CN107591519B - Modified lithium nickel cobalt manganese cathode material and preparation method thereof - Google Patents
Modified lithium nickel cobalt manganese cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a modified lithium nickel cobalt manganese cathode material and a preparation method thereof. The general formula of the modified lithium nickel cobalt manganese cathode material is LiaNixCoyMnzMγO2‑δRδ. Wherein a is more than or equal to 1.03 and less than or equal to 1.23 and 0<x≤0.9，0<y≤1，0<z≤1，x+y+z＝1，0<γ≤0.075，0<Delta is less than or equal to 0.05, the doping element M is selected from one or more of Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al and B, the doping element R is selected from one or more of N, P, S, Si and Se, and the doping element M and the doping element R are both positioned at the crystal boundary. In the invention, the conventional lithium nickel cobalt manganese cathode material is subjected to grain boundary doping, and the obtained modified lithium nickel cobalt manganese cathode material still has a very stable structure in the repeated charge-discharge process of a strong current.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a modified lithium nickel cobalt manganese cathode material and a preparation method thereof.
Background
Compared with other traditional secondary batteries, the lithium ion battery has the advantages of small volume, high voltage, high energy density and the like, and has made a series of great progress in the consumer electronics field such as mobile phones and notebooks. With the vigorous development of new energy utilities, more and more researchers are actively developing lithium ion batteries with high power density, high cycle stability and high safety, so that the lithium ion batteries are expected to be used as power batteries of electric vehicles.
Among the cathode materials used in lithium ion batteries, the lithium Nickel Cobalt Manganese (NCM) cathode material with a layered structure is considered to be one of the best choices for the cathode material of future power lithium ion batteries due to its characteristics of high discharge capacity, good safety performance, stable structure and low cost. However, the rate performance of lithium nickel cobalt manganese cathode materials is not good compared to lithium cobalt oxide, lithium manganese oxide cathode materials.
To improve the rate capability, most of the current researches are conductedFocus has been on reducing particle size, bulk doping or surface modification. Researchers find that doping with a proper amount of Zr can increase the diffusion coefficient of lithium ions in the lithium nickel cobalt manganese positive electrode material, and further improve the cycle retention rate and rate capability (see the literature of Improvement of electrochemical properties of layered LiNi)1/3Co1/3Mn1/3O2Positive electrode by zirconium diode, Solid State Ionics, Volume 189, Issue 1,6May 2011, Pages 69-73). Chinese patent CN200710035746 applied on 9/14/2007 discloses LiNi1/3Co1/ 3Mn1/3O2The surface is coated with a layer of porous AlF3The porous film can inhibit the side reaction between the electrolyte and the anode material, and further improve the electrochemical performance of the electrolyte at high magnification. Gao Po et al synthesized well-crystallized, nano-scale monodisperse LiNi by a sol-gel method1/3Co1/3Mn1/3O2Particles that exhibit high capacity and cycle retention when discharged at high current (see also the Po Gao, Gang Yang, Haidong Liu, Lu Wang, Haishan Zhou, Lithiumdifferential interference noise and improved high rate capacity of LiNi)1/3Co1/3Mn1/3O2ascathode material for lithium batteries,Solid State Ionics 207(2012),50-56)。
However, in practical applications, the NCM material having a small particle size has a large specific surface area and a large contact area with an electrolyte, and thus has excellent kinetic properties, but at the same time, the NCM material has a fast side reaction and poor storage properties, and if the bulk doping or surface coating method is used, the discharge capacity or power performance is lost. Therefore, how to take power performance and storage performance into consideration is always a difficult problem of the application of the lithium nickel cobalt manganese cathode material in the high-rate or high-power lithium ion battery.
Disclosure of Invention
In view of the problems in the background art, an object of the present invention is to provide a modified lithium nickel cobalt manganese cathode material and a preparation method thereof, which can achieve the power performance, the cycle performance and the high-temperature storage performance of a lithium ion battery.
To achieve aboveIn a first aspect, the present invention provides a modified lithium nickel cobalt manganese cathode material having the general formula LiaNixCoyMnzMγO2-δRδ. Wherein a is more than or equal to 1.03 and less than or equal to 1.23 and 0<x≤0.9，0<y≤1，0<z≤1，x+y+z＝1，0<γ≤0.075，0<Delta is less than or equal to 0.05, the doping element M is selected from one or more of Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al and B, the doping element R is selected from one or more of N, P, S, Si and Se, and the doping element M and the doping element R are both positioned at the crystal boundary.
In a second aspect of the present invention, the present invention provides a method for preparing a modified lithium nickel cobalt manganese positive electrode material, for preparing the modified lithium nickel cobalt manganese positive electrode material according to the first aspect of the present invention, comprising the steps of: (1) preparing nickel salt, cobalt salt and manganese salt into a mixed solution according to the atomic ratio of Ni to Co to Mn to x to y to z, then dropwise adding the mixed solution and a solution of a first doping compound into a reaction container for reaction, and drying after the reaction is finished to obtain a precursor (Ni)xCoyMnz)(OH)2/MγRδThe first doping compound is selected from MR and MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3One or more of the above; (2) mixing the precursor (Ni)xCoyMnz)(OH)2/MγRδUniformly mixing with lithium salt according to the atomic ratio of Li (Ni + Co + Mn) ═ a:1, calcining to obtain LiaNixCoyMnzMγO2-δRδAnd finishing the preparation of the modified lithium nickel cobalt manganese cathode material. Wherein a is more than or equal to 1.03 and less than or equal to 1.23 and 0<x≤0.9，0<y≤1，0<z≤1，x+y+z＝1，0<γ≤0.075，0<Delta is less than or equal to 0.05, the doping element M is selected from one or more of Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al and B, and the doping element R is selected from one or more of N, P, S, Si and Se.
In a third aspect of the invention, the invention provides another modified lithium nickel cobalt manganese positive electrode material comprising: a kernel; and a coating layerCoated on the surface of the inner core. Wherein the core is Li according to the first aspect of the inventionaNixCoyMnzMγO2-δRδ. The general formula of the coating layer is LiM'cObOr M'cObM' is selected from one or more of Ni, Co, Mn, Sn, Mg, Ti, Zr, V, Nb, Mo, W, Al, B, Si, Zn and Bi, 0<c≤2，0<b/c≤3。
In a fourth aspect of the present invention, the present invention provides another preparation method of a modified lithium nickel cobalt manganese positive electrode material, for preparing the modified lithium nickel cobalt manganese positive electrode material according to the third aspect of the present invention, comprising the steps of: (1) preparing nickel salt, cobalt salt and manganese salt into a mixed solution according to the atomic ratio of Ni to Co to Mn to x to y to z, then dropwise adding the mixed solution and a solution of a first doping compound into a reaction container for reaction, and drying after the reaction is finished to obtain a precursor (Ni)xCoyMnz)(OH)2/MγRδThe first doping compound is selected from MR and MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3One or more of the above; (2) mixing the precursor (Ni)xCoyMnz)(OH)2/MγRδUniformly mixing with lithium salt according to the atomic ratio of Li (Ni + Co + Mn) ═ a:1, calcining to obtain LiaNixCoyMnzMγO2-δRδ(ii) a (3) Preparing a first coating compound LiM'cObOr M'cObWith LiaNixCoyMnzMγO2-δRδAnd uniformly mixing and calcining to complete the preparation of the modified lithium nickel cobalt manganese cathode material. Wherein a is more than or equal to 1.03 and less than or equal to 1.23 and 0<x≤0.9，0<y≤1，0<z≤1，x+y+z＝1，0<γ≤0.075，0<δ≤0.05，0<c≤2，0<B/c is less than or equal to 3, the doping element M is selected from one or more of Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al and B, the doping element R is selected from one or more of N, P, S, Si and Se, and M' is selected from Ni, Co, Mn, Sn, Mg, Ti, Se,One or more of Zr, V, Nb, Mo, W, Al, B, Si, Zn and Bi.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, the conventional lithium nickel cobalt manganese cathode material is subjected to grain boundary doping, and the obtained modified lithium nickel cobalt manganese cathode material still has a very stable structure in the repeated charge-discharge process of a strong current.
The lithium ion battery adopting the modified lithium nickel cobalt manganese anode material has higher power output characteristic, good cycle performance and high-temperature storage stability when being applied to the fields of HEV (hybrid electric vehicle), UPS (uninterrupted power supply), power battery (power-cell), start-stop power supply and the like, and can effectively meet the requirements of high power density, long service life and high safety of the lithium ion battery.
Drawings
Fig. 1 is a schematic diagram of a modified lithium nickel cobalt manganese cathode material.
Detailed Description
The modified lithium nickel cobalt manganese cathode material and the preparation method thereof according to the present invention are explained in detail below.
First, the modified lithium nickel cobalt manganese positive electrode material according to the first aspect of the present invention will be explained.
The general formula of the modified lithium nickel cobalt manganese cathode material according to the first aspect of the invention is LiaNixCoyMnzMγO2-δRδ. Wherein a is more than or equal to 1.03 and less than or equal to 1.23 and 0<x≤0.9，0<y≤1，0<z≤1，x+y+z＝1，0<γ≤0.075，0<Delta is less than or equal to 0.05, the doping element M is selected from one or more of Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al and B, the doping element R is selected from one or more of N, P, S, Si and Se, and the doping element M and the doping element R are both positioned at the crystal boundary.
In the modified lithium nickel cobalt manganese positive electrode material according to the first aspect of the present invention, the grain boundaries refer to interfaces between crystal grains having the same structure but different orientations. The grain boundaries may be located inside the primary particles, and may also be located inside the secondary particles. Referring to fig. 1, 1 indicates crystal grains, and 2 indicates grain boundaries. The positions of the doping element M and the doping element R can be confirmed by a spherical aberration-corrected TEM electron microscope.
In the modified lithium nickel cobalt manganese positive electrode material according to the first aspect of the present invention, the doping element M and the doping element R are easily aggregated at the grain boundary due to the ionic radius, the electron shell distribution, and the like. Therefore, the doping element M and the doping element R can play a role in reducing the interface impedance of lithium ions in the transmission process and reducing the interface energy barrier in the rapid lithium ion de-intercalation process at the crystal boundary, so that the power performance of the lithium ion battery is improved, meanwhile, the obtained positive electrode material still has a very stable structure in the repeated charge and discharge process of strong current, and finally, the cycle performance and the high-temperature storage performance of the lithium ion battery under the high multiplying power are improved. In conventional bulk doping, the doping elements are located at the positions of the substituted transition metal ions or the positions of the lithium ions, which affect the gram capacity performance and voltage plateau of the lithium nickel cobalt manganese cathode material, resulting in power density loss. In the conventional surface coating, the coating element is only located on the surface of the lithium nickel cobalt manganese cathode material, and the structural stability and lithium ion transmission characteristics of the internal intergranular interface cannot be improved, resulting in deterioration of power performance.
In the modified lithium nickel cobalt manganese positive electrode material according to the first aspect of the present invention, the average particle diameter (D50) of the primary particles is 0.1 to 2 μm, and the average particle diameter (D50) of the secondary particles is 2 to 7 μm. By further controlling the average particle size of the particles, the lithium ion battery with higher power density can be obtained.
In the modified lithium nickel cobalt manganese positive electrode material according to the first aspect of the present invention, the specific surface area of the modified lithium nickel cobalt manganese positive electrode material is 0.3m2/g～2m2A/g, preferably of 0.8m2/g～1.5m2(ii) in terms of/g. The specific surface area of the modified lithium nickel cobalt manganese cathode material is in the range, and the power performance of the lithium ion battery is further improved. The specific surface area is too large, and the stability of the modified lithium nickel cobalt manganese cathode material is reduced.
In the modified lithium nickel cobalt manganese positive electrode material according to the first aspect of the present invention, the doping amount of the doping element M is too high, which is not favorable for increasing the power and energy density of the lithium ion battery. Preferably, 0.0001. ltoreq. gamma. ltoreq.0.02.
In the modified lithium nickel cobalt manganese positive electrode material according to the first aspect of the present invention, the doping amount of the doping element R is too high, which is not favorable for increasing the power and energy density of the lithium ion battery. Preferably, 0.0003. ltoreq. delta. ltoreq.0.015.
In the modified lithium nickel cobalt manganese positive electrode material according to the first aspect of the present invention, x, y, z are selected from one of the following combinations: x is 1/3, y is 1/3, and z is 1/3; x is 0.35, y is 0.35, and z is 0.30; x is 0.4, y is 0.2, and z is 0.4; x is 0.5, y is 0.25, and z is 0.25; x is 0.5, y is 0.2, and z is 0.3; x is 0.8, y is 0.1, and z is 0.1; x is 0.85, y is 0.075, and z is 0.0075.
Next, a description is given of a method for preparing a modified lithium nickel cobalt manganese positive electrode material according to a second aspect of the present invention, for preparing the modified lithium nickel cobalt manganese positive electrode material according to the first aspect of the present invention, including the steps of: (1) preparing nickel salt, cobalt salt and manganese salt into a mixed solution according to the atomic ratio of Ni to Co to Mn to x to y to z, then dropwise adding the mixed solution and a solution of a first doping compound into a reaction container for reaction, and drying after the reaction is finished to obtain a precursor (Ni)xCoyMnz)(OH)2/MγRδThe first doping compound is selected from MR and MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3One or more of the above; (2) mixing the precursor (Ni)xCoyMnz)(OH)2/MγRδUniformly mixing with lithium salt according to the atomic ratio of Li (Ni + Co + Mn) ═ a:1, calcining to obtain LiaNixCoyMnzMγO2-δRδAnd finishing the preparation of the modified lithium nickel cobalt manganese cathode material. Wherein a is more than or equal to 1.03 and less than or equal to 1.23 and 0<x≤0.9，0<y≤1，0<z≤1，x+y+z＝1，0<γ≤0.075，0<Delta is less than or equal to 0.05, the doping element M is selected from one or more of Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al and B, and the doping element R is selected from one or more of N, P, S, Si and Se.
In the preparation method of the modified lithium nickel cobalt manganese cathode material according to the second aspect of the present invention, the first doping compound is added in the process of synthesizing the precursor, the first doping compound is gathered at the grain edge of the precursor in advance, and finally, the first doping compound is easily adsorbed to the grain edge due to the surface energy effect while the precursor is formed, and the first doping compound is diffused and reacted at the grain edge during calcination, so that the nucleation path is greatly shortened, the calcination temperature and time can be reduced, and grain boundary doping is formed.
In the method for preparing the modified lithium nickel cobalt manganese cathode material according to the second aspect of the present invention, the first doping compound in step (1) is selected from Mg3N2、WS2、MoS2、VP2、CoP3、MnP4、NiP2、NbP、Sn4P3、TiP2、ZrP2、WSe2、WP2And one or more of TiP.
In the preparation method of the modified lithium nickel cobalt manganese cathode material according to the second aspect of the invention, the pH value of the reaction system in the step (1) is 10.8-12.0. The pH value of the reaction system is controlled, so that the modified lithium nickel cobalt manganese cathode material with smaller particle size and more concentrated distribution can be obtained.
In the preparation method of the modified lithium nickel cobalt manganese cathode material according to the second aspect of the present invention, the reaction temperature in step (1) is 50 ℃ to 80 ℃. The reaction temperature is controlled, so that the modified lithium nickel cobalt manganese cathode material with smaller particle size and more concentrated distribution can be obtained.
In the method for preparing the modified lithium nickel cobalt manganese cathode material according to the second aspect of the present invention, the calcination temperature in step (2) is 400 ℃ to 950 ℃.
A modified lithium nickel cobalt manganese positive electrode material according to the third aspect of the present invention, which is an alternative embodiment of the modified lithium nickel cobalt manganese positive electrode material according to the first aspect of the present invention, will be described again.
The modified lithium nickel cobalt manganese cathode material according to the third aspect of the present invention comprises: a kernel; and a coating layer coated on the surface of the inner core. Wherein the core is Li according to the first aspect of the inventionaNixCoyMnzMγO2-δRδ. The general formula of the coating layer is LiM'cObOr M'cObM' is selected from one or more of Ni, Co, Mn, Sn, Mg, Ti, Zr, V, Nb, Mo, W, Al, B, Si, Zn and Bi, 0<c≤2，0<b/c≤3。
In the modified lithium nickel cobalt manganese cathode material according to the third aspect of the present invention, the conventional lithium nickel cobalt manganese material is subjected to grain boundary doping modification and surface coating modification at the same time. The doping element M and the doping element R play a role in reducing the interface impedance of lithium ions in the transmission process and reducing the interface energy barrier in the rapid lithium ion deintercalation process at the crystal boundary, and meanwhile, the coating layer can play a role in stabilizing the crystal interface structure and inhibiting the occurrence of the conditions of phase change and the like of the anode material caused by the excessively low concentration of lithium ions on the surface due to the rapid deintercalation of the lithium ions. Finally, the power performance, the cycle performance under high magnification and the high-temperature storage performance of the lithium ion battery are improved.
In the modified lithium nickel cobalt manganese cathode material according to the third aspect of the present invention, M' and Li in the coating layeraNixCoyMnzMγO2-δRδIs β:1, preferably 0<β is less than or equal to 0.015, in the range, the lithium ion battery with better power performance, cycle performance under large multiplying power and high-temperature storage performance is obtained, β is too large, and the power performance of the lithium ion battery is deteriorated.
Next, a description will be given of a method for producing a modified lithium nickel cobalt manganese positive electrode material according to a fourth aspect of the present invention, for producing the modified lithium nickel cobalt manganese positive electrode material according to the third aspect of the present invention, including the steps of: (1) preparing nickel salt, cobalt salt and manganese salt into a mixed solution according to the atomic ratio of Ni to Co to Mn to x to y to z, then dropwise adding the mixed solution and a solution of a first doping compound into a reaction container for reaction, and drying after the reaction is finished to obtain a precursor (Ni)xCoyMnz)(OH)2/MγRδThe first doping compound is selected from MR and MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3One or more of the above; (2) mixing the precursor (Ni)xCoyMnz)(OH)2/MγRδUniformly mixing with lithium salt according to the atomic ratio of Li (Ni + Co + Mn) ═ a:1, calcining to obtain LiaNixCoyMnzMγO2-δRδ(ii) a (3) Preparing a first coating compound LiM'cObOr M'cObWith LiaNixCoyMnzMγO2-δRδAnd uniformly mixing and calcining to complete the preparation of the modified lithium nickel cobalt manganese cathode material. Wherein a is more than or equal to 1.03 and less than or equal to 1.23 and 0<x≤0.9，0<y≤1，0<z≤1，x+y+z＝1，0<γ≤0.075，0<δ≤0.05，0<c≤2，0<B/c is less than or equal to 3, the doping element M is selected from one or more of Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al and B, the doping element R is selected from one or more of N, P, S, Si and Se, and M' is selected from one or more of Ni, Co, Mn, Sn, Mg, Ti, Zr, V, Nb, Mo, W, Al, B, Si, Zn and Bi.
In the method for preparing a modified lithium nickel cobalt manganese positive electrode material according to the fourth aspect of the present invention, the first coating compound LiM 'in step (3)'cObOr M'cObM' and Li in (1)aNixCoyMnzMγO2-δRδIn a molar ratio of β:1, 0<β≤0.015。
In the method for preparing a modified lithium nickel cobalt manganese cathode material according to the fourth aspect of the present invention, the first doping compound in step (1) is selected from Mg3N2、WS2、MoS2、VP2、CoP3、MnP4、NiP2、NbP、Sn4P3、TiP2、ZrP2、WSe2、WP2And one or more of TiP.
In the method for preparing the modified lithium nickel cobalt manganese cathode material according to the fourth aspect of the present invention, the first coating compound in the step (3) is selected from MgO and Al2O3、SiO2、ZrO2、ZnO、TiO2、B2O3、Bi2O3、Nb2O5、MoO2、MoO3、NiO、MnO2、V2O5、WO2、WO3、SnO2、LiNbO3、Li2TiO3、Li2ZrO3、LiMn2O4、Li2MoO4One or more of them.
In the preparation method of the modified lithium nickel cobalt manganese cathode material according to the fourth aspect of the invention, the pH value of the reaction system in the step (1) is 10.8-12.0.
In the method for preparing the modified lithium nickel cobalt manganese cathode material according to the fourth aspect of the present invention, the reaction temperature in step (1) is 50 ℃ to 80 ℃.
In the method for preparing the modified lithium nickel cobalt manganese cathode material according to the fourth aspect of the present invention, the calcination temperature in step (2) is 400 ℃ to 950 ℃.
In the method for preparing the modified lithium nickel cobalt manganese cathode material according to the fourth aspect of the present invention, the calcination temperature in step (3) is 400 ℃ to 950 ℃.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
Comparative example 1
Mixing NiSO4、CoSO4、MnSO4A mixed aqueous solution was prepared in which the total concentration of cations was 2mo1/L at an atomic ratio of Ni, Co, and Mn of 0.35:0.35: 0.30.
And (3) dropwise adding the mixed aqueous solution, 2mol/L NaOH solution and 3mol/L ammonia water solution into a reaction container, controlling the pH value of the system to be 11.0 +/-0.2, and heating in a water bath to 50 ℃ for reaction. And stopping feeding after controlling the D50 of the precipitate to reach 3-4 mu m, aging for 2h, and performing filter pressing, washing and forced air drying for 8h to obtain precursor powder.
Mixing the obtained precursor powder with lithium salt Li2CO3According to the atomic ratio of Li (Ni + Co + M)n) ═ 1.1:1, ball milling, mixing, sintering at 910 deg.C for 18 hr in a sintering furnace in air atmosphere, grinding and sieving to obtain pure phase Li with lamellar crystal structure1.1(Ni0.35Co0.35Mn0.30)O2And (3) a positive electrode material.
Comparative example 2
Mixing NiSO4、CoSO4、MnSO4A mixed aqueous solution was prepared in which the total concentration of cations was 2mo1/L at an atomic ratio of Ni, Co, and Mn of 0.35:0.35: 0.30.
And (3) dropwise adding the mixed aqueous solution, 2mol/L NaOH solution and 3mol/L ammonia water solution into a reaction container, controlling the pH value of the system to be 11.0 +/-0.2, and heating in a water bath to 50 ℃ for reaction. And stopping feeding after controlling the D50 of the precipitate to reach 3-4 mu m, aging for 2h, and performing filter pressing, washing and forced air drying for 8h to obtain precursor powder.
Mixing the obtained precursor powder with lithium salt Li2CO3The first coating compound ZrO2Ball-milling and mixing uniformly, wherein the atomic ratio of Li (Ni + Co + Mn) is 1.1:1, the atomic ratio of Zr (Ni + Co + Mn) is 0.0005:1 (corresponding to β in Table 1 is 0.0005), placing the mixture into a sintering furnace in an air atmosphere, sintering at 910 ℃ for 18h, and grinding and screening to obtain the product with the surface coated with ZrO2Li of (2)1.1(Ni0.35Co0.35Mn0.30)O2And (3) a positive electrode material.
Comparative example 3
ZrSO4、NiSO4、CoSO4、MnSO4A mixed aqueous solution was prepared in which the atomic ratio of Ni to Co to Mn was 0.35 to 0.30 and the atomic ratio of Zr (Ni + Co + Mn) was 0.0005 to 1 (corresponding to γ of Table 1 being 0.0005), wherein the total concentration of cations was 2mo 1/L.
And (3) dropwise adding the mixed aqueous solution, 2mol/L NaOH solution and 3mol/L ammonia water solution into a reaction container, controlling the pH value of the system to be 11.0 +/-0.2, and heating in a water bath to 50 ℃ for reaction. And stopping feeding after controlling the D50 of the precipitate to reach 3-4 mu m, aging for 2h, and performing filter pressing, washing and forced air drying for 8h to obtain Zr-doped precursor powder.
The obtained precursor powderWith lithium salts Li2CO3Uniformly ball-milling and mixing Li (Ni + Co + Mn + Zr) in an atomic ratio of 1.1:1, placing the mixture in a sintering furnace in an air atmosphere, sintering the mixture for 18 hours at 910 ℃, and grinding and screening the sintered mixture to obtain the Zr-doped anode material with a layered crystal structure.
Example 1
Mixing NiSO4、CoSO4、MnSO4A mixed aqueous solution was prepared in which the total concentration of cations was 2mo1/L at an atomic ratio of Ni, Co, and Mn of 0.35:0.35: 0.30.
Mixing the mixed aqueous solution, 2mol/L NaOH solution, 3mol/L ammonia water solution and a first doping compound ZrP2And dropwise adding the aqueous dispersion into a reaction container together, controlling the pH value of the system to be 11.0 +/-0.2, and heating in a water bath to 50 ℃ for reaction. Wherein the first doping compound ZrP2Is added in an amount to ensure that the atomic ratio P (Ni + Co + Mn) is 0.0005:1 (i.e., δ is 0.0005, γ is 0.00025). And stopping feeding after controlling the D50 of the precipitate to reach 3-4 mu m, aging for 2h, and performing filter pressing, washing and forced air drying for 8h to obtain precursor powder.
Mixing the obtained precursor powder with lithium salt Li2CO3Uniformly ball-milling and mixing Li (Ni + Co + Mn) in an atomic ratio of 1.1:1, placing the mixture in a sintering furnace in an air atmosphere, sintering the mixture for 18 hours at 910 ℃, and grinding and screening the mixture to obtain the positive electrode material doped with Zr and P elements at the crystal boundary position, thereby completing the preparation of the final modified lithium-nickel-cobalt-manganese positive electrode material.
Example 2
Mixing NiSO4、CoSO4、MnSO4A mixed aqueous solution was prepared in which the total concentration of cations was 2mo1/L at an atomic ratio of Ni, Co, and Mn of 0.35:0.35: 0.30.
Mixing the mixed aqueous solution, 2mol/L NaOH solution, 3mol/L ammonia water solution and a first doping compound ZrP2And dropwise adding the aqueous dispersion into a reaction container together, controlling the pH value of the system to be 11.0 +/-0.2, and heating in a water bath to 50 ℃ for reaction. Wherein the first doping compound ZrP2Is added in an amount to ensure that the atomic ratio P (Ni + Co + Mn) is 0.0005:1 (i.e., δ is 0.0005, γ is 0.00025). Stopping feeding after controlling the D50 of the precipitate to reach 3-4 mu m, and agingAnd 2h, carrying out filter pressing, washing and forced air drying for 8h to obtain precursor powder.
Mixing the obtained precursor powder with lithium salt Li2CO3Uniformly ball-milling and mixing Li (Ni + Co + Mn) in an atomic ratio of 1.1:1, placing the mixture into a sintering furnace in an air atmosphere, sintering the mixture for 18 hours at 910 ℃, and then grinding and screening the mixture to obtain the positive electrode material doped with Zr and P elements at the grain boundary position.
Mixing the above-mentioned positive electrode material powder and first coating compound ZrO2Ball-milling and mixing uniformly, wherein the first coating compound ZrO2The addition amount of the positive electrode material is ensured to be 0.0005:1 (namely β is 0.0005) according to the atomic ratio Zr (Ni + Co + Mn), the positive electrode material is placed in a sintering furnace in the air atmosphere, sintered for 8 hours at 700 ℃, and then ground and sieved to obtain the modified lithium nickel cobalt manganese positive electrode material which is simultaneously subjected to interface doping modification and surface coating modification.
Examples 3 to 14 were prepared in the same manner as in example 2, except that the kind and content of the first dopant compound and the kind and content of the first cladding compound were different, as can be seen from Table 1.
The positive electrode materials prepared in comparative examples 1 to 3 and examples 1 to 14 were tested for their specific surface BET using a specific surface tester (Tristar302), and the results are shown in table 1.
Respectively mixing the positive electrode materials prepared in comparative examples 1-3 and examples 1-14 with a mixture of conductive agent super-P and CNT and a polyvinylidene fluoride (PVDF) binder in a mass ratio of 94:2:1:3 in an N-methyl pyrrolidone (NMP) solvent, stirring for 12 hours at normal temperature, transferring and coating on an Al foil current collector with the thickness of 16 mu m, performing vacuum drying at 120 ℃, cold pressing, slitting and slitting with a graphite negative electrode sheet, and winding into a lithium ion battery with the model of 426080 and the capacity of 2Ah, wherein the electrolyte adopts 1mol/L LiPF6As the lithium salt, EC/EMC ═ 3:7(V/V) was used as an organic solvent, and a separator was usedThe separating membrane adopts a polypropylene (PP) porous membrane.
Next, performance tests of the lithium ion battery are explained.
(1) Power performance testing of lithium ion batteries
At 25 ℃, constant current charging was performed at a current density of 0.4A with a charge cut-off voltage of 4.2V, constant voltage charging was performed at 4.2V until the current density was 0.1A, and constant current discharging was performed at a current density of 0.4A until the current density was 2.8V, and the obtained discharge capacity was taken as the rated capacity Cn (i.e., 100% SOC) of the lithium ion battery.
At 25 ℃, the lithium ion battery is charged to 50 percent (namely 50 percent SOC) of the rated capacity at the current density of 0.2 ℃, and then the discharge power density of 50 percent SOC discharge of the lithium ion battery at 25 ℃ and-20 ℃ is tested by adopting an HPPC method and using 10C as pulse current respectively at 25 ℃ and-20 ℃.
(2) Cycle performance testing of lithium ion batteries
And at the temperature of 25 ℃, carrying out charge-discharge cycle test on the lithium ion battery at the current density of 3C, and setting the voltage interval to be 2.8V-4.2V.
(3) High temperature storage performance testing of lithium ion batteries
Fully charging to 4.2V at the current density of 0.5C at 25 ℃, then placing in a thermostat at 60 ℃ for storage for 30 days, taking out, testing the volume of the lithium ion battery by adopting a drainage method, discharging to 2.8V by adopting the current density of 0.5C, testing the recoverable capacity at 100% SOC, comparing the recoverable capacity with the volume and the discharge capacity obtained by testing at 25 ℃, and calculating the volume change rate and the remaining capacity retention rate of the lithium ion battery.
As can be seen from the data in table 2, the lithium nickel cobalt manganese cathode material in comparative example 1 is not modified, and the performance of the lithium ion battery is poor, especially the power performance is poor. In comparative example 2, the lithium nickel cobalt manganese cathode material was surface-coated, and the cycle performance and high-temperature storage performance of the lithium ion battery were improved, but the power performance was deteriorated. Comparative example 3 conventional bulk phase doping of a lithium nickel cobalt manganese cathode material can achieve the effect of improving cycle performance to a certain extent, but cannot give consideration to both power performance and high-temperature storage performance.
In the embodiment 1, the interface doping modification is performed on the lithium-nickel-cobalt-manganese cathode material, so that the power performance, the cycle performance and the high-temperature storage performance of the lithium ion battery are improved. In examples 2 to 14, the interface doping modification and the surface coating modification are simultaneously performed on the lithium nickel cobalt manganese positive electrode material, so that the power performance at room temperature and low temperature is improved, and the cycle performance and the high-temperature storage performance are improved.
Those skilled in the art to which the present invention pertains can also make appropriate alterations and modifications to the above-described embodiments, in light of the above disclosure. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (14)
1. A modified lithium nickel cobalt manganese anode material, which is characterized in that,
the general formula of the modified lithium nickel cobalt manganese cathode material is LiaNixCoyMnzMγO2-δRδ；
Wherein a is more than or equal to 1.03 and less than or equal to 1.23, x is more than or equal to 0 and less than or equal to 0.9, y is more than 0 and less than or equal to 1, z is more than 0 and less than or equal to 1, x + y + z is 1, gamma is more than 0 and less than or equal to 0.075, delta is more than 0 and less than or equal to 0.05, the doping element M is selected from one or more of Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al and B, the doping element R is selected from one or more of N, P, S, Si and Se, and the doping element M and the doping element R are positioned at a crystal.
2. The modified lithium nickel cobalt manganese positive electrode material of claim 1, wherein γ is 0.0001. ltoreq. γ.ltoreq.0.02, and δ is 0.0003. ltoreq. δ.ltoreq.0.015.
3. The method of claim 1The modified lithium nickel cobalt manganese cathode material is characterized in that the specific surface area of the modified lithium nickel cobalt manganese cathode material is 0.3m2/g～2m2/g。
4. The modified lithium nickel cobalt manganese positive electrode material of claim 1, wherein the modified lithium nickel cobalt manganese positive electrode material has a specific surface area of 0.8m2/g～1.5m2/g。
5. A preparation method of a modified lithium nickel cobalt manganese cathode material, which is used for preparing the modified lithium nickel cobalt manganese cathode material as claimed in any one of claims 1 to 4, and is characterized by comprising the following steps:
(1) preparing nickel salt, cobalt salt and manganese salt into a mixed solution according to the atomic ratio of Ni to Co to Mn to x to y to z, then dropwise adding the mixed solution and a solution of a first doping compound into a reaction container for reaction, and drying after the reaction is finished to obtain a precursor (Ni)xCoyMnz)(OH)2/MγRδThe first doping compound is selected from MR and MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3One or more of the above;
(2) mixing the precursor (Ni)xCoyMnz)(OH)2/MγRδUniformly mixing with lithium salt according to the atomic ratio of Li (Ni + Co + Mn) ═ a:1, calcining to obtain LiaNixCoyMnzMγO2-δRδCompleting the preparation of the modified lithium nickel cobalt manganese cathode material;
wherein a is more than or equal to 1.03 and less than or equal to 1.23, x is more than 0 and less than or equal to 0.9, y is more than 0 and less than or equal to 1, z is more than 0 and less than or equal to 1, x + y + z is 1, gamma is more than 0 and less than or equal to 0.075, delta is more than 0 and less than or equal to 0.05, the doping element M is selected from one or more of Ni, Co, Mn, Sn, Mg, Ca, Ti, Zr, V, Nb, Mo, W, Al and B, and the doping element R is selected from one or more of N, P, S, Si and Se.
6. The method for preparing the modified lithium nickel cobalt manganese positive electrode material according to claim 5, characterized in thatCharacterized in that the first doping compound in step (1) is selected from Mg3N2、WS2、MoS2、VP2、CoP3、MnP4、NiP2、NbP、Sn4P3、TiP2、ZrP2、WSe2、WP2And one or more of TiP.
7. The preparation method of the modified lithium nickel cobalt manganese cathode material according to claim 5, wherein the pH value of the reaction system in the step (1) is 10.8-12.0, and the reaction temperature in the step (1) is 50-80 ℃.
8. A modified lithium nickel cobalt manganese positive electrode material comprising:
a kernel; and
the coating layer is coated on the surface of the inner core;
it is characterized in that the preparation method is characterized in that,
the core is Li according to any one of claims 1 to 4aNixCoyMnzMγO2-δRδ；
The general formula of the coating layer is LiM'cObOr M'cObM' is selected from one or more of Ni, Co, Mn, Sn, Mg, Ti, Zr, V, Nb, Mo, W, Al, B, Si, Zn and Bi, 0<c≤2，0<b/c≤3。
9. The modified lithium nickel cobalt manganese positive electrode material of claim 8, wherein M' and Li in the coating layeraNixCoyMnzMγO2-δRδIn a molar ratio of β:1, 0<β≤0.015。
10. A method for preparing a modified lithium nickel cobalt manganese cathode material for preparing the modified lithium nickel cobalt manganese cathode material according to any one of claims 8 to 9, comprising the steps of:
(1) mixing nickel salt, cobalt salt and manganese salt according to the atomic ratio of Ni, Co, Mn, x, y and zMixing the solution, then adding the solution and the solution of the first doping compound dropwise into a reaction vessel for reaction, and drying after the reaction is finished to obtain a precursor (Ni)xCoyMnz)(OH)2/MγRδThe first doping compound is selected from MR and MR2、MR3、MR4、M3R2、M4R3、M2R、M2R3One or more of the above;
(2) mixing the precursor (Ni)xCoyMnz)(OH)2/MγRδUniformly mixing with lithium salt according to the atomic ratio of Li (Ni + Co + Mn) ═ a:1, calcining to obtain LiaNixCoyMnzMγO2-δRδ；
(3) Preparing a first coating compound LiM'cObOr M'cObWith LiaNixCoyMnzMγO2-δRδUniformly mixing and calcining to complete the preparation of the modified lithium nickel cobalt manganese cathode material;
wherein a is more than or equal to 1.03 and less than or equal to 1.23, x is more than or equal to 0 and less than or equal to 0.9, y is more than 0 and less than or equal to 1, z is more than 0 and less than or equal to 1, x + y + z is 1, gamma is more than or equal to 0.075, delta is more than or equal to 0.05, c is more than or equal to 0 and less than or equal to 2, B/c is more than or equal to 0 and less than or equal to 3, the doping element M is selected from one or more of Ni, Co, Mn, Sn, Zr, V, Nb, Mo, W, Al and B, the doping element R is selected from one or more of N, P, S, Si and Se, and M' is selected from one or more of Ni, Co, Mn, Sn, Mg, Ti, Zr, V, Nb, Mo, W, Al, B, Si, Zn.
11. The method for preparing a modified lithium nickel cobalt manganese cathode material according to claim 10, wherein the first coating compound LiM 'in step (3)'cObOr M'cObM' and Li in (1)aNixCoyMnzMγO2-δRδIn a molar ratio of β:1, 0<β≤0.015。
12. The method of claim 10The preparation method of the modified lithium nickel cobalt manganese cathode material is characterized in that the first doping compound in the step (1) is selected from Mg3N2、WS2、MoS2、VP2、CoP3、MnP4、NiP2、NbP、Sn4P3、TiP2、ZrP2、WSe2、WP2And one or more of TiP.
13. The method of claim 10, wherein the first coating compound in step (3) is selected from MgO and Al2O3、SiO2、ZrO2、ZnO、TiO2、B2O3、Bi2O3、Nb2O5、MoO2、MoO3、NiO、MnO2、V2O5、WO2、WO3、SnO2、LiNbO3、Li2TiO3、Li2ZrO3、LiMn2O4、Li2MoO4One or more of them.
14. The preparation method of the modified lithium nickel cobalt manganese cathode material according to claim 10, wherein the pH value of the reaction system in step (1) is 10.8-12.0, and the reaction temperature in step (1) is 50-80 ℃.
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