CN110581269A - Lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material and preparation method thereof - Google Patents

Lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material and preparation method thereof Download PDF

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CN110581269A
CN110581269A CN201910952126.1A CN201910952126A CN110581269A CN 110581269 A CN110581269 A CN 110581269A CN 201910952126 A CN201910952126 A CN 201910952126A CN 110581269 A CN110581269 A CN 110581269A
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phosphate
single crystal
nickel single
crystal ternary
lithium ion
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原长洲
张文衡
梁龙伟
赵飞
葛凤跃
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University of Jinan
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of preparation of new energy lithium ion battery cathode materials, and particularly relates to a preparation method of a lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material. Firstly, dissolving phosphate in distilled water, and uniformly stirring until the phosphate is completely dissolved to obtain a phosphate solution; then dispersing the high-nickel single crystal ternary precursor in phosphate solution, and uniformly mixing to obtain mixed suspension; and finally, stirring the obtained mixed suspension at a high temperature and drying water to obtain a precipitate. And mixing lithium, grinding and calcining the dried precipitate in pure oxygen to obtain the lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material. The surface of the high-nickel single crystal ternary cathode material for the lithium ion battery prepared by the method is uniformly coated with a layer of lithium phosphate. The prepared material has better specific capacity, rate capability and cycling stability, effectively prolongs the service life of the lithium ion battery and has excellent cost performance advantage.

Description

Lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of new energy lithium ion battery cathode materials, and particularly relates to a preparation method of a lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material.
Technical Field
the lithium ion battery has the advantages of high energy density, high working voltage, excellent cycle performance and the like, and is widely applied to various new energy fields such as portable electronic products, hybrid electric vehicles and pure electric vehicles. With the development of the electric automobile industry, higher requirements are put forward on the energy density and the cycle life of the lithium ion battery.
Ni-based ternary positive electrode material LiNixCoyMnzO2(x + y + z =1), in particular x>0.8, has higher working voltage (>4.3 V vs. Li/Li+) And a theoretical specific discharge capacity of up to 200 mAh/g, and has been widely regarded and studied. However, in the process of lithium ion desorption and intercalation of the traditional high-nickel ternary cathode material, secondary particles are crushed and pulverized; in addition, the cycle performance is degraded by a serious elution of transition metal ions. The former can reduce the phenomena of crushing and pulverization by changing the micro-morphology of the high-nickel ternary cathode material, and the latter can be relieved by coating a physical protective layer on the surface. The high coating method commonly used commercially today is solid phase hybrid coating, which results in non-uniform coating. In the reported liquid phase coating method, most of the high nickel ternary cathode material is dispersed in the aqueous solution of the coating material. During the coating process, the high nickel ternary cathode material reacts with water to form Li2CO3And LiOH impurities, which severely deteriorate the electrochemical performance of the material.
disclosure of Invention
in order to overcome the defects and shortcomings, the invention aims to provide a lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material, wherein the coating layer of the cathode material is uniform, and the stability of the material is enhanced.
The invention also aims to provide a preparation method of the material, which avoids the contact of the high-nickel ternary cathode material and water and reduces Li in the coating process by coating the single-crystal high-nickel ternary precursor2CO3And LiOH impurities are formed, so that the cycle performance of the material is effectively improved.
the purpose of the invention is realized by the following scheme:
A lithium phosphate coated lithium ion battery high-nickel single crystal ternary positive electrode material is disclosed, wherein the chemical formula of the high-nickel single crystal ternary positive electrode material is LiNi0.8Co0.1Mn0.1O2The particle size was 5 μm ~ 13 μm.
A preparation method of the lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material comprises the following steps:
(1) weighing phosphate, adding the phosphate into distilled water, and uniformly dispersing to obtain a phosphate solution;
(2) Adding a high-nickel single crystal ternary precursor Ni into the phosphate solution obtained in the step (1)0.8Co0.1Mn0.1(OH)2Uniformly mixing to obtain mixed suspension;
(3) Drying the mixed suspension prepared in the step (2) under the condition of stirring and heating to obtain a precipitate finally;
(4) weighing LiOH ∙ H monohydrate2O, carrying out solid phase grinding on the precipitate obtained in the step (3), and uniformly mixing to obtain a mixture;
(5) calcining the mixture in the step (4) in air and naturally cooling, and then calcining in pure oxygen step by step and naturally cooling to room temperature.
Preferably, the phosphate in the step (1) is relative to the high-nickel single crystal ternary precursor Ni in the step (2)0.8Co0.1Mn0.1(OH)2The molar ratio of (B) was 0.5 ~ 5%.
Preferably, the phosphate in step (1) is a mixture of 1 or more of sodium tripolyphosphate, sodium hexametaphosphate, ammonium phosphate trihydrate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate dihydrate and disodium hydrogen phosphate heptahydrate.
Preferably, the lithium hydroxide monohydrate LiOH ∙ H in the step (4)2the molar ratio of O to the precipitate obtained in step (3) is 1.03: 1 ~ 1.05.05: 1.
preferably, the calcination temperature of the calcination in air in the step (5) is 400 ~ 500oC, calcining for 3 ~ 5 h, and heating rate of 2oC/min。
Preferably, the pure oxygen of step (5) is calcined step by step, and the step by step calcination is firstly 500oKeeping the temperature for 4 hours under C, and then continuously increasing the temperature to 700 ~ 800oC, continuing to preserve heat for 12 hours at the temperature rising rate of 2oC/min。
Preferably, the specific preparation method comprises the following steps:
(1) Relative to high nickel single crystal ternary precursor Ni0.8Co0.1Mn0.1(OH)2weighing phosphate with the molar ratio of 0.5 ~ 5% and dissolving the phosphate in 50 mL of distilled water, and fully and uniformly stirring to obtain a phosphate solution;
(2) 5 g of high nickel single crystal ternary precursor Ni is added into the phosphate solution0.8Co0.1Mn0.1(OH)2Uniformly stirring and mixing to obtain a mixed suspension;
(3) Mixing the above mixed suspension at 100oC, drying water while stirring to finally obtain a precipitate;
(4) weighing LiOH ∙ H monohydrate2Mixing O with the precipitate obtained in the step (3), and grinding and mixing the mixture in a solid phase to obtain a mixture, wherein the lithium hydroxide monohydrate LiOH ∙ H2The molar ratio of O to the precipitate from the step is 1.03: 1 ~ 1.05.05: 1;
(5) the mixture obtained in step (4) is firstly treated with 400 ~ 500 in airoCalcining for 3 ~ 5 h under C, naturally cooling, and then calcining in pure oxygen atmosphere for 500 hoKeeping the temperature for 4 hours under C, and then continuously risingThe temperature is 700 ~ 800oC, keeping the temperature for 12 hours, naturally cooling, wherein the heating rate in the whole calcining process is 2oC/min。
Advantageous effects
1. The method for coating by using lithium phosphate is different from the common liquid phase coating method, the prepared coating layer is more uniform, and the stability of the material is enhanced.
2. according to the preparation method, the single-crystal high-nickel ternary precursor is coated, so that the structural stability of the material is improved and the cycle performance of the material is effectively improved on the premise of not changing the electrochemical performance of the material.
Drawings
FIG. 1 is an SEM image of (a) a conventional nickel-rich spherical ternary positive electrode material for a lithium ion battery on the market and (b) a nickel-rich single crystal ternary positive electrode material for a lithium ion battery used in the present invention;
FIG. 2 is an XRD pattern of a lithium ion battery high nickel single crystal ternary cathode material coated with lithium phosphate in examples 1-3 of the present invention;
FIG. 3 is a graph comparing the first pass efficiency of lithium ion button half cells made in examples 1 and 4 of the present invention and comparative examples 1 and 2;
FIG. 4 is a graph comparing the cycle performance of lithium ion button half cells made in examples 1 and 4 of the present invention and comparative examples 1 and 2;
FIG. 5 is a graph comparing rate performance of lithium ion button half cells fabricated in examples 1 and 4 of the present invention and comparative examples 1 and 2;
Fig. 6 is a graph comparing the cycle performance of the lithium ion pouch full cells fabricated in example 1 of the present invention and comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
example 1
(1) Relative to high nickel single crystal ternary precursor Ni0.8Co0.1Mn0.1(OH)2Weighing 0.0003 mol of sodium tripolyphosphate (0.5 mol%), dissolving in 50 mL of distilled water, and fully and uniformly stirring to obtain a sodium tripolyphosphate solution;
(2) 0.0541 mol of high-nickel single crystal ternary precursor Ni is added into the sodium tripolyphosphate solution0.8Co0.1Mn0.1(OH)2Uniformly stirring and mixing to obtain mixed suspension;
(3) Mixing the above mixed suspension at 100oC, drying water while stirring to finally obtain a precipitate;
(4) 0.0596 mol of lithium hydroxide monohydrate LiOH ∙ H is weighed2O, lithium hydroxide monohydrate LiOH ∙ H2The molar ratio of O to the precipitate is 1.05: 1, and the mixture is obtained by solid phase grinding and mixing;
(5) the mixture obtained is first of all in air 500oCalcining for 4 h under C, naturally cooling, and then 500 g in pure oxygen atmosphereokeeping the temperature for 4 hours under C, and then continuously increasing the temperature to 750oc, keeping the temperature for 12 hours, naturally cooling, wherein the heating rate in the whole calcining process is 2oC/min。
Example 2
(1) relative to high nickel single crystal ternary precursor Ni0.8Co0.1Mn0.1(OH)2Weighing 0.0016 mol of sodium hexametaphosphate (3% mol), dissolving in 50 mL of distilled water, and fully and uniformly stirring to obtain a sodium hexametaphosphate solution;
(2) 0.0541 mol of high-nickel single crystal ternary precursor Ni is added into the sodium hexametaphosphate solution0.8Co0.1Mn0.1(OH)2uniformly stirring and mixing to obtain mixed suspension;
(3) Mixing the above mixed suspension at 100oC, drying water while stirring to finally obtain a precipitate;
(4) Weighing 0.0854 mol of lithium hydroxide monohydrate LiOH ∙ H2O, lithium hydroxide monohydrate LiOH ∙ H2The molar ratio of O to the precipitate is 1.03: 1, and the mixture is obtained by solid phase grinding and mixing;
(5) The mixture obtained is first of all in air 400oCalcining for 3 h under C, naturally cooling, and then 500 g in pure oxygen atmosphereoKeeping the temperature for 4 hours under C, and then continuously heating to 700 DEG CoC, keeping the temperature for 12 hours, naturally cooling, wherein the heating rate in the whole calcining process is 2oC/min。
Example 3
(1) Relative to high nickel single crystal ternary precursor Ni0.8Co0.1Mn0.1(OH)2Weighing 0.0027 mol of NH4H2PO4(5% mol) is dissolved in 50 mL of distilled water and fully and uniformly stirred to obtain NH4H2PO4A solution;
(2) To the above-mentioned NH4H2PO40.0541 mol of high nickel single crystal ternary precursor Ni is added into the solution0.8Co0.1Mn0.1(OH)2Uniformly stirring and mixing to obtain mixed suspension;
(3) Mixing the above mixed suspension at 100oC, drying water while stirring to finally obtain a precipitate;
(4) Weighing 0.0647 mol of lithium hydroxide monohydrate LiOH ∙ H2O, lithium hydroxide monohydrate LiOH ∙ H2The molar ratio of O to the precipitate is 1.04: 1, and the mixture is obtained by solid phase grinding and mixing;
(5) The mixture obtained is first of all in air 500oCalcining for 5 h under C, naturally cooling, and then 500 g in pure oxygen atmosphereoKeeping the temperature for 4 hours under C, and then continuously heating to 800 DEG Coc, keeping the temperature for 12 hours, naturally cooling, wherein the heating rate in the whole calcining process is 2oC/min。
Example 4
(1) Relative to high nickel single crystal ternary precursor Ni0.8Co0.1Mn0.1(OH)2weighing 0.0011 mol of sodium tripolyphosphate (2% mol), dissolving in 50 mL of distilled water, and fully and uniformly stirring to obtain a sodium tripolyphosphate solution;
(2) 0.0541 mol of high-nickel single crystal tripolyphosphate is added into the sodium tripolyphosphate solutionElement precursor Ni0.8Co0.1Mn0.1(OH)2Uniformly stirring and mixing to obtain mixed suspension;
(3) Mixing the above mixed suspension at 100oC, drying water while stirring to finally obtain a precipitate;
(4) weighing 0.0672 mol of lithium hydroxide monohydrate LiOH ∙ H2o, lithium hydroxide monohydrate LiOH ∙ H2the molar ratio of O to the precipitate is 1.05: 1, and the mixture is obtained by solid phase grinding and mixing;
(5) the mixture obtained is first of all in air 500oCalcining for 4 h under C, naturally cooling, and then 500 g in pure oxygen atmosphereoKeeping the temperature for 4 hours under C, and then continuously increasing the temperature to 750oc, keeping the temperature for 12 hours, naturally cooling, wherein the heating rate in the whole calcining process is 2oC/min。
comparative example 1
(1) high nickel single crystal ternary precursor and lithium hydroxide monohydrate LiOH ∙ H2according to the molar ratio of 1: 1.05, 0.0541 mol of high-nickel single crystal ternary precursor Ni is weighed respectively0.8Co0.1Mn0.1(OH)2And 0.0569 mol of lithium hydroxide monohydrate LiOH ∙ H2O, grinding and mixing the solid phase to obtain a mixture;
(2) the mixture obtained is first of all in air 500oCalcining for 4 h under C, naturally cooling, and then 500 g in pure oxygen atmosphereokeeping the temperature for 4 hours under C, and then continuously increasing the temperature to 750oC, keeping the temperature for 12 hours, naturally cooling, wherein the heating rate in the whole calcining process is 2oC/min。
Comparative example 2
(1) Relative to high nickel single crystal ternary precursor Ni0.8Co0.1Mn0.1(OH)2Weighing 0.0076 mol of sodium tripolyphosphate (14% mol), dissolving in 50 mL of distilled water, and fully and uniformly stirring to obtain a sodium tripolyphosphate solution;
(2) 0.0541 mol of high-nickel single crystal ternary precursor Ni is added into the sodium tripolyphosphate solution0.8Co0.1Mn0.1(OH)2Uniformly stirring and mixing to obtain mixed suspension;
(3) Mixing the above mixed suspension at 100oC, drying water while stirring to finally obtain a precipitate;
(4) 0.1286 mol of lithium hydroxide monohydrate LiOH ∙ H is weighed2O, lithium hydroxide monohydrate LiOH ∙ H2The molar ratio of O to the precipitate is 1.05: 1, and the mixture is obtained by solid phase grinding and mixing;
(5) the mixture obtained is first of all in air 500oCalcining for 4 h under C, naturally cooling, and then 500 g in pure oxygen atmosphereoKeeping the temperature for 4 hours under C, and then continuously increasing the temperature to 750oC, keeping the temperature for 12 hours, naturally cooling, wherein the heating rate in the whole calcining process is 2oC/min。
Lithium ion battery assembly and testing
the ternary material prepared by the invention is used as the anode of the lithium ion battery, and the cathode of the lithium ion battery is made of a metal lithium sheet and a carbon-silicon material, and the lithium ion battery is respectively assembled into a lithium ion half battery and a lithium ion full battery.
The assembled lithium ion half-cell is subjected to charge-discharge cycle test and rate test on a test instrument, the test voltage ranges are 3.0 ~ 4.3.3V, in the cycle test process, the current density of the first 3 circles is 0.1C (C =180 mAh/g), the current density of the 4 th 4 ~ 200 circle is 1.0C, in the rate test, the current density is sequentially increased by the current densities of 0.1C, 0.2C, 0.5C, 1.0C, 2.0C, 5.0C and 10.0C, and charging and discharging are carried out for 5 circles under each current density.
The assembled lithium ion full cell is subjected to charge and discharge cycle test on a test instrument, the test voltage ranges from 2.9 ~ 4.2.2V, and in the cycle test process, the current density of the first 3 circles is 0.1C (C =180 mAh/g), and the current density of the 4 th 4 ~ 250 circle is 1.0C.
Fig. 1 is SEM pictures of lithium ion battery high nickel spherical (a) and single crystal (b) ternary cathode materials, respectively. Most of ternary materials in the market are in a secondary particle spherical shape consisting of primary particles, serious intercrystalline cracks can be caused by expansion and contraction of crystal lattices in the charging and discharging processes, and the appearance of the intercrystalline cracks can be effectively slowed down by the single crystal shape.
in FIG. 2, a is LiNi which is a high nickel single crystal ternary positive electrode material with different lithium phosphate coating contents and is prepared in examples 1 to 30.8Co0.1Mn0.1O2XRD characterization pattern of (a). As can be seen from the figure, the coated material has all of the alpha-NaFeO2The layered rock salt structure of (2) belongs to the hexagonal system. In the figure, the diffraction peak of each sample is sharp, and no impurity peak appears, which proves that the crystallinity of each sample is good. In addition, as can be seen from the b diagram, the diffraction peak intensity of lithium phosphate gradually increases with the increase of the coating amount, which indicates that the lithium phosphate is successfully coated on the surface of the material.
fig. 3-5 show the first-pass efficiency curves, cycling performance and rate performance of the lithium-ion button half-cells of examples 1, 4 and comparative examples 1, 2, respectively. Uncoated high-nickel single crystal ternary positive electrode material LiNi0.8Co0.1Mn0.1O2The first discharge specific capacity is 181.1 mAh/g, the lithium phosphate coating capacity is 0.5%, the first discharge capacities of 2% and 14% samples are 192.4 mAh/g, 186.0 mAh/g and 142.1 mAh/g respectively, and the electrochemical performance of the high-nickel single crystal ternary cathode material is effectively improved through proper lithium phosphate coating. The electrochemical performance of the sample with the lithium phosphate coating amount of 14 percent is obviously lower than that of the other three samples, which shows that the lithium phosphate coating amount which is too thick cannot improve the LiNi of the nickel single crystal ternary cathode material0.8Co0.1Mn0.1O2Instead, the performance of (2) plays the opposite role.
Fig. 6 shows the cycle performance of the lithium ion pouch full cells of example 1 and comparative example 1. The lithium phosphate is coated on the surface of the material to form a complete physical protective layer, so that the side reaction between the high-nickel single crystal ternary cathode material and the electrolyte is inhibited, therefore, the electrochemical performance of the sample with the lithium phosphate coating amount of 0.5 percent is superior to that of the uncoated sample,
The technical features of the above embodiments and experimental examples may be arbitrarily combined, and all possible features of the embodiments are not described for the sake of brevity of description, reduction of variables of the comparative experiment, and increase of the reliability of the result of the comparative experiment, however, as long as there is no contradiction between the combinations of the technical features, the combination should be considered as the scope of the description in this specification.
The above-mentioned embodiments only express the centralized implementation mode of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. The lithium phosphate-coated lithium ion battery high-nickel single crystal ternary cathode material is characterized in that the chemical formula of the high-nickel single crystal ternary cathode material is LiNi0.8Co0.1Mn0.1O2The particle size was 5 μm ~ 13 μm.
2. The preparation method of the lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material according to claim 1, characterized by comprising the following steps:
Weighing phosphate, adding the phosphate into distilled water, and uniformly dispersing to obtain a phosphate solution;
Adding a high-nickel single crystal ternary precursor Ni into the phosphate solution obtained in the step (1)0.8Co0.1Mn0.1(OH)2Uniformly mixing to obtain mixed suspension;
Drying the mixed suspension prepared in the step (2) under the condition of stirring and heating to obtain a precipitate finally;
Weighing LiOH ∙ H monohydrate2O, carrying out solid phase grinding on the precipitate obtained in the step (3), and uniformly mixing to obtain a mixture;
calcining the mixture in the step (4) in air and naturally cooling, and then calcining in pure oxygen step by step and naturally cooling to room temperature.
3. The method of claim 2, wherein step (1) is performed in the presence of a catalystPhosphate is relative to the high-nickel single crystal ternary precursor Ni in the step (2)0.8Co0.1Mn0.1(OH)2The molar ratio of (B) was 0.5 ~ 5%.
4. The method according to claim 2, wherein the phosphate salt of step (1) is a mixture of 1 or more of sodium tripolyphosphate, sodium hexametaphosphate, ammonium phosphate trihydrate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate dihydrate, and disodium hydrogen phosphate heptahydrate.
5. The method of claim 2, wherein the lithium hydroxide monohydrate LiOH ∙ H of step (4)2the molar ratio of O to the precipitate in the step (3) is 1.03: 1 ~ 1.05.05: 1.
6. The method of claim 2, wherein the calcination temperature of the calcination in air in the step (5) is 400 ~ 500oC, calcining for 3 ~ 5 h, and heating rate of 2oC/min。
7. The method of claim 2, wherein the pure oxygen of step (5) is calcined step by step, and the step by step calcination is first 500okeeping the temperature for 4 hours under C, and then continuously increasing the temperature to 700 ~ 800oC, continuing to preserve heat for 12 hours at the temperature rising rate of 2oC/min。
8. the method according to any one of claims 1 to 7, characterized in that the specific preparation method employs the following steps:
Relative to high nickel single crystal ternary precursor Ni0.8Co0.1Mn0.1(OH)2Weighing 0.5 ~ 5% of phosphate according to the molar ratio, dissolving the phosphate in 50 mL of distilled water, and fully and uniformly stirring to obtain a phosphate solution;
5 g of high nickel single crystal ternary precursor Ni is added into the phosphate solution0.8Co0.1Mn0.1(OH)2And the mixture is evenly stirred and mixed,obtaining mixed suspension;
Mixing the above mixed suspension at 100oC, drying water while stirring to finally obtain a precipitate;
Weighing LiOH ∙ H monohydrate2Mixing O with the precipitate obtained in the step (3), and grinding and mixing the mixture in a solid phase to obtain a mixture, wherein the lithium hydroxide monohydrate LiOH ∙ H2The molar ratio of O to the precipitate in the step (3) is 1.03: 1 ~ 1.05.05: 1;
the mixture obtained in step (4) is firstly treated with 400 ~ 500 in airocalcining for 3 ~ 5 h under C, naturally cooling, and then calcining in pure oxygen atmosphere for 500 hoKeeping the temperature for 4 hours under C, and then continuously increasing the temperature to 700 ~ 800oC, keeping the temperature for 12 hours, naturally cooling, wherein the heating rate in the whole calcining process is 2oC/min。
CN201910952126.1A 2019-10-09 2019-10-09 Lithium phosphate coated lithium ion battery high-nickel single crystal ternary cathode material and preparation method thereof Pending CN110581269A (en)

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CN111490241A (en) * 2020-04-16 2020-08-04 南开大学 Lithium phosphate in-situ coated lithium-rich manganese-based positive electrode material and preparation method thereof
CN111682170A (en) * 2020-05-20 2020-09-18 广东邦普循环科技有限公司 Single crystal ternary cathode material and preparation method and application thereof
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CN112599736A (en) * 2020-12-11 2021-04-02 湖南杉杉能源科技股份有限公司 Boron-doped lithium phosphate coated lithium ion battery positive electrode material and preparation method thereof
CN112670487A (en) * 2020-12-28 2021-04-16 天津巴莫科技有限责任公司 Multi-dense-coated high-nickel positive electrode material for power and preparation method thereof
CN112864372A (en) * 2021-04-12 2021-05-28 中国科学院化学研究所 Lithium ion battery nickel-rich single crystal positive electrode material with double functional interfaces and preparation method thereof
CN113066980A (en) * 2021-03-19 2021-07-02 中国科学院化学研究所 Method for preparing phosphomolybdic acid modified high-nickel single crystal positive electrode material
CN113488620A (en) * 2021-06-28 2021-10-08 恒大新能源技术(深圳)有限公司 Ternary positive electrode precursor and preparation method thereof, ternary positive electrode material and preparation method thereof, and lithium ion battery
CN113725410A (en) * 2021-08-05 2021-11-30 华中科技大学 Lithium metaphosphate in-situ coated ternary cathode material and preparation method and application thereof
CN113782715A (en) * 2021-08-12 2021-12-10 西安交通大学 Preparation method and application of lithium phosphate modified high-nickel cobalt lithium manganate positive electrode material
WO2022033375A1 (en) * 2020-08-14 2022-02-17 比亚迪股份有限公司 Composite positive electrode material, positive electrode sheet, manufacturing method therefor, and battery
CN114079046A (en) * 2020-08-14 2022-02-22 比亚迪股份有限公司 Mixed positive electrode material, positive electrode plate, manufacturing method of positive electrode plate and battery
CN114261996A (en) * 2021-12-24 2022-04-01 广西师范大学 Preparation method and application of single crystal high-nickel ternary material with completely modified surface
CN114975914A (en) * 2022-05-09 2022-08-30 北京理工大学 High-nickel NCM ternary positive electrode material with surface coated with multiple substances and application thereof

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CN111180702A (en) * 2020-01-06 2020-05-19 天能帅福得能源股份有限公司 Preparation method of coated lithium manganate positive electrode material and positive electrode material thereof
CN111490241A (en) * 2020-04-16 2020-08-04 南开大学 Lithium phosphate in-situ coated lithium-rich manganese-based positive electrode material and preparation method thereof
CN111682170A (en) * 2020-05-20 2020-09-18 广东邦普循环科技有限公司 Single crystal ternary cathode material and preparation method and application thereof
CN112331821A (en) * 2020-06-28 2021-02-05 深圳市海洋王照明工程有限公司 Composition, preparation method and application in preparation of positive electrode material
WO2022033375A1 (en) * 2020-08-14 2022-02-17 比亚迪股份有限公司 Composite positive electrode material, positive electrode sheet, manufacturing method therefor, and battery
CN114079046B (en) * 2020-08-14 2024-01-09 比亚迪股份有限公司 Mixed positive electrode material, positive electrode plate, manufacturing method of positive electrode plate and battery
CN114079047A (en) * 2020-08-14 2022-02-22 比亚迪股份有限公司 Composite positive electrode material, positive electrode plate, manufacturing method of positive electrode plate and battery
CN114079046A (en) * 2020-08-14 2022-02-22 比亚迪股份有限公司 Mixed positive electrode material, positive electrode plate, manufacturing method of positive electrode plate and battery
CN114079047B (en) * 2020-08-14 2023-12-12 比亚迪股份有限公司 Composite positive electrode material, positive electrode plate, manufacturing method of positive electrode plate and battery
CN112164790A (en) * 2020-08-27 2021-01-01 荆门市格林美新材料有限公司 Precursor for coated lithium battery, lithium battery positive electrode material and preparation method of lithium battery positive electrode material
CN112599736A (en) * 2020-12-11 2021-04-02 湖南杉杉能源科技股份有限公司 Boron-doped lithium phosphate coated lithium ion battery positive electrode material and preparation method thereof
CN112670487A (en) * 2020-12-28 2021-04-16 天津巴莫科技有限责任公司 Multi-dense-coated high-nickel positive electrode material for power and preparation method thereof
CN112670487B (en) * 2020-12-28 2022-07-15 天津巴莫科技有限责任公司 Multi-dense-coated high-nickel positive electrode material for power and preparation method
CN113066980A (en) * 2021-03-19 2021-07-02 中国科学院化学研究所 Method for preparing phosphomolybdic acid modified high-nickel single crystal positive electrode material
CN112864372A (en) * 2021-04-12 2021-05-28 中国科学院化学研究所 Lithium ion battery nickel-rich single crystal positive electrode material with double functional interfaces and preparation method thereof
CN112864372B (en) * 2021-04-12 2022-08-02 中国科学院化学研究所 Lithium ion battery nickel-rich single crystal positive electrode material with double functional interfaces and preparation method thereof
CN113488620A (en) * 2021-06-28 2021-10-08 恒大新能源技术(深圳)有限公司 Ternary positive electrode precursor and preparation method thereof, ternary positive electrode material and preparation method thereof, and lithium ion battery
CN113725410A (en) * 2021-08-05 2021-11-30 华中科技大学 Lithium metaphosphate in-situ coated ternary cathode material and preparation method and application thereof
CN113782715A (en) * 2021-08-12 2021-12-10 西安交通大学 Preparation method and application of lithium phosphate modified high-nickel cobalt lithium manganate positive electrode material
CN114261996B (en) * 2021-12-24 2023-09-22 广西师范大学 Preparation method and application of single crystal high nickel ternary material with completely modified surface
CN114261996A (en) * 2021-12-24 2022-04-01 广西师范大学 Preparation method and application of single crystal high-nickel ternary material with completely modified surface
CN114975914A (en) * 2022-05-09 2022-08-30 北京理工大学 High-nickel NCM ternary positive electrode material with surface coated with multiple substances and application thereof
CN114975914B (en) * 2022-05-09 2024-04-12 北京理工大学 High-nickel NCM ternary positive electrode material with surface coated with various substances simultaneously and application thereof

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Application publication date: 20191217