CN114512645A - High-nickel positive electrode material, preparation method thereof and lithium secondary battery - Google Patents
High-nickel positive electrode material, preparation method thereof and lithium secondary battery Download PDFInfo
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- CN114512645A CN114512645A CN202111643611.4A CN202111643611A CN114512645A CN 114512645 A CN114512645 A CN 114512645A CN 202111643611 A CN202111643611 A CN 202111643611A CN 114512645 A CN114512645 A CN 114512645A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 72
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000007774 positive electrode material Substances 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 73
- 239000013078 crystal Substances 0.000 claims abstract description 69
- 239000010405 anode material Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 31
- 239000011159 matrix material Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- 238000007873 sieving Methods 0.000 claims description 11
- 229910013716 LiNi Inorganic materials 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 34
- 238000011065 in-situ storage Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 9
- 230000004927 fusion Effects 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 1
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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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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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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Abstract
The invention provides a high-nickel anode material, a preparation method thereof and a lithium secondary battery. The high-nickel anode material provided by the invention has a specific morphology, and the crystal grains are refined at the outer edge of the single crystal through the in-situ composite growth of the small crystal grains on the surface of the single crystal, so that the residual stress of the single crystal material is reduced, the risks of crystal lattice slippage and particle fracture of the single crystal material in the charge-discharge process are relieved, and the problems of low specific capacity and poor cycle performance of the material are solved.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a high-nickel positive electrode material, a preparation method thereof and a lithium secondary battery.
Background
The high-nickel single crystal anode material has a small quantity of internal crystal boundaries, so that microcracks can be prevented from generating and spreading in the charging and discharging processes, and the safety and the cycle life of the battery are effectively improved.
However, the electrochemical performance of the high nickel single crystal material is still greatly influenced due to the structural change of the high nickel single crystal material after the nickel content is increased.
The prior art generally coats the surface of a high nickel single crystal material with one or more layers of a protective material, such as Al2O3、ZrO2、Co3O4And the nano oxide is added, so that the direct exposure of the material to the electrolyte is inhibited as much as possible, and the cycling stability of the material is effectively improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-nickel cathode material, a preparation method thereof and a lithium secondary battery.
The invention provides a high-nickel anode material which comprises a high-nickel single crystal material substrate and high-nickel refined grains distributed on the surface layer of the high-nickel single crystal material substrate.
According to the invention, high-valence W, Mo and other elements are uniformly distributed in gaps on the surface of a small-particle precursor through precursor coating treatment, and during lithiation, during the growth process of crystal grains, high-valence ions in the gaps on the surface of the precursor cannot form layered crystal lattices together with Li and O, so that the continuous growth of high-nickel oxide crystal grains at the gaps on the boundary is limited, the crystal grains on the outer edge of the single crystal are refined, and the purpose of in-situ composite growth of small crystal grains on the surface of a large-particle single crystal is achieved. The small crystal grains on the surface of the single crystal grow in situ in a compounding manner, the crystal grains are refined at the outer edge of the single crystal, the mechanical rigidity of the whole particle is reduced, the toughness is improved, the advantages of the single crystal material are fully utilized, meanwhile, the residual stress in the large single crystal particles is buffered by the crystal grains refined on the surface, and the structural stability of the material in the charging and discharging processes is improved.
It should be noted that the high nickel single crystal material substrate of the present invention can be a high nickel single crystal material commonly used in the prior art, and the composition of the high nickel single crystal material substrate is represented by the chemical formula LiNixCoyMn1-x-yO2Wherein x is 0.8. ltoreq. x < 1, and y is 0. ltoreq. y.ltoreq.0.1, such as LiNi0.88Co0.09Mn0.03O2，LiNi0.91Co0.06Mn0.03O2And the morphology is single crystal particles.
Furthermore, the size D50 of the high-nickel single crystal material matrix is 3-5 μm, and the size of the high-nickel refined grains is 0.1-0.3 μm.
Further preferably, the size D50 of the high-nickel single crystal material matrix is 3.5-4.5 μm, and the size of the high-nickel refined grains is 0.15-0.25 μm.
Further, the high-nickel refined grains account for 5-30 wt% of the high-nickel single crystal material matrix. Furthermore, the high-nickel cathode material is doped or coated with an element M, wherein M comprises at least one of Al, B, Mg, Ca, Zn, Zr, W, V, Mo, Ti, Sm and Y.
Other metal doping or coating modifications are commonly performed on high nickel positive electrode materials for other purposes in the art, for example, to inhibit the material from being directly exposed to air or electrolyte as much as possible, nano-oxide Al is usually coated in an amount of 0.5-2.0 wt.%2O3、ZrO2And the like.
The invention also provides a preparation method of the high-nickel cathode material.
The preparation method provided by the invention comprises the step of modifying the hydroxide precursor of the high-nickel single crystal material matrix by at least one element of W, Mo, Ti and V.
In one embodiment of the invention, the modifying element is W and the modifying material is preferably WO3。
In another embodiment of the present invention, the modifying element is Mo and the modifying material is preferably MoO3。
Preferably, the modification employs high energy mechanical mixing.
Further, the preparation method further comprises the following steps: and mixing the modified precursor with lithium hydroxide to obtain a lithium mixed material, and then roasting, crushing and sieving the lithium mixed material.
In a specific embodiment of the present invention, the preparation method comprises the steps of:
step 1: modifying a precursor: carrying out high-energy mechanical fusion on the high-nickel hydroxide precursor and 2-3 wt.% of oxide of at least one element of W, Mo, Ti and V;
step 2: preparing a lithium mixture: mixing the modified precursor obtained in the step 1 with excessive lithium hydroxide according to the proportion of the target molecular formula to obtain a lithium mixed material;
and step 3: roasting treatment: roasting the mixed material obtained in the step 2 under pure oxygen atmosphere;
and 4, step 4: and (4) crushing and sieving the material prepared in the step (3) to obtain a final product.
Wherein D50 of the high-nickel hydroxide precursor in the step 1 is 3-5 μm.
The roasting condition in the step 3 is that the multistage roasting of 450 ℃ 4h +780 ℃ 20h is carried out according to the temperature rising speed of 5 ℃/min.
The invention also provides a lithium secondary battery which comprises the high-nickel cathode material. The lithium secondary battery assembled by the high-nickel anode material provided by the invention has effectively improved discharge specific capacity and cycle performance.
The invention provides a high-nickel anode material, a preparation method thereof and a lithium secondary battery.
Drawings
FIG. 1 is an XRD diffraction spectrum of a high nickel single crystal material prepared in example 1;
FIG. 2 is a 0.1C charge and discharge curve for example 1 and comparative example 1;
FIG. 3 is a 1C capacity retention rate curve for example 1 and comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the test reagents and materials used in the examples of the present invention are commercially available.
Unless otherwise specified, the technical means used in the examples of the present invention are conventional means well known to those skilled in the art.
Example 1
This example provides a high nickel positive electrode material, wherein the particle diameter D50 is 4.08 μm, and the particle matrix is large single crystal particles (the chemical composition of the matrix is LiNi) with a particle diameter of about 3 to 5 μm0.88Co0.09Mn0.03O2) The surface layer of the particles is refined grains with the grain diameter of about 0.1-0.3 mu m.
The preparation method comprises the following steps:
step 1: modifying a precursor: high nickel hydroxide precursor Ni with D50 of 3-5 mu m0.88Co0.09Mn0.03(OH)2With 2 wt.% of MoO3Carrying out high-energy mechanical fusion;
step 2: preparing a lithium mixture: according to the formula LiNi0.88Co0.09Mn0.03O2Adding the modified precursor in the step 1 and excessive lithium hydroxide of 3 wt.% into a mixing tank, and fully mixing and stirring until the mixture is uniform to obtain a lithium mixed material;
and step 3: roasting treatment: placing the mixed material obtained in the step 2 in a muffle furnace, and performing multistage roasting at 450 ℃ for 4h +780 ℃ for 20h in a pure oxygen atmosphere at a heating rate of 5 ℃/min;
and 4, step 4: crushing and sieving the material prepared in the step 3 to obtain the final product LiNi with the surface refined crystal grains of the single crystal growing in situ0.88Co0.09Mn0.03O2High nickel positive electrode material.
The electrochemical performance test is carried out on the buckle battery, the constant-current charge-discharge cutoff voltage is 2.5-4.3V, the first discharge specific capacity of 0.1C is 213.3mAh/g, the first charge-discharge coulombic efficiency is 89.0%, and the capacity retention rate of 1C circulation 50 weeks is 97.1%. Compared with the single crystal material with the same components in the comparative example 1, the discharge specific capacity and the cycle performance are effectively improved. Specifically, the specific capacity is improved slightly, the cycle performance is improved obviously, and the advantage of the nickel-rich material subjected to surface grain refinement is more and more prominent along with the gradual increase of the charging and discharging times.
Wherein FIG. 1 is an XRD diffraction spectrum of the high nickel single crystal material prepared in example 1; FIG. 2 is a 0.1C charge and discharge curve for example 1 and comparative example 1; FIG. 3 is a 1C capacity retention rate curve for example 1 and comparative example 1.
Example 2
This example provides a high nickel positive electrode material, wherein the particle diameter D50 is 3.95 μm, and the particle matrix is large single crystal particles (the chemical composition of the matrix is LiNi) with a particle diameter of about 3 to 5 μm0.91Co0.06Mn0.03O2) The surface layer of the particles is a crystal grain with a grain diameter of about 0.1 to 0.3 μm.
The preparation method comprises the following steps:
step 1: modifying a precursor: using a high-nickel hydroxide precursor Ni with D50 of 3-5 μm0.91Co0.06Mn0.03(OH)2With 2.5 wt.% of WO3Carrying out high-energy mechanical fusion;
step 2: preparing a lithium mixture: according to the formula LiNi0.91Co0.06Mn0.03O2Adding the modified precursor in the step 1 and excessive lithium hydroxide of 3 wt.% into a mixing tank, and fully mixing and stirring until the mixture is uniform to obtain a lithium mixed material;
and step 3: roasting treatment: placing the mixed material obtained in the step 2 in a muffle furnace, and performing multistage roasting at 450 ℃ for 4h +760 ℃ for 20h in a pure oxygen atmosphere at a temperature rise speed of 5 ℃/min;
and 4, step 4: crushing and sieving the material prepared in the step 3 to obtain the final product LiNi with the surface refined crystal grains of the single crystal growing in situ0.91Co0.06Mn0.03O2High nickel positive electrode material.
The electrochemical performance test is carried out on the buckle battery, the constant-current charge-discharge cutoff voltage is 2.5-4.3V, the measured specific discharge capacity is 216.2mAh/g, the first charge-discharge coulombic efficiency is 88.7%, and the capacity retention rate is 96.2% after 1C circulation for 50 weeks.
Example 3
This example provides a high nickel positive electrode material having a particle diameter D50 of 4.12 μm and a particle matrix of large single crystal particles having a particle diameter of about 3 to 5 μm (the matrix chemical composition is LiNi)0.94Co0.03Mn0.03O2) The surface layer of the particles is a crystal grain with a grain diameter of about 0.1 to 0.3 μm.
The preparation method comprises the following steps:
step 1: modifying a precursor: high nickel hydroxide precursor Ni with D50 of 3-5 mu m0.94Co0.03Mn0.03(OH)2With 2 wt.% of MoO3Carrying out high-energy mechanical fusion;
step 2: preparing a lithium mixture: according to the formula LiNi0.94Co0.03Mn0.03O2Adding the modified precursor in the step 1 and excessive lithium hydroxide of 3 wt.% into a mixing tank, and fully mixing and stirring until the mixture is uniform to obtain a lithium mixed material;
and step 3: roasting treatment: placing the mixed material obtained in the step 2 in a muffle furnace, and performing multistage roasting at 450 ℃ for 4h +740 ℃ for 20h in a pure oxygen atmosphere at a heating rate of 5 ℃/min;
and 4, step 4: crushing and sieving the material prepared in the step 3 to obtain the final product LiNi with the surface refined crystal grains of the single crystal growing in situ0.94Co0.03Mn0.03O2High nickel positive electrode material.
The electrochemical performance test is carried out on the buckle battery, the constant-current charge-discharge cut-off voltage is 2.5-4.3V, the measured discharge specific capacity is 221.2mAh/g, the first charge-discharge coulombic efficiency is 88.9%, and the capacity retention rate is 95.8% after 1C circulation for 50 weeks.
Example 4
This example provides a high nickel positive electrode material, wherein the particle diameter D50 is 4.0 μm, and the particle matrix is large single crystal particles (the chemical composition of the matrix is LiNi) with a particle diameter of about 3 to 5 μm0.96Co0.03Mn0.01O2) The surface layer of the particles is a crystal grain with a grain diameter of about 0.1 to 0.3 μm.
The preparation method comprises the following steps:
step 1: modifying a precursor: high nickel hydroxide precursor Ni with D50 of 3-5 mu m0.96Co0.03Mn0.01(OH)2With 2.5 wt.% of WO3Carrying out high-energy mechanical fusion;
step 2: preparing a lithium mixture: according to the formula LiNi0.96Co0.03Mn0.01O2Adding the modified precursor in the step 1 and excessive lithium hydroxide of 3 wt.% into a mixing tank, and fully mixing and stirring until the mixture is uniform to obtain a lithium mixed material;
and step 3: roasting treatment: placing the mixed material obtained in the step 2 in a muffle furnace, and performing multistage roasting at 450 ℃ for 4h +720 ℃ for 20h in a pure oxygen atmosphere at a heating rate of 5 ℃/min;
and 4, step 4: crushing and sieving the material prepared in the step 3 to obtain the final product LiNi with the surface refined crystal grains of the single crystal growing in situ0.96Co0.03Mn0.01O2A material.
The electrochemical performance test is carried out on the buckle battery, the constant-current charge-discharge cutoff voltage is 2.5-4.3V, the measured specific discharge capacity is 225.2mAh/g, the first charge-discharge coulombic efficiency is 89.1%, and the capacity retention rate is 95.1% after 1C circulation for 50 weeks.
Comparative example 1 (example 1 without any modification of the same substrate)
The comparative example provides a high nickel single crystal material having the chemical composition: LiNi0.88Co0.09Mn0.03O2The particle size D50 is 4.0 μm, and the morphology is single crystal particle.
The preparation method comprises the following steps:
step 1: preparing a lithium mixture: according to the formula LiNi0.88Co0.09Mn0.03O2The high nickel hydroxide precursor Ni with D50 of 3-5 μm0.88Co0.09Mn0.03(OH)2Adding lithium hydroxide with the excessive amount of 3 wt.% into a mixing tank, fully mixing and stirring until the mixture is uniform to obtain a lithium mixed material;
step 2: roasting treatment: and (3) placing the mixed material obtained in the step (1) in a muffle furnace, and carrying out multistage roasting at 450 ℃ for 4h +780 ℃ for 20h in a pure oxygen atmosphere at a heating rate of 5 ℃/min.
And step 3: and (3) crushing and sieving the material prepared in the step (2) to obtain the material.
The electrochemical performance test is carried out on the buckle battery, the constant-current charge-discharge cutoff voltage is 2.5-4.3V, the measured specific discharge capacity is 207.4mAh/g, the first charge-discharge coulombic efficiency is 88.5%, and the capacity retention rate is 94.8% after 1C circulation for 50 weeks.
Comparative example 2 (example 2 using conventional Al for the same substrate2O3Coating modification)
The comparative example provides a high nickel cathode material, the matrix chemical composition of which is: LiNi0.91Co0.06Mn0.03O2The particle size D50 is 4.0 μm, and the morphology is single crystal particle.
The preparation method comprises the following steps:
step 1: preparing a lithium mixture: according to the formula LiNi0.91Co0.06Mn0.03O2The high nickel hydroxide precursor Ni with D50 of 3-5 μm0.91Co0.06Mn0.03(OH)2Adding lithium hydroxide with the excessive amount of 3 wt.% into a mixing tank, fully mixing and stirring until the mixture is uniform to obtain a lithium mixed material;
step 2: roasting treatment: placing the mixed material obtained in the step 1 in a muffle furnace, and performing multistage roasting at 450 ℃ for 4h +760 ℃ for 20h in a pure oxygen atmosphere at a temperature rise speed of 5 ℃/min;
and step 3: crushing and sieving the material prepared in the step 2;
and 4, step 4: for the material obtained in step 3 and 1 wt.% of Al2O3Mixing the nano oxides and then carrying out high-energy mechanical fusion to obtain Al2O3Nano oxide surface coating modified LiNi0.91Co0.06Mn0.03O2High nickel positive electrode material.
The electrochemical performance test is carried out on the buckle battery, the constant-current charge-discharge cutoff voltage is 2.5-4.3V, the measured specific discharge capacity is 209.7mAh/g, the first charge-discharge coulombic efficiency is 88.4%, and the capacity retention rate is 89.1% after 1C circulation for 50 weeks.
Comparative example 3 (in example 3, the same substrate is modified by conventional Zr element surface doping)
The comparative example provides a high nickel cathode material, the matrix chemical composition of which is: LiNi0.94Co0.03Mn0.03O2The particle size D50 is 4.0 μm, and the morphology is single crystal particle.
The preparation method comprises the following steps:
step 1: modifying a precursor: high nickel hydroxide precursor Ni with D50 of 3-5 mu m0.94Co0.03Mn0.03(OH)2With 2.0 wt.% ZrO2Carrying out high-energy mechanical fusion;
step 2: preparing a lithium mixture: according to the formula LiNi0.94Co0.03Mn0.03O2Adding the modified precursor obtained in the step 1 and lithium hydroxide with an excessive amount of 3 wt.% into a mixing tank, and fully mixing and stirring until the mixture is uniform to obtain a lithium mixed material;
and step 3: roasting treatment: placing the mixed material obtained in the step 2 in a muffle furnace, and performing multistage roasting at 450 ℃ for 4h +740 ℃ for 20h in a pure oxygen atmosphere at a heating rate of 5 ℃/min;
and 4, step 4: crushing and sieving the material prepared in the step 3 to obtain the LiNi with the surface doped and modified with the Zr element0.94Co0.03Mn0.03O2High nickel positive electrode material.
The electrochemical performance test is carried out on the buckle battery, the constant-current charge-discharge cutoff voltage is 2.5-4.3V, the measured specific discharge capacity is 212.2mAh/g, the first charge-discharge coulombic efficiency is 89.2%, and the capacity retention rate is 87.4% after 1C circulation for 50 weeks.
Comparative example 4 (example 4 wherein the same substrate used conventional Co3O4Surface cobalt-rich modification)
The comparative example provides a high nickel cathode material, the matrix chemical composition of which is: LiNi0.96Co0.03Mn0.01O2The particle size D50 is 4.0 μm, and the morphology is single crystal particle.
The preparation method comprises the following steps:
step 1: modifying a precursor: high nickel hydroxide precursor Ni with D50 of 3-5 mu m0.96Co0.03Mn0.01(OH)2With 2.5 wt.% Co3O4Carrying out high-energy mechanical fusion;
step 2: preparing a lithium mixture: according to the formula LiNi0.96Co0.03Mn0.01O2Adding the modified precursor obtained in the step 1 and lithium hydroxide with an excessive amount of 3 wt.% into a mixing tank, and fully mixing and stirring until the mixture is uniform to obtain a lithium mixed material;
and step 3: roasting treatment: placing the mixed material obtained in the step 2 in a muffle furnace, and performing multistage roasting at 450 ℃ for 4h +720 ℃ for 20h in a pure oxygen atmosphere at a heating rate of 5 ℃/min;
and 4, step 4: crushing and sieving the material prepared in the step 3 to obtain Co3O4Surface-modified LiNi0.96Co0.03Mn0.01O2High nickel positive electrode material.
The electrochemical performance test is carried out on the buckle battery, the constant-current charge-discharge cutoff voltage is 2.5-4.3V, the measured discharge specific capacity is 214.3mAh/g, the first charge-discharge coulombic efficiency is 88.7%, and the capacity retention rate is 83.2% after 1C circulation for 50 weeks.
From the results, it can be seen that the high nickel single crystal material is not modified or is modified by a conventional method, and the specific discharge capacity and the cycle performance of the high nickel single crystal material are not as good as those of the high nickel single crystal material modified by the modification method provided by the embodiment of the invention.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The high-nickel anode material is characterized by comprising a high-nickel single crystal material matrix and high-nickel refined grains distributed on the surface layer of the high-nickel single crystal material matrix.
2. The high-nickel positive electrode material according to claim 1, wherein the size D50 of the high-nickel single crystal material matrix is 3 to 5 μm, and the size of the high-nickel refined grains is 0.1 to 0.3 μm.
3. The high-nickel positive electrode material according to claim 2, wherein the size D50 of the high-nickel single crystal material matrix is 3.5 to 4.5 μm, and the size of the high-nickel refined grains is 0.15 to 0.25 μm.
4. The high-nickel positive electrode material according to claim 1, wherein the high-nickel refined grains account for 5 to 30 wt.% of the high-nickel single crystal material matrix.
5. The high nickel positive electrode material according to any one of claims 1 to 4, wherein the high nickel single crystal material matrix is composed of LiNi of the chemical formulaxCoyMn1-x-yO2Wherein x is more than or equal to 0.8 and less than 1, and y is more than or equal to 0 and less than or equal to 0.1.
6. The high nickel positive electrode material according to claim 5, further doped or clad with an element M, M comprising at least one of Al, B, Mg, Ca, Zn, Zr, W, V, Mo, Ti, Sm, Y.
7. The method for producing a high-nickel positive electrode material according to any one of claims 1 to 6, comprising a step of modifying a hydroxide precursor of the high-nickel single crystal material matrix with at least one element selected from the group consisting of W, Mo, Ti and V.
8. The method for preparing a high-nickel cathode material according to claim 7, wherein the modification is performed by high-energy mechanofusion.
9. The method for producing a high nickel positive electrode material according to claim 7, further comprising: and mixing the modified precursor with lithium hydroxide to obtain a lithium mixed material, and then roasting, crushing and sieving the lithium mixed material.
10. A lithium secondary battery comprising the high nickel positive electrode material according to any one of claims 1 to 6.
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