably, the sintering temperature in step (2) is 200-500 ℃, such as 200 ℃, 300 ℃, 400 ℃ or 500 ℃, but not limited to the recited values, and other unrecited values within the range of values are equally applicable.
Preferably, the sintering time in step (2) is 3-10h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the sintering of step (2) is carried out at a temperature increase rate of 1-3 deg.C/min, such as 1 deg.C/min, 1.5 deg.C/min, 2 deg.C/min, 2.5 deg.C/min, or 3 deg.C/min, but not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the sintering of step (2) is performed in an atmosphere furnace.
Preferably, the sintering of step (2) is performed in an oxygen atmosphere and/or an air atmosphere.
Preferably, the step (2) further comprises crushing the sintered product.
As a preferable technical scheme of the invention, the high-nickel positive electrode material in the step (1) is a high-nickel single crystal positive electrode material. The single crystal material is adopted because the high-nickel single crystal material has wide application prospect in the field of future power batteries, but the material has the defects of high surface residual alkali, low first coulombic efficiency and the like which need to be improved.
As a preferable technical scheme of the invention, the high-nickel single crystal cathode material is prepared according to the following method:
(1') synthesizing a high-nickel precursor;
(1 ') mixing a second lithium source with the high-nickel precursor in the step (1') and sintering to obtain the high-nickel single-crystal cathode material.
Preferably, the method of synthesis in step (1') is a coprecipitation method.
Preferably, the high nickel precursor of step (1') has the chemical formula of Ni1-x-yCoxMny(OH)2Where 0 < x.ltoreq.0.10, e.g.x is 0.01, 0.02, 0.04, 0.06, 0.08 or 0.1 etc., 0. ltoreq.y.ltoreq.0.15, e.g.y is 0, 0.2, 0.4, 0.6, 0.8, 0.9, 1.0, 1.1, 1.3 or 1.5 etc.
Preferably, the high nickel precursor in step (1') has a median particle size of 2.0-4.0 μm, such as 2.0 μm, 2.5 μm, 3.0 μm, 3.5 μm, or 4.0 μm, but not limited to the recited values, and other values not recited in the range of values are also applicable, and the use of the above-mentioned precursor with a median particle size is advantageous for the synthesis of a single crystal high nickel cathode material.
Preferably, in step (1 "), the second lithium source comprises any one of lithium hydroxide, lithium nitrate or lithium carbonate, or a combination of at least two thereof.
Preferably, in step (1 "), the molar ratio of the second lithium source to the high nickel precursor is 1.05-1.10, such as 1.05:1, 1.06:1, 1.07:1, 1.08:1, 1.09:1, or 1.10:1, but not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, the sintering temperature in step (1') is 850-.
Preferably, the sintering time in step (1') is 8-12h, such as 8h, 9h, 10h, 11h, or 12h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
As a further preferable technical scheme of the preparation method, the method comprises the following steps:
(1') synthesizing a high nickel precursor by a coprecipitation method, wherein the chemical formula of the high nickel precursor is Ni1-x-yCoxMny(OH)2Wherein x is more than 0 and less than or equal to 0.10 and 0Y is not less than 0.15, and the median particle size of the high-nickel precursor is 2.0-4.0 mu m;
(1 ') mixing a second lithium source with the high-nickel precursor in the step (1') according to a molar ratio of 1.05:1-1.10:1, and sintering at 850-1000 ℃ for 8-12h to obtain the high-nickel single-crystal positive electrode material, wherein the chemical formula of the high-nickel single-crystal positive electrode material is LiNi1-x-yCoxMnyO2Wherein x is more than 0 and less than or equal to 0.10, and y is more than or equal to 0 and less than or equal to 0.15;
(1) mixing the high-nickel anode material, the first lithium source and the metal oxide in the step (1'), and sintering for 5-10h at the temperature of 500-800 ℃ in an atmosphere furnace to obtain a sintered product;
wherein the addition amount of the first lithium source is 500-2000ppm and the addition amount of the metal oxide is 500-2000ppm based on the mass of the high-nickel cathode material;
(2) mixing the sintered product in the step (1) with an acid solution with the concentration of 0.05-0.1mol/L, reacting under stirring at the rotating speed of 500-;
wherein the solid-liquid mass ratio of the sintered product to the acid solution is 1.0-1.5.
In a second aspect, the present invention provides a high nickel positive electrode material with repaired surface structure obtained by the method of the first aspect.
Preferably, the high-nickel cathode material is a high-nickel single-crystal cathode material.
In a third aspect, the present invention provides a lithium ion battery comprising the high nickel cathode material according to the second aspect.
Compared with the prior art, the invention has the following beneficial effects:
in the method provided by the invention, lithium hydroxide and metal oxide are added, wherein the lithium hydroxide can be mixed with Ni on the surface of the high-nickel cathode material in the sintering processxO and other impurities react to generate layered lithium metal oxide, and the metal oxide can react with residual lithium salt(s) on the surface of the high-nickel cathode materialLiOH and Li2CO3) The lithium metal oxide is synthesized by chemical synthesis, after sintering, not only can the impurity phase on the surface of the matrix be eliminated, but also a protective layer is formed on the surface of the matrix, so that the matrix material is protected, and the corrosion of the matrix material during the next acid treatment is avoided; then adding acid solution with specific concentration, wherein the acid is mainly combined with residual LiOH and Li on the surface of the material2CO3Reaction to reduce the alkalinity of the material and improve the processability of the material, and Li formed by the reaction2MoO3，Li2WO4，LiBO2，Li3PO4The lithium ion conductor is attached to the surface of the material, and has a high lithium ion diffusion coefficient, so that the coulomb efficiency of the material can be improved, and the cycle performance of the material can be improved. The first discharge capacity of the high-nickel anode material with the surface structure repaired by the method provided by the invention can reach 216mAh/g, the first coulombic efficiency can reach 91%, the discharge retention rate of 2.0C discharge compared with 0.5C discharge can reach 94.5%, and the capacity retention rate after 50-week circulation can reach 97%.
Drawings
FIG. 1 is an SEM image of a precursor prepared in example 1;
FIG. 2 is an SEM image of the surface structure-repaired high-nickel single-crystal positive electrode material obtained in example 1;
FIG. 3 is an XRD pattern of the high nickel single crystal positive electrode material with repaired surface structure obtained in example 1;
FIG. 4 is an SEM image of the high-nickel single-crystal cathode material with the surface structure repaired obtained in example 2;
FIG. 5 is an XRD pattern of the high nickel single crystal cathode material with repaired surface structure obtained in example 2;
FIG. 6 is an SEM image of the high-nickel single-crystal cathode material with the surface structure repaired obtained in example 3;
FIG. 7 is an SEM image of a high nickel single crystal positive electrode material obtained in comparative example 1;
fig. 8 is an SEM image of the high nickel single crystal positive electrode material obtained in comparative example 2.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The following are typical but non-limiting examples of the invention:
example 1
The embodiment provides a method for repairing a surface structure of a high-nickel single-crystal cathode material, which comprises the following steps:
(1) carrying out coprecipitation reaction on a mixed solution containing nickel sulfate, cobalt sulfate and manganese sulfate, 8mol/L sodium hydroxide solution and 13.3mol/L ammonia water solution, wherein the molar ratio of Ni, Co and Mn is 8.3:1.1:0.6, so as to obtain a nickel cobalt manganese hydroxide precursor with D50 being 3.5 mu m;
(2) uniformly mixing the precursor obtained in the step (1) with lithium hydroxide (the molar ratio of the lithium hydroxide to the precursor is 1.05:1), and sintering at 880 ℃ for 10h to obtain the high-nickel single-crystal positive electrode material (the chemical formula is LiNi) serving as a matrix8.3Co1.1Mn0.6O2)；
(3) And (3) uniformly mixing the high-nickel single crystal positive electrode material serving as the matrix obtained in the step (2), 500ppm of lithium hydroxide and 1000ppm of aluminum oxide, and sintering at 750 ℃ for 5 hours in an oxygen atmosphere to obtain the secondary sintering material.
(4) And (3) adding the secondary sintering material obtained in the step (3) into a molybdic acid solution with the concentration of 0.05mol/L (the solid-liquid mass ratio of the secondary sintering material to the acid solution is 1.1), stirring and reacting for 30min at 1000r/min, then performing oil bath evaporation at 100 ℃, putting the mixture into an atmosphere furnace, heating to 450 ℃ at the heating rate of 2 ℃/min in the air atmosphere, sintering for 5h, and crushing to obtain the high-nickel single crystal anode material with the surface structure repaired.
The observation of a scanning electron microscope shows that the particle morphology of the cathode material is single crystal particles, the particles are uniformly distributed, the median particle size is 4.0 mu m, and the specific surface area is 0.45m2(ii)/g, powder compacted density is 3.0g/cm3。
The electrochemical performance test results of the high nickel cathode material with the repaired surface structure obtained in this example are shown in table 1.
Fig. 1 is an SEM image of the precursor prepared in step (1) of this example, and it can be seen from the SEM image that the volume particle size D50 of the precursor is substantially around 3.5 μm, and the particle size distribution is concentrated.
Fig. 2 is an SEM image of the high nickel single crystal cathode material with repaired surface structure obtained in this example, and it can be seen from the SEM image that the surface of the material is uniformly coated with a nano-scale coating layer.
Fig. 3 is an XRD pattern of the high nickel single crystal positive electrode material with repaired surface structure obtained in this example, from which it can be seen that the structure of the matrix is not changed by surface coating, and at the same time, the diffraction peak of lithium molybdate can be seen, and the lithium molybdate coating layer is indeed present on the surface of the material.
Example 2
The embodiment provides a method for repairing a surface structure of a high-nickel single-crystal cathode material, which comprises the following steps:
(1) the precursor obtained in the step (1) of example 1 and lithium hydroxide were uniformly mixed (molar ratio of lithium hydroxide to precursor was 1.05:1), and the mixture was sintered at 880 ℃ for 10 hours to obtain a high-nickel single-crystal positive electrode material (chemical formula LiNi) as a substrate8.3Co1.1Mn0.6O2)；
(2) And (2) uniformly mixing the high-nickel single crystal positive electrode material serving as the matrix obtained in the step (1), 500ppm of lithium hydroxide and 1000ppm of zirconium oxide, and sintering at 750 ℃ for 8 hours in an oxygen atmosphere to obtain the secondary sintering material.
(3) And (3) adding the secondary sintering material obtained in the step (2) into a tungstic acid solution with the concentration of 0.05mol/L (the solid-to-liquid ratio of the secondary sintering material to an acid solution is 1.1), stirring and reacting at 1000r/min for 30min, then performing oil bath evaporation at 100 ℃, putting the mixture into an atmosphere furnace, heating to 500 ℃ at the heating rate of 2 ℃/min in the air atmosphere, sintering for 5h, and crushing to obtain the high-nickel single crystal anode material with the surface structure repaired.
The observation of a scanning electron microscope shows that the particle morphology of the cathode material is single crystal particles, the particles are uniformly distributed, the median particle size is 4.5 mu m, and the specific surface area is 0.65m2(ii)/g, powder compacted density is 3.1g/cm3。
The electrochemical performance test results of the high nickel cathode material with the repaired surface structure obtained in this example are shown in table 1.
Fig. 4 is an SEM image of the high nickel single crystal positive electrode material with repaired surface structure obtained in this example, and it can be seen from the SEM image that there is a discontinuous coating layer on the surface of the material.
Fig. 5 is an XRD pattern of the high nickel single crystal cathode material with repaired surface structure obtained in this example, from which it can be seen that the matrix structure of the material is not changed, and simultaneously, a diffraction peak of lithium tungstate with a certain intensity is present, indicating that a lithium tungstate coating layer is successfully formed on the surface of the material.
Example 3
The embodiment provides a method for repairing a surface structure of a high-nickel single-crystal cathode material, which comprises the following steps:
(1) the precursor obtained in the step (1) of example 1 and lithium hydroxide were uniformly mixed (molar ratio of lithium hydroxide to precursor was 1.05:1), and the mixture was sintered at 880 ℃ for 10 hours to obtain a high-nickel single-crystal positive electrode material (chemical formula LiNi) as a substrate8.3Co1.1Mn0.6O2)；
(2) And (2) uniformly mixing the high-nickel single crystal positive electrode material serving as the matrix obtained in the step (1), 500ppm of lithium hydroxide and 1000ppm of titanium oxide, and sintering at 750 ℃ in an oxygen atmosphere for 10 hours to obtain the secondary sintering material.
(3) And (3) adding the secondary sintering material obtained in the step (2) into a boric acid solution with the concentration of 0.1mol/L (the solid-to-liquid ratio of the secondary sintering material to the acid solution is 1.5), stirring and reacting for 30min at 1000r/min, then performing oil bath evaporation at 100 ℃, putting the mixture into an atmosphere furnace, heating to 500 ℃ at the heating rate of 2 ℃/min in the air atmosphere, sintering for 5h, and crushing to obtain the high-nickel single crystal anode material with the surface structure repaired.
The observation of a scanning electron microscope shows that the particle morphology of the cathode material is single crystal particles, the particles are uniformly distributed, the median particle size is 5.0 mu m, and the specific surface area is 0.50m2(g), the powder compacted density is 2.9g/cm3。
The electrochemical performance test results of the high nickel cathode material with the repaired surface structure obtained in this example are shown in table 1.
Fig. 6 is an SEM image of the high nickel single crystal positive electrode material with the repaired surface structure obtained in this example, and it can be seen from the SEM image that a continuous and uniform coating layer is formed on the surface of the material.
Example 4
The embodiment provides a method for repairing a surface structure of a high-nickel single-crystal cathode material, which comprises the following steps:
(1) the high nickel single crystal positive electrode material (chemical formula LiNi) obtained in example 1 as a substrate was used8.3Co1.1Mn0.6O2) And uniformly mixing 1000ppm of lithium hydroxide and 500ppm of titanium oxide, and sintering at 500 ℃ in an oxygen atmosphere for 10 hours to obtain the secondary sintering material.
(2) And (2) adding the secondary sintering material obtained in the step (1) into a molybdic acid solution with the concentration of 0.07mol/L (the solid-liquid mass ratio of the secondary sintering material to the acid solution is 1.1), stirring at 500r/min for reaction for 45min, then performing oil bath evaporation at 80 ℃ to dryness, putting the mixture into an atmosphere furnace, heating to 200 ℃ at the heating rate of 1 ℃/min in an oxygen atmosphere, sintering for 10h, and crushing to obtain the high-nickel single crystal anode material with the surface structure repaired.
The electrochemical performance test results of the high nickel cathode material with the repaired surface structure obtained in this example are shown in table 1.
Example 5
The embodiment provides a method for repairing a surface structure of a high-nickel single-crystal cathode material, which comprises the following steps:
(1) the high nickel single crystal positive electrode material (chemical formula LiNi) obtained in example 1 as a substrate was used8.3Co1.1Mn0.6O2) Uniformly mixing 2000ppm of lithium hydroxide and 2000ppm of titanium oxide, and sintering at 800 ℃ in an oxygen atmosphere for 5 hours to obtain the secondary sintering material.
(2) And (2) adding the secondary sintering material obtained in the step (1) into a molybdic acid solution with the concentration of 0.06mol/L (the solid-liquid mass ratio of the secondary sintering material to the acid solution is 1.0), stirring at 2000r/min for reaction for 60min, then performing oil bath evaporation at 120 ℃ to dryness, putting the mixture into an atmosphere furnace, heating to 480 ℃ at the heating rate of 3 ℃/min in the air atmosphere, sintering for 3h, and crushing to obtain the high-nickel single crystal anode material with the surface structure repaired.
The electrochemical performance test results of the high nickel cathode material with the repaired surface structure obtained in this example are shown in table 1.
Example 6
Referring to example 1, the method for repairing the surface structure of the high-nickel single-crystal cathode material in the embodiment is different in that the ratio of nickel sulfate, cobalt sulfate and manganese sulfate in step (1) is such that the molar ratio of Ni, Co and Mn is 0.75:0.1:0.15, and D50 of the precursor is controlled to be 2.0 μm; in the step (2), the molar ratio of the lithium hydroxide to the precursor is 1.08:1, the sintering temperature is 850 ℃, and the sintering time is 12 hours.
The electrochemical performance test results of the high nickel cathode material with the repaired surface structure obtained in this example are shown in table 1.
Example 7
Referring to example 1, the method for repairing the surface structure of the high-nickel single-crystal cathode material in the embodiment is different in that the ratio of nickel sulfate, cobalt sulfate and manganese sulfate in step (1) is such that the molar ratio of Ni, Co and Mn is 0.94:0.05:0.01, and D50 of the precursor is controlled to be 4.0 μm; in the step (2), the molar ratio of the lithium hydroxide to the precursor is 1.10:1, the sintering temperature is 1000 ℃, and the sintering time is 8 hours.
The electrochemical performance test results of the high nickel cathode material with the repaired surface structure obtained in this example are shown in table 1.
Comparative example 1
The comparative example provides a method for repairing a surface structure of a high-nickel single-crystal positive electrode material, which comprises the following steps:
(1) the precursor obtained in the step (1) of example 1 and lithium hydroxide were uniformly mixed (molar ratio of lithium hydroxide to precursor was 1.05:1), and the mixture was sintered at 880 ℃ for 10 hours to obtain a high-nickel single-crystal positive electrode material (chemical formula LiNi) as a substrate8.3Co1.1Mn0.6O2)；
(2) And (2) uniformly mixing the high-nickel single crystal positive electrode material serving as the matrix obtained in the step (1), 500ppm of lithium hydroxide and 1000ppm of aluminum oxide, and sintering at 750 ℃ for 5 hours in an oxygen atmosphere to obtain a secondary sintered material serving as a positive electrode material product.
The observation of a scanning electron microscope shows that the particle morphology of the cathode material is secondary particles, the particles are uniformly distributed, the median particle size is 4.0 mu m, and the specific surface area is 0.36m2(ii)/g, powder compacted density is 3.1g/cm3；
The results of the electrochemical performance test of the high nickel cathode material obtained in this comparative example are shown in table 1.
Fig. 7 is an SEM image of the high nickel single crystal positive electrode material obtained in the present comparative example, from which it can be seen that an aluminum compound clad layer is present on the surface of the material.
Comparative example 2
The comparative example provides a method for repairing a surface structure of a high-nickel single-crystal positive electrode material, which comprises the following steps:
(1) the precursor obtained in the step (1) of example 1 and lithium hydroxide were uniformly mixed (molar ratio of lithium hydroxide to precursor was 1.05:1), and the mixture was sintered at 880 ℃ for 10 hours to obtain a high-nickel single-crystal positive electrode material (chemical formula LiNi) as a substrate8.3Co1.1Mn0.6O2)；
(2) And (2) uniformly mixing the high-nickel single crystal positive electrode material serving as the matrix obtained in the step (1), 500ppm of lithium hydroxide and 1000ppm of zirconium oxide, and sintering at 750 ℃ for 5 hours in an oxygen atmosphere to obtain a secondary sintered material serving as a positive electrode material product.
The observation of a scanning electron microscope shows that the particle morphology of the cathode material is secondary particles, the particles are uniformly distributed, the median particle size is 4.5 mu m, and the specific surface area is 0.48m2(ii)/g, powder compacted density is 3.0g/cm3；
The results of the electrochemical performance test of the high nickel cathode material obtained in this comparative example are shown in table 1.
Fig. 8 is an SEM image of the high nickel single crystal positive electrode material obtained in the present comparative example, from which it can be seen that a zirconium compound coating layer is present on the surface of the material.
Comparative example 3
The operation of the comparative example refers to example 1, and the difference is only that the operation of the step (4) is that the secondary sintering material obtained in the step (3) is put into an atmosphere furnace and is heated to 450 ℃ at the heating rate of 2 ℃/min in the air atmosphere for sintering for 5h, and the secondary sintering material is crushed to obtain the treated high-nickel single crystal cathode material.
The results of the electrochemical performance test of the high nickel cathode material obtained in this comparative example are shown in table 1.
Comparative example 4
The operation of this comparative example is as in example 1 except that in step (3), no lithium hydroxide is added.
The results of the electrochemical performance test of the high nickel cathode material obtained in this comparative example are shown in table 1.
Comparative example 5
The operation of this comparative example is as in example 1 except that in step (3), no alumina is added.
The results of the electrochemical performance test of the high nickel cathode material obtained in this comparative example are shown in table 1.
Comparative example 6
This comparative example was subjected to electrochemical performance test using the high nickel single crystal positive electrode material obtained in step (2) of example 1 as a base, and the results thereof are shown in table 1.
Performance test method
The cathode material finally obtained in each example and comparative example is used as a cathode active substance to prepare a lithium ion battery, and the preparation method comprises the steps of mixing the cathode active substance, the PVDF binder and the SP conductive agent in the NMP according to the ratio of 96:2:2 to obtain slurry, controlling the solid content to be 70%, and coating the slurry on an aluminum foil to obtain a cathode; a lithium sheet is used as a negative electrode; using 1mol/L LiPF6Button cells were prepared from the electrolyte/EC + DMC + EMC (v/v ═ 1:1:1) and Celgard2400 separator. Electrochemical tests were performed with this cell.
And (3) adopting a blue battery test system, carrying out 0.1C/0.1C charge and discharge under the conditions of 25 ℃ and a voltage interval of 3.0-4.3V, and testing the first discharge capacity and the first coulombic efficiency.
A blue battery test system is adopted, 0.5C charging and 0.5C/1.0C/2.0C multiplying power discharging are respectively carried out under the conditions that the temperature is 25 ℃ and the voltage range is 3.0-4.3V, and the discharge capacity retention ratio of 2.0C/0.5C is tested.
A blue battery test system is adopted, charging is carried out at 0.5C under the condition that the temperature is 25 ℃ and the voltage range is 3.0-4.3V, discharging is carried out at 1.0C, and the capacity retention ratio after 50-week circulation is tested.
The test results are given in the following table:
TABLE 1
Combining the above examples and comparative examples, it can be seen that the surface structure repairing methods of examples 1-7 first remove a portion of the impurity phase on the surface of the material and form a protective layer on the surface of the material by the respective synthesis reactions of the first lithium source and the metal oxide with the nickel oxide and the residual lithium on the surface of the material; and then weak acid is utilized to further remove impurities on the surface of the material, and a lithium ion conductor coating layer is formed on the surface of the material, so that the discharge capacity and the first effect of the battery are improved, and the cycle performance and the safety performance are improved.
The comparative examples 1 and 2 do not carry out the mixing reaction of the sintered product and the acid solution, evaporation to dryness and subsequent sintering operation, which results in higher surface residual lithium salt and influences the processing performance, discharge capacity and capacity retention rate of the material.
Comparative example 3 although the subsequent sintering operation was performed, the previous operation of mixing the secondary sintered product with an acid solution was not performed, resulting in low ionic conductivity, affecting discharge capacity and cycle retention at high rate.
Comparative example 4, in which the first lithium source was not added, resulted in a material having a reduced discharge capacity compared to example 1 and poor cycle and rate performance.
Comparative example 5 no metal oxide was added, resulting in a higher residual lithium on the surface of the material, affecting processability, and poor rate capability and cycle performance.
Comparative example 6 does not perform surface structure repair on the high nickel single crystal positive electrode material, and thus its performance is inferior to examples 1 to 3 in various aspects.
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. A method for repairing the surface structure of a high-nickel cathode material is characterized by comprising the following steps:
(1) mixing a high-nickel positive electrode material, a first lithium source and a metal oxide, and sintering to obtain a sintered product;
(2) and (2) mixing the sintered product obtained in the step (1) with an acid solution, reacting, evaporating to dryness, and sintering to obtain the high-nickel cathode material with the repaired surface structure.
2. The method of claim 1, wherein the high nickel cathode material of step (1) has a chemical formula of LiNi1-x-yCoxMnyO2Wherein x is more than 0 and less than or equal to 0.10, and y is more than or equal to 0 and less than or equal to 0.15;
preferably, the first lithium source of step (1) comprises any one of lithium hydroxide, lithium acetate or lithium nitrate or a combination of at least two thereof;
preferably, the metal oxide in step (1) comprises any one of alumina, titania, zirconia, yttria, cobalt oxide, molybdenum oxide or niobium oxide or a combination of at least two thereof.
3. The method as set forth in claim 1 or 2, wherein the first lithium source is added in an amount of 500-2000ppm based on the mass of the high nickel positive electrode material in step (1);
preferably, the addition amount of the metal oxide is 500-2000ppm based on the mass of the high-nickel cathode material in the step (1);
preferably, the sintering temperature in the step (1) is 500-800 ℃;
preferably, the sintering time in the step (1) is 5-10 h;
preferably, the sintering of step (1) is carried out in an atmosphere furnace;
preferably, the sintering of step (1) is performed in an oxygen atmosphere.
4. The method according to any one of claims 1 to 3, wherein the concentration of the acid solution in the step (2) is 0.05 to 0.1 mol/L;
preferably, the acid of step (2) comprises H2MoO4，H2WO4，H3BO3Or H3PO4Any one or a combination of at least two of;
preferably, in the step (2), the solid-liquid mass ratio of the sintered product to the acid solution is 1.0 to 1.5.
5. The process according to any one of claims 1 to 4, wherein the reaction in step (2) is accompanied by stirring;
preferably, the rotation speed of the stirring is 500-;
preferably, the reaction time of the step (2) is 30-60 min;
preferably, the temperature for evaporating in the step (2) is 80-120 ℃;
preferably, said evaporating to dryness of step (2) is heated with an oil bath or water bath;
preferably, the sintering temperature in the step (2) is 200-500 ℃;
preferably, the sintering time in the step (2) is 3-10 h;
preferably, the temperature rise rate of the sintering in the step (2) is 1-3 ℃/min;
preferably, the sintering of step (2) is carried out in an atmosphere furnace;
preferably, the sintering of step (2) is performed in an oxygen atmosphere and/or an air atmosphere;
preferably, the step (2) further comprises crushing the sintered product.
6. The method according to any one of claims 1 to 5, wherein the high nickel cathode material of step (1) is a high nickel single crystal cathode material.
7. The method of claim 6, wherein the high nickel single crystal positive electrode material is prepared as follows:
(1') synthesizing a high-nickel precursor;
(1 ') mixing a second lithium source with the high-nickel precursor in the step (1') and sintering to obtain the high-nickel single-crystal positive electrode material;
preferably, the method of synthesis in step (1') is a coprecipitation method;
preferably, the high nickel precursor of step (1') has the chemical formula of Ni1-x-yCoxMny(OH)2Wherein x is more than 0 and less than or equal to 0.10, and y is more than or equal to 0 and less than or equal to 0.15;
preferably, the high nickel precursor of step (1') has a median particle size of from 2.0 to 4.0 μm;
preferably, in step (1 "), the second lithium source comprises any one of lithium hydroxide, lithium nitrate or lithium carbonate or a combination of at least two thereof;
preferably, in step (1 "), the molar ratio of the second lithium source to the high nickel precursor is from 1.05:1 to 1.10: 1;
preferably, the sintering temperature in step (1') is 850-1000 ℃;
preferably, the sintering time in step (1') is 8-12 h.
8. The method according to any one of claims 1-7, characterized in that the method comprises the steps of:
(1') synthesizing a high nickel precursor by a coprecipitation method, wherein the chemical formula of the high nickel precursor is Ni1-x-yCoxMny(OH)2Wherein x is more than 0 and less than or equal to 0.10, y is more than or equal to 0 and less than or equal to 0.15, and the median particle size of the high-nickel precursor is 2.0-4.0 mu m;
(1') subjectingMixing a second lithium source with the high-nickel precursor in the step (1') according to a molar ratio of 1.05:1-1.10:1, and sintering at 850-1000 ℃ for 8-12h to obtain a high-nickel single-crystal positive electrode material, wherein the chemical formula of the high-nickel single-crystal positive electrode material is LiNi1-x- yCoxMnyO2Wherein x is more than 0 and less than or equal to 0.10, and y is more than or equal to 0 and less than or equal to 0.15;
(1) mixing the high-nickel anode material, the first lithium source and the metal oxide in the step (1'), and sintering for 5-10h at the temperature of 500-800 ℃ in an atmosphere furnace to obtain a sintered product;
wherein the addition amount of the first lithium source is 500-2000ppm and the addition amount of the metal oxide is 500-2000ppm based on the mass of the high-nickel cathode material;
(2) mixing the sintered product in the step (1) with an acid solution with the concentration of 0.05-0.1mol/L, reacting under stirring at the rotating speed of 500-;
wherein the solid-liquid mass ratio of the sintered product to the acid solution is 1.0-1.5.
9. A surface-structure-repaired high nickel positive electrode material obtained by the method of any one of claims 1 to 8.
10. A lithium ion battery comprising the high nickel positive electrode material of claim 9.
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| PCT/CN2020/112971 WO2021114746A1 (en) | 2019-12-11 | 2020-09-02 | Method for repairing surface structure of high-nickel positive electrode material, high-nickel positive electrode material obtained therefrom, and lithium ion battery |
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Family Cites Families (11)
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| CN103247797B (en) * | 2013-05-20 | 2015-10-28 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of anode material for lithium-ion batteries and preparation method thereof |
| JP6248639B2 (en) * | 2014-01-07 | 2017-12-20 | 日立金属株式会社 | Positive electrode active material for lithium ion secondary battery, positive electrode for lithium ion secondary battery and lithium ion secondary battery using the same, and method for producing positive electrode active material for lithium ion secondary battery |
| CN105185954B (en) * | 2015-06-17 | 2018-10-16 | 电子科技大学 | A kind of LiAlO2Coat LiNi1-xCoxO2Anode material for lithium-ion batteries and preparation method thereof |
| CN105070896B (en) * | 2015-07-03 | 2017-09-01 | 湖南杉杉新能源有限公司 | Nickelic polynary positive pole material of secondary lithium batteries and preparation method thereof |
| CN108206277A (en) * | 2016-12-20 | 2018-06-26 | 宁德时代新能源科技股份有限公司 | Modified high-nickel ternary cathode material, preparation method thereof and lithium ion battery |
| CN108206278A (en) * | 2016-12-20 | 2018-06-26 | 宁德时代新能源科技股份有限公司 | Modified lithium ion battery positive electrode material, preparation method thereof and lithium ion battery |
| CN107871864B (en) * | 2017-04-27 | 2020-12-18 | 乳源东阳光磁性材料有限公司 | Titanium modified high-nickel multi-element positive electrode material and preparation method thereof |
| JP7273262B2 (en) * | 2018-02-07 | 2023-05-15 | 住友金属鉱山株式会社 | Coated positive electrode active material for lithium ion secondary battery, method for producing the same, and evaluation method for the coated positive electrode active material |
| CN108598400B (en) * | 2018-04-11 | 2020-12-04 | 桑顿新能源科技有限公司 | Three-layer core-shell structure cathode material, preparation method and lithium ion battery |
| CN109244416A (en) * | 2018-09-29 | 2019-01-18 | 北京泰丰先行新能源科技有限公司 | A method of improving the nickelic ternary material chemical property of lithium ion battery |
| CN109950498A (en) * | 2019-03-29 | 2019-06-28 | 宁波容百新能源科技股份有限公司 | A kind of nickelic positive electrode and preparation method thereof with uniform clad |
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| CN113753971A (en) * | 2021-09-29 | 2021-12-07 | 蜂巢能源科技有限公司 | Single crystal ternary cathode material and preparation method and application thereof |
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| CN116093332A (en) * | 2023-04-07 | 2023-05-09 | 四川新能源汽车创新中心有限公司 | High-nickel positive electrode material, preparation method thereof and lithium ion battery |
| CN116093332B (en) * | 2023-04-07 | 2023-12-05 | 四川新能源汽车创新中心有限公司 | High-nickel positive electrode material, preparation method thereof and lithium ion battery |
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