CN113764658B - Anion-cation co-doped high-nickel monocrystal ternary cathode material, and preparation method and application thereof - Google Patents

Anion-cation co-doped high-nickel monocrystal ternary cathode material, and preparation method and application thereof Download PDF

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CN113764658B
CN113764658B CN202111017272.9A CN202111017272A CN113764658B CN 113764658 B CN113764658 B CN 113764658B CN 202111017272 A CN202111017272 A CN 202111017272A CN 113764658 B CN113764658 B CN 113764658B
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nickel
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CN113764658A (en
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纪效波
倪炼山
侯红帅
邹国强
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Central South University
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    • 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
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    • H01—ELECTRIC ELEMENTS
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    • H01M10/05—Accumulators with non-aqueous electrolyte
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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Abstract

The invention discloses an anion-cation co-doped high-nickel monocrystal ternary cathode material, a preparation method and application thereof, and the molecular formula is as follows: li (Li) 1+a Ni x Co y Mn z M a O 2‑b Q b The method comprises the steps of carrying out a first treatment on the surface of the Wherein: m is one or more of Mg, sf, al, zr, nb, ta, mo, ti, Y, W and V; q is one or more of F, N, P, S and Se; 1 > x > y > z > 0, x > 0.5, and x+y+z=1. The element Q and the element M of the anion-cation co-doped high-nickel monocrystal ternary cathode material respectively replace oxygen sites and transition metal nickel, cobalt and manganese sites, so that capacity attenuation and voltage drop of the high-nickel monocrystal ternary cathode material in a circulating process can be restrained, circulating stability, thermal stability and intrinsic conductivity can be improved, rate performance is improved, and capacity attenuation and microcrack of the high-nickel monocrystal ternary cathode material in the circulating process can be effectively restrained.

Description

Anion-cation co-doped high-nickel monocrystal ternary cathode material, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium ion battery materials, relates to a lithium ion battery positive electrode material and a preparation method thereof, and in particular relates to an anion-cation co-doped high-nickel monocrystal ternary positive electrode material and a preparation method and application thereof.
Background
Along with the development of society and the progress of science and technology, clean and efficient energy storage and conversion become a research hotspot in the energy field.
The lithium ion battery is used as a novel secondary power supply, has the advantages of high specific energy, no memory effect, long cycle life, little environmental pollution and the like, and fills fresh blood for the vigorous development of an energy network. The lithium ion electric automobile is an important component in a new energy automobile family, and the high-energy density lithium ion power battery is used as a heart of the electric automobile, so that the problem of mileage anxiety in the field of electric automobiles can be effectively solved. In recent years, the demand of lithium ion power batteries has been increasing, and high-energy-density positive electrode materials have been receiving extensive attention from researchers as a key part of lithium ion power batteries.
The high-nickel ternary positive electrode material has higher specific capacity (about 200 mAh/g) due to higher Ni content, and is one of the most potential positive electrode materials of next-generation high-energy-density lithium ion batteries. However, it is difficult to synthesize high nickel ternary materials that meet the stoichiometric composition, limited by thermodynamic considerations. Due to Li + And Ni 2+ The ionic radius of (2) is extremely close in size, resulting in a portion of Ni 2+ Is easy to migrate to the lithium layer to occupy lithium position, causing Li + /Ni 2+ Cation mixing and discharging. Serious lithium nickel mixed discharge defects can increase the internal resistance of the material, prevent the deintercalation of lithium ions and deteriorate the electrochemical performance. In addition, the higher the Ni content of the high-nickel ternary anode is, the more serious the phase transition of H2-H3 is, so that the crystal lattice is severely contracted, anisotropic strain is generated by primary particles, microcracks are generated, electrolyte permeates into the particles along the cracks, side reactions continuously occur to form an insulating rock salt phase layer, even pulverization of an electrode material is caused, the impedance of the material is increased, and the dynamic performance is reduced. After a certain number of times of cyclic charge and discharge, the material structure change causes the loss of active substances due to the dissolution of Ni, co and Mn metal elements, and the capacityThe amount is further reduced. Therefore, there is an urgent need to solve the problem of neck with poor stability of high nickel ternary structure and thermal stability.
In the prior art, in order to solve the above-mentioned problems, ion doping is generally focused on the ternary cathode material, and the doping mainly includes bulk doping and surface doping.
However, both bulk and surface doping in the prior art suffer from certain drawbacks: the doped inactive substance elements can lead to the capacity reduction of the battery, and the ternary positive electrode material after the doping is generally spherical secondary particles, the doping is also limited on the surfaces of the secondary particles, the primary particles do not effectively participate in the doping process, and the cycling stability and the safety of the battery under high voltage still need to be improved. Therefore, in the prior art, regarding the method for doping ternary cathode materials, there are many problems that the doping elements are unevenly distributed in the cathode materials, thereby affecting the capacity and stability thereof, and the doping substances and doping methods in the doping steps thereof still need to be improved. In addition, another scheme is that a large-particle single crystal ternary positive electrode material is adopted, and primary particle grain boundaries are not existed, so that microcracks caused by anisotropic strain among primary particles are restrained, the structural stability and the safety are greatly improved, but the lithium ion transmission path is increased due to the large-particle single crystal, and the rate performance is deteriorated.
Therefore, the search for suitable dopants and efficient bulk doping methods is critical to improving the structural stability and the rate capability and safety of high nickel ternary single crystal positive electrode materials.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide an anion-cation co-doped high-nickel monocrystal ternary cathode material, a preparation method and application thereof, which can inhibit microcrack generation in the circulation process, and can improve intrinsic conductivity, so that capacity attenuation and voltage drop in the circulation process are relieved, and the problems of poor rate capability, serious capacity and voltage attenuation in the circulation process and the like of the conventional cathode material can be effectively solved.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a high nickel monocrystal ternary positive electrode material co-doped with anions and cations has a molecular formula as follows: liNi x Co y Mn z M a O 2-b Q b
Wherein:
m is one or more of Mg, sr, al, zr, nb, ta, mo, ti, Y, W and V;
q is one or more of F, N, P, S and Se;
1 > x > y > z > 0, x > 0.5, and x+y+z+a=1.
In the technical scheme, in the molecular formula of the high-nickel monocrystal ternary positive electrode material, a is more than or equal to 0.001 and less than or equal to 0.05,0.001, and b is more than or equal to 0.1.
In the technical scheme, the co-doping elements M and Q are uniformly distributed in the high-nickel single crystal ternary cathode material.
In the technical scheme, the high-nickel single crystal ternary cathode material has a layered structure.
In the technical scheme, the capacity of the high-nickel monocrystal ternary cathode material is more than or equal to 190mAh/g when the discharge multiplying power is 0.1C, and the capacity retention rate after 150 times of circulation is more than 85%.
The invention also provides a preparation method of the anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
mixing the precursor containing nickel, cobalt and manganese with lithium source raw material, cation doping agent containing element M and fluxing agent proportionally, melting at 500-900 under oxygen atmosphere, cooling, grinding into powder, washing and drying, mixing with anion doping agent containing element Q proportionally, heating and sintering at 500-800 under argon atmosphere, cooling, washing and drying, and heating and sintering at 500-800 under oxygen atmosphere.
In the above technical scheme, the high-temperature melting is two-stage high-temperature melting, and specifically includes: preserving heat at 500-700 deg.C for 5-10h, and preserving heat at 680-900 deg.C for 8-48h.
Preferably, in the above technical solution, the cooling rate after the high-temperature melting is 2.5-4.5 /min.
Further preferably, in the above technical scheme, the temperature rising speed after the heat preservation at 500-700 is 2-3.6 /min.
In the technical scheme, the temperature and the heat preservation time of the primary heating sintering are respectively 500-800 and 5-10 hours;
preferably, in the above technical scheme, the cooling speed after the primary heating sintering is 2-4.5 /min.
In the technical scheme, the temperature and the heat preservation time of the secondary heating sintering are respectively 500-800 and 5-10h.
Preferably, in the above technical scheme, the cooling rate after the secondary heating sintering is 3-5.5 /min.
Further, in the above technical solution, the precursor containing nickel, cobalt and manganese is one or more of carbonate, hydroxide and acetate containing nickel, cobalt and manganese.
Further, in the above technical scheme, the lithium source raw material is one or more of lithium carbonate, lithium hydroxide monohydrate, lithium hydroxide, lithium acetate and lithium nitrate.
Further, in the above technical scheme, the cation dopant containing the element M is MgO or Al 2 O 3 ZrO 2 TiO 2 SrONb 2 O 5 MoO 3 Ta 2 O 5 V 2 O 5 Y 2 O 3 And WO 3 One or more of the following.
Further, in the above technical scheme, the anionic dopant containing the element Q is one or more of ammonium fluoride, monoammonium phosphate, urea, sodium hypophosphite, thiourea, sulfur powder and selenium powder.
Further, in the above technical solution, the fluxing agent is one or more of lithium chloride, sodium chloride, potassium chloride, lithium nitrate, sodium nitrate, potassium nitrate, lithium sulfate, sodium sulfate, potassium sulfate, lithium carbonate, sodium carbonate and potassium carbonate.
Still further, in the above technical scheme, the addition mass of the fluxing agent is 0.1-15 times of the precursor containing nickel, cobalt and manganese.
Still further, in the above technical scheme, the molar excess coefficient of the lithium source raw material is 1 to 10%.
In one specific embodiment of the invention, the preparation method of the anion-cation co-doped high nickel single crystal ternary cathode material comprises the following steps:
s1, uniformly mixing a precursor containing nickel, cobalt and manganese with a lithium source raw material, a cation doping agent containing an element M and a fluxing agent in proportion to obtain a raw material mixture containing the cation doping agent;
s2, placing the raw material mixture in the S1 in an oxygen atmosphere, firstly preserving heat at 500-700 for 5-10h, then heating to 680-900 at a speed of 2-3.6 /min, preserving heat for 8-48h, and then cooling to normal temperature at a speed of 2.5-4.5 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, washing and filtering with deionized water and absolute ethyl alcohol, and vacuum drying to obtain cation doped intermediate powder;
S4, uniformly mixing the cation doped intermediate powder in the S3 and the anion doping agent containing the element Q according to a proportion, placing the mixture in an argon atmosphere, preserving heat at 500-800 , heating and sintering for 5-10h at one time, and cooling to normal temperature at a speed of 2-4.5 /min to obtain a high-nickel monocrystal ternary anode material mixture containing the co-doping of anions and cations;
s5, filtering and washing the mixture containing the high nickel single crystal ternary positive electrode material co-doped with anions and cations obtained in the step S4 with CS2 solution to remove redundant anion doping agent, washing and filtering with deionized water and absolute ethyl alcohol, and vacuum drying to obtain high nickel single crystal ternary positive electrode material intermediate powder co-doped with anions and cations;
s6, transferring the intermediate powder of the anion-cation co-doped high-nickel monocrystal ternary cathode material in the S5 into a corundum square boat again, then placing the corundum square boat in an oxygen atmosphere, preserving heat at 500-800 , carrying out secondary heating sintering for 5-10h, and cooling to normal temperature at a speed of 3-5.5 /min to obtain the anion/cation co-doped monocrystal ternary cathode material.
The invention also provides a positive electrode plate which comprises the high nickel monocrystal ternary positive electrode material co-doped with anions and cations.
The invention further provides a lithium ion battery, which comprises the positive electrode plate.
Compared with the prior art, the invention has the following advantages:
(1) The element Q replaces the oxygen site in the high-nickel single-crystal ternary positive electrode material, so that excessive oxidation of lattice oxygen can be restrained under high potential, lattice oxygen loss can be relieved, super-oxygen free radicals generated in the lattice oxygen oxidation process can be eliminated, electrolyte decomposition caused by the super-oxygen free radicals can be relieved, and capacity attenuation and voltage drop of the high-nickel single-crystal ternary positive electrode material in the circulation process can be cooperatively restrained;
(2) According to the anion-cation co-doped high-nickel monocrystal ternary cathode material provided by the invention, the element M is distributed in the high-nickel monocrystal ternary cathode material, so that the crystal structure can be stabilized in the charge-discharge process, the oxygen vacancy forming energy is improved, the generation of microcracks is inhibited, and the cycle stability and the thermal stability are improved; in addition, the cation doping can also induce lattice defects, improve the intrinsic conductivity and improve the rate capability;
(3) According to the preparation method of the anion-cation co-doped high-nickel monocrystal ternary cathode material, provided by the invention, the specific cosolvent is added, so that the melting point of a raw material mixture is reduced, the sintering temperature is reduced, the sintering time is shortened, the process cost is reduced, in addition, the raw material mixture is melted to form uniform fluid, the dopant is promoted to be uniformly diffused to a cathode phase, and the particle dispersion is uniform, and the anion-cation co-doped high-nickel monocrystal ternary cathode material with the primary particle size of more than 0.5 mu m can be obtained by matching with the optimized staged heating and cooling procedures;
(4) The preparation process of the anion-cation co-doped high-nickel monocrystal ternary cathode material provided by the invention is simple and easy to popularize, and is a method for effectively inhibiting capacity attenuation and microcracking of the high-nickel ternary cathode material in the circulation process.
Drawings
FIG. 1 is a SEM photograph at a magnification of 6000 of an NCM sample prepared according to example 1 of the present invention;
FIG. 2 is an SEM photograph of an NCM sample obtained in example 1 of the present invention at 13000 magnification;
FIG. 3 is a SEM photograph of a Nb-Se-NCM sample at 2300 magnification of the sample prepared in example 2 of the present invention;
FIG. 4 is a SEM photograph of a Nb-Se-NCM sample at 10000 times magnification of the sample prepared in example 2 according to the present invention;
FIG. 5 is an X-ray diffraction pattern of the NCM sample obtained in example 1 and the Nb-Se-NCM sample obtained in example 2 of the present invention;
FIG. 6 is a first charge-discharge curve of a button cell of which NCM sample prepared in example 1 and Nb-Se-NCM sample prepared in example 2 are used as positive electrode materials of a lithium ion battery to prepare a positive electrode sheet;
fig. 7 is a mass specific capacity curve of a button cell in which the NCM sample prepared in example 1 and the Nb-Se-NCM sample prepared in example 2 of the present invention are used as a positive electrode material for a lithium ion battery to prepare a positive electrode sheet, which is cycled 150 times at a current density of 1C.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the examples, all means used are conventional in the art unless otherwise specified.
The terms "comprising," "including," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
In the examples of the present invention, the nickel, cobalt and manganese containing precursor used was the commercially available composite product Mn 0.83 Co 0.11 Ni 0.06 (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the The rest experimental raw materials are all conventional commercial products.
In the embodiment of the invention, all the equipment, instruments and the like can be purchased in the market or prepared by the prior art.
Example 1
The embodiment of the invention provides a preparation method of a high-nickel monocrystal ternary positive electrode material, which comprises the following steps of:
s1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture;
s2, transferring the raw material mixture in the step S1 into a corundum ark, then placing the corundum ark under an oxygen atmosphere, heating to 500 at a speed of 3 /min, then preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying at 80 for 12h to obtain intermediate powder;
s4, transferring the intermediate powder in the step S3 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, preserving heat and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the high-nickel monocrystal ternary anode material NCM.
Example 2
The embodiment of the invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
S1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.000025mol Nb 2 O 5 0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing Nb ion doping agent;
s2, transferring the raw material mixture containing the Nb ion doping agent in S1 into a corundum ark, then placing the corundum ark under an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying for 12h at 80 to obtain Nb doped intermediate powder;
s4, placing the Nb-doped intermediate powder and 0.00005mol Se powder in the S3 into an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing the solid mixture in an argon atmosphere, heating to 700 at a speed of 3 /min, preserving heat and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain a high-nickel monocrystal ternary cathode material mixture containing Nb-Se co-doping;
s5, respectively washing and filtering the mixture containing the Nb-Se co-doped high-nickel monocrystal ternary cathode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain Nb-Se co-doped high-nickel monocrystal ternary cathode material intermediate powder;
S6, transferring the Nb-Se co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, performing heat preservation and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the anion-cation co-doped high-nickel single crystal ternary cathode material Nb-Se-NCM.
Example 3
The embodiment of the invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
s1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.00005mol ZrO 2 0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing Zr ion doping agent;
s2, transferring the raw material mixture containing the Zr ion dopant in the S1 into a corundum ark, then placing the corundum ark under an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying at 80 for 12h to obtain Zr-doped intermediate powder;
S4, placing Zr-doped intermediate powder in the S3 and 0.00005mol of ammonium fluoride in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, placing in an argon atmosphere, performing heat preservation and sintering at 700 for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain a Zr-F co-doped high-nickel monocrystal ternary cathode material mixture;
s5, respectively washing and filtering the mixture containing the Zr-F co-doped high-nickel single crystal ternary positive electrode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain Zr-F co-doped high-nickel single crystal ternary positive electrode material intermediate powder;
s6, transferring the Zr-F co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, carrying out heat preservation and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the anionic-cationic co-doped high-nickel single crystal ternary cathode material Zr-F-NCM.
Example 4
The embodiment of the invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
S1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.00005mol SrO0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing Sr ion doping agent;
s2, transferring the raw material mixture containing the Sr ion doping agent in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying at 80 for 12h to obtain Sr-doped intermediate powder;
s4, placing the Sr-doped intermediate powder in the S3 and 0.00005mol of ammonium dihydrogen phosphate in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing in an argon atmosphere, carrying out heat preservation and sintering at 700 for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain a Sr-P co-doped high-nickel monocrystal ternary cathode material mixture;
s5, respectively washing and filtering the mixture containing the Sr-P co-doped high-nickel monocrystal ternary cathode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain Sr-P co-doped high-nickel monocrystal ternary cathode material intermediate powder;
S6, transferring the Sr-P co-doped high-nickel monocrystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, performing heat preservation and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the anionic-cationic co-doped high-nickel monocrystal ternary cathode material Sr-P-NCM.
Example 5
The embodiment of the invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
s1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.00005mol MgO0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing Mg ion doping agent;
s2, transferring the raw material mixture containing the Mg ion dopant in the S1 into a corundum ark, then placing the corundum ark under an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying at 80 for 12h to obtain Mg-doped intermediate powder;
S4, placing the Mg-doped intermediate powder and 0.00005mol of sulfur powder in the S3 into an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, placing the solid mixture in an argon atmosphere, performing heat preservation and sintering at 700 for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain a high-nickel single crystal ternary positive electrode material mixture containing Mg-S co-doping;
s5, respectively washing and filtering the mixture containing the Mg-S co-doped high-nickel monocrystal ternary cathode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain Mg-S co-doped high-nickel monocrystal ternary cathode material intermediate powder;
s6, transferring the Mg-S co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, carrying out heat preservation and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the anion-cation co-doped high-nickel single crystal ternary cathode material Mg-S-NCM.
Example 6
The embodiment of the invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
S1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.000025mol Ta 2 O 5 0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing Ta ion doping agent;
s2, transferring the raw material mixture containing the Ta ion doping agent in the S1 into a corundum ark, then placing the corundum ark under an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying at 80 for 12h to obtain Ta doped intermediate powder;
s4, placing the Ta-doped intermediate powder in the S3 and 0.000025mol of urea in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, placing the solid mixture in an argon atmosphere, performing heat preservation and sintering at 700 for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain a Ta-N co-doped high-nickel monocrystal ternary cathode material mixture;
s5, respectively washing and filtering the mixture containing the Ta-N co-doped high-nickel monocrystal ternary cathode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain Ta-N co-doped high-nickel monocrystal ternary cathode material intermediate powder;
S6, transferring the Ta-N co-doped high-nickel monocrystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, preserving heat and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the anionic-cationic co-doped high-nickel monocrystal ternary cathode material Ta-N-NCM.
Example 7
The embodiment of the invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
s1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.000025mol Al 2 O 3 0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing Al ion doping agent;
s2, transferring the raw material mixture containing the Al ion doping agent in the S1 into a corundum ark, then placing the corundum ark under an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying at 80 for 12h to obtain Al-doped intermediate powder;
S4, placing the Al-doped intermediate powder in the S3 and 0.00005mol of ammonium fluoride in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, placing the solid mixture in an argon atmosphere, performing heat preservation and sintering at 700 for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain a high-nickel single crystal ternary cathode material mixture containing Al-F co-doping;
s5, respectively washing and filtering the mixture containing the Al-F co-doped high-nickel single crystal ternary positive electrode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain Al-F co-doped high-nickel single crystal ternary positive electrode material intermediate powder;
s6, transferring the Al-F co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, carrying out heat preservation and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the anionic-cationic co-doped high-nickel single crystal ternary cathode material Al-F-NCM.
Example 8
The embodiment of the invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
S1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.000025mol Y 2 O 3 0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing Y ion doping agent;
s2, transferring the raw material mixture containing the Y ion dopant in the S1 into a corundum ark, then placing the corundum ark under an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying at 80 for 12h to obtain Y-doped intermediate powder;
s4, placing the Y-doped intermediate powder in the S3 and 0.00005mol of ammonium fluoride in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, placing the solid mixture in an argon atmosphere, performing heat preservation and sintering at 700 for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain a Y-F co-doped high-nickel monocrystal ternary cathode material mixture;
s5, respectively washing and filtering the mixture containing the Y-F co-doped high-nickel single crystal ternary positive electrode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain Y-F co-doped high-nickel single crystal ternary positive electrode material intermediate powder;
S6, transferring the Y-F co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, carrying out heat preservation and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the anion-cation co-doped high-nickel single crystal ternary cathode material Y-F-NCM.
Example 9
The embodiment of the invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
s1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.00005mol WO 3 0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing W ion doping agent;
s2, transferring the raw material mixture containing the W ion dopant in the S1 into a corundum ark, then placing the corundum ark under an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying at 80 for 12h to obtain W-doped intermediate powder;
S4, placing the W-doped intermediate powder in the S3 and 0.00005mol Se powder in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, placing in an argon atmosphere, performing heat preservation and sintering at 700 for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain a W-Se co-doped high-nickel monocrystal ternary cathode material mixture;
s5, respectively washing and filtering the mixture containing the W-Se co-doped high-nickel single crystal ternary positive electrode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain W-Se co-doped high-nickel single crystal ternary positive electrode material intermediate powder;
s6, transferring the W-Se co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, performing heat preservation and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the anionic-cationic co-doped high-nickel single crystal ternary cathode material W-Se-NCM.
Example 10
The embodiment of the invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
S1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.00005mol TiO 2 0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing Ti ion doping agent;
s2, transferring the raw material mixture containing the Ti ion doping agent in the S1 into a corundum ark, then placing the corundum ark under an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying at 80 for 12h to obtain Ti-doped intermediate powder;
s4, placing the Ti-doped intermediate powder in the S3 and 0.00005mol of sulfur powder in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, placing the solid mixture in an argon atmosphere, performing heat preservation and sintering at 700 for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain a Ti-S co-doped high-nickel monocrystal ternary cathode material mixture;
s5, respectively washing and filtering the mixture containing the Ti-S co-doped high-nickel single crystal ternary positive electrode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain Ti-S co-doped high-nickel single crystal ternary positive electrode material intermediate powder;
S6, transferring the Ti-S co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, carrying out heat preservation and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the cathode-anode co-doped high-nickel single crystal ternary cathode material Ti-S-NCM.
Comparative example 1
The invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which specifically comprises the following steps:
s1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.000025mol Nb 2 O 5 0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing Nb ion doping agent;
s2, transferring the raw material mixture containing the Nb cation doping agent in S1 into a corundum ark, then placing the corundum ark under an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 9 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying for 12h at 80 to obtain Nb doped intermediate powder;
S4, placing the Nb-doped intermediate powder and 0.00005mol Se powder in the S3 into an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing the solid mixture in an argon atmosphere, heating to 700 at a speed of 3 /min, preserving heat and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain a high-nickel monocrystal ternary cathode material mixture containing Nb-Se co-doping;
s5, respectively washing and filtering the mixture containing the Nb-Se co-doped high-nickel monocrystal ternary cathode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain Nb-Se co-doped high-nickel monocrystal ternary cathode material intermediate powder;
s6, transferring the Nb-Se co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, performing heat preservation and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the anion-cation co-doped high-nickel single crystal ternary cathode material Nb-Se-NCM.
Comparative example 2
The embodiment of the invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
S1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.00005mol ZrO 2 0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing Zr ion doping agent;
s2, transferring the raw material mixture containing the Zr ion dopant in the S1 into a corundum ark, then placing the corundum ark under an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying at 80 for 12h to obtain Zr-doped intermediate powder;
s4, placing Zr-doped intermediate powder in the S3 and 0.00005mol of ammonium fluoride in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, heating to 420 at a speed of 3 /min, preserving heat and sintering for 6 hours, and cooling to normal temperature at a speed of 6 /min to obtain a Zr-F co-doped high-nickel monocrystal ternary cathode material mixture;
s5, respectively washing and filtering the mixture containing the Zr-F co-doped high-nickel single crystal ternary positive electrode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain Zr-F co-doped high-nickel single crystal ternary positive electrode material intermediate powder;
S6, transferring the Zr-F co-doped high-nickel single crystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 700 at a speed of 3 /min, carrying out heat preservation and sintering for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the anionic-cationic co-doped high-nickel single crystal ternary cathode material Zr-F-NCM.
Comparative example 3
The embodiment of the invention provides a preparation method of an anion-cation co-doped high-nickel monocrystal ternary cathode material, which comprises the following steps:
s1, 0.02mol of Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 0.00005mol SrO0.0702mol LiOHH 2 O0.0966mol LiNO 3 And 0.0132mol LiCl are placed in an agate ball milling tank, and mixed for 2 hours in a dry environment to obtain a raw material mixture containing Sr ion doping agent;
s2, transferring the raw material mixture containing the Sr ion doping agent in the S1 into a corundum ark, then placing the corundum ark in an oxygen atmosphere, heating to 500 at a speed of 3 /min, preserving heat for 5 hours, heating to 800 at a speed of 3 /min, preserving heat for 12 hours, and then cooling to normal temperature at a speed of 3 /min to obtain a solid molten material;
s3, grinding the solid molten material in the step S2 into powder, stirring for 30min by using deionized water, carrying out suction filtration and washing for 3 times by using deionized water and absolute ethyl alcohol respectively, and finally, carrying out vacuum drying at 80 for 12h to obtain Sr-doped intermediate powder;
S4, placing the Sr-doped intermediate powder in the S3 and 0.00005mol of ammonium dihydrogen phosphate in an agate ball milling tank, mixing for 2 hours in a dry environment to obtain a solid mixture, then placing in an argon atmosphere, carrying out heat preservation and sintering at 700 for 6 hours, and cooling to normal temperature at a speed of 3 /min to obtain the Sr-P co-doped high-nickel monocrystal ternary cathode material mixture.
S5, respectively washing and filtering the mixture containing the Sr-P co-doped high-nickel monocrystal ternary cathode material obtained in the step S4 with CS2 solution, deionized water and absolute ethyl alcohol for 1 time, and finally vacuum drying for 12 hours at 80 to obtain Sr-P co-doped high-nickel monocrystal ternary cathode material intermediate powder.
S6, transferring the Sr-P co-doped high-nickel monocrystal ternary cathode material intermediate powder in the S5 into a corundum ark again, placing the corundum ark under an oxygen atmosphere, heating to 420 at a speed of 3 /min, carrying out heat preservation and sintering for 6 hours, and cooling to normal temperature at a speed of 6 /min to obtain the anionic-cationic co-doped high-nickel monocrystal ternary cathode material Sr-P-NCM.
The NCM sample prepared in example 1 and the Nb-Se-NCM sample prepared in example 2 were characterized.
FIGS. 1 and 2 are SEM pictures at 6000 and 13000 magnification of NCM samples obtained according to example 1 of the present invention, respectively; FIGS. 3 and 4 are SEM pictures at 2300 times and 10000 times, respectively, of Nb-Se-NCM samples obtained in example 2 of the present invention.
As can be seen from fig. 1-4, the samples produced all consisted of primary microparticles and were sized around 1 m; in addition, as can be seen from comparison of FIGS. 1 to 4, the microscopic morphology of the doped Nb-Se-NCM high-nickel single crystal ternary cathode material sample prepared in example 2 was not significantly changed compared to the NCM sample prepared in example 1.
FIG. 5 is an X-ray diffraction pattern of the NCM sample obtained in example 1 and the Nb-Se-NCM sample obtained in example 2 of the present invention.
As can be seen from fig. 5, the prepared samples are all in a layered structure, and the corresponding space group is R-3m; in addition, the peak intensity ratio of diffraction peaks (003)/(104) is larger than 1.2, which proves that Li/Ni mixed discharge is weak; notably, the peak intensity ratio of (003)/(104) increases after doping Nb and Se elements, indicating that the degree of Li/Ni miscibility decreases; in addition, both pairs of cleavage peaks (006)/(102) and (108)/(110) were markedly split, confirming that a good layered structure was obtained.
The samples prepared in examples 1 to 10 and comparative examples 1 to 2 were used as positive electrode materials for lithium ion batteries, respectively, to prepare positive electrode sheets, and the specific procedures were as follows:
(1) Mixing the prepared powdery positive electrode material with acetylene black (conductive agent) and polyvinylidene fluoride (PVDF, adhesive) according to a mass ratio of 8:1:1, uniformly mixing, dropwise adding a proper amount of N-methyl pyrrolidone (NMP) as a dispersing agent, and grinding into slurry; then, uniformly coating the slurry on an aluminum foil, drying the aluminum foil in vacuum at 120 for 12 hours, and transferring the aluminum foil into an argon atmosphere glove box for standby;
(2) The half cell was assembled in an argon atmosphere glove box with metallic lithium as the counter electrode and LiPF 6 Ethylene carbonate (EC: DMC: dec=1:1:1) was used as an electrolyte, and a button cell having an assembly specification of CR2016 was charged and discharged in a constant current charge and discharge mode.
FIG. 6 is a graph showing the first charge and discharge curves of button cells prepared from the NCM sample prepared in example 1 and the Nb-Se-NCM sample prepared in example 2 as positive electrode materials for lithium ion batteries; as can be seen from FIG. 6, the first-turn discharge capacities were 199.4mAh/g (NCM) and 196.3 (Nb-Se-NCM) mAh/g, respectively, and the corresponding coulombic efficiencies were 88.9% (NCM) and 89.5% (Nb-Se-NCM), respectively.
The first-turn discharge capacity and coulombic efficiency measured after the positive electrode sheet was prepared from each of the samples prepared in Table 1
Table 1 shows the results of the first-turn discharge capacity and coulombic efficiency of button cells prepared from each of the samples prepared in the examples and comparative examples according to the present invention as positive electrode materials for lithium ion batteries.
As can be seen from the results of fig. 6 and table 1, the first coulomb efficiency of the button cell prepared by using the sample prepared by co-doping the anions and cations as the positive electrode material of the lithium ion battery is significantly improved, which indicates that the irreversible capacity loss of the high nickel monocrystal ternary positive electrode material co-doped by the anions and cations in the charging process is significantly inhibited.
FIG. 7 is a graph showing the mass specific capacity curves of a button cell prepared from the NCM sample prepared in example 1 and the Nb-Se-NCM sample prepared in example 2 as a positive electrode material for a lithium ion battery, wherein the button cell circulates 150 times at a current density of 1C; as can be seen from FIG. 7, the retention rates after 150 cycles at a current density of 1C were 87.6% (Nb-Se-NCM) and 41.2% (NCM), respectively.
The samples prepared in Table 2 were subjected to a cycle of 150 times after preparing the positive electrode sheet
Table 2 shows the results of the retention rate after 150 cycles of button cells prepared from each of the examples and comparative examples of the present invention as a positive electrode material for lithium ion batteries.
As can be seen from the results of fig. 7 and table 2, the sample prepared after co-doping of anions and cations is used as a positive electrode material of a lithium ion battery, which can effectively inhibit capacity fade of a button cell during cycling.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention.
It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (11)

1. A high nickel monocrystal ternary positive electrode material co-doped with anions and cations is characterized in that,
the molecular formula is as follows: li (Li) 1+a Ni x Co y Mn z M a O 2-b Q b
Wherein:
m is one or more of Mg, sr, al, zr, nb, ta, mo, ti, Y, W and V;
q is one or more of F, N, P, S and Se;
1 > x > y > z > 0, x > 0.5, and x+y+z=1=1; a is more than or equal to 0.001 and less than or equal to 0.05,0.001, b is more than or equal to 0.1;
the preparation method comprises the following steps:
uniformly mixing a precursor containing nickel, cobalt and manganese with a lithium source raw material, a cation doping agent containing an element M and a fluxing agent in proportion, melting at a high temperature of 500-900 under an oxygen atmosphere, cooling, grinding into powder, washing and drying, uniformly mixing with an anion doping agent containing an element Q in proportion, heating and sintering at 500-800 under an argon atmosphere, cooling, washing and drying, and heating and sintering at 500-800 for the second time under an oxygen atmosphere;
the high-temperature melting is two-section high-temperature melting, and specifically comprises the following steps: preserving heat at 500-700 deg.C for 5-10 h, and preserving heat at 680-900 deg.C for 8-48 h;
the cooling speed after high-temperature melting is 2.5-4.5 /min.
2. The negative and positive ion co-doped high nickel single crystal ternary positive electrode material according to claim 1, wherein,
And the co-doping elements M and Q are uniformly distributed in the high-nickel single crystal ternary cathode material.
3. The negative and positive ion co-doped high nickel single crystal ternary positive electrode material according to claim 1 or 2, wherein,
the high-nickel monocrystal ternary anode material has a layered structure;
and/or the capacity of the high-nickel monocrystal ternary positive electrode material is more than or equal to 190 mAh/g when the discharge multiplying power is 0.1 and C, and the capacity retention rate is more than 85% after 150 times of circulation.
4. A method for preparing an anion-cation co-doped high nickel single crystal ternary cathode material according to any one of claims 1-3, which is characterized in that,
comprising the following steps: mixing the precursor containing nickel, cobalt and manganese with lithium source raw material, cation doping agent containing element M and fluxing agent proportionally, melting at 500-900 under oxygen atmosphere, cooling, grinding into powder, washing and drying, mixing with anion doping agent containing element Q proportionally, heating and sintering at 500-800 under argon atmosphere, cooling, washing and drying, and heating and sintering at 500-800 under oxygen atmosphere.
5. The method for preparing a ternary cathode material of an anion-cation co-doped high nickel monocrystal according to claim 4, wherein the heating rate after heat preservation at 500-700 is 2-3.6 /min.
6. The method for preparing the anion-cation co-doped high nickel single crystal ternary cathode material according to claim 4, wherein the method is characterized in that,
the temperature and the heat preservation time of the primary heating sintering are 500-800 and 5-10 h respectively; and/or the number of the groups of groups,
the temperature and the heat preservation time of the secondary heating sintering are 500-800 and 5-10 h respectively.
7. The method for preparing the ternary cathode material of the anion-cation co-doped high nickel monocrystal, according to claim 4, wherein the cooling speed after primary heating sintering is 2-4.5 /min;
and/or the number of the groups of groups,
the cooling speed after the secondary heating sintering is 3-5.5 /min.
8. The method for preparing the anion-cation co-doped high nickel single crystal ternary cathode material according to any one of claims 4 to 7, wherein the method is characterized in that,
the precursor containing nickel, cobalt and manganese is one or more of carbonate, hydroxide and acetate containing nickel, cobalt and manganese;
and/or the lithium source raw material is one or more of lithium carbonate, lithium hydroxide monohydrate, lithium hydroxide, lithium acetate and lithium nitrate;
and/or the dopant containing the element M is MgO and Al 2 O 3 ZrO 2 TiO 2 SrONb 2 O 5 MoO 3 Ta 2 O 5 V 2 O 5 Y 2 O 3 And WO 3 One or more of the following;
and/or the doping agent containing the element Q is one or more of ammonium fluoride, monoammonium phosphate, urea, sodium hypophosphite, thiourea, sulfur powder and selenium powder;
And/or the fluxing agent is one or more of lithium chloride, sodium chloride, potassium chloride, lithium nitrate, sodium nitrate, potassium nitrate, lithium sulfate, sodium sulfate, potassium sulfate, lithium carbonate, sodium carbonate and potassium carbonate.
9. The method for preparing the anion-cation co-doped high nickel single crystal ternary cathode material according to claim 8, wherein the method is characterized in that,
the addition mass of the fluxing agent is 0.1-15 times of that of the precursor containing nickel, cobalt and manganese;
and/or the molar excess coefficient of the lithium source raw material is 1-10%.
10. A positive electrode plate is characterized in that,
the positive electrode plate comprises the high nickel monocrystal ternary positive electrode material co-doped with anions and cations according to any one of claims 1-3.
11. A lithium ion battery is characterized in that,
the lithium ion battery comprises the positive electrode sheet of claim 10.
CN202111017272.9A 2021-08-31 2021-08-31 Anion-cation co-doped high-nickel monocrystal ternary cathode material, and preparation method and application thereof Active CN113764658B (en)

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