CN114188515A - Polymer-coated high-nickel ternary cathode material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a polymer-coated high-nickel ternary cathode material and a preparation method and application thereof, wherein the high-nickel ternary cathode material is coated with a polymer I, the polymer I is formed by polymerizing a transition metal oxygen cluster compound, a low molecular weight polyether precursor and isocyanate under the action of an initiator, and the molar ratio of the low molecular weight polyether precursor to the isocyanate is 1: 1-1: 1.5; the molar ratio of the transition metal oxygen cluster compound to the low molecular weight polyether precursor is 0.0005-0.01: 1. the invention can obviously improve the cycling stability and the rate capability of the battery.
Description
Technical Field
The invention relates to a high-nickel ternary cathode material of a lithium ion battery, in particular to a preparation method and application of a coated high-nickel ternary cathode material.
Background
With the continuous development and progress of society, the energy consumption demand is gradually increased, and the acquisition and the use of renewable energy have important practical significance. The successful commercialization of lithium ion batteries has changed the energy consumption form of people greatly over the last two decades. However, with the increasing popularization of large energy storage power grids and electric vehicles, people have higher and higher requirements on the energy density of lithium ion batteries.
The positive electrode material, as an important component of the lithium ion battery, determines the energy density of the lithium ion battery to a great extent. Compared with traditional positive electrode material (such as lithium iron phosphate, lithium cobaltate, etc.), ternary nickel cobalt manganese positive electrode material (molecular formula: Li [ Ni ]xMnyCo1-x-y]O2NMC for short) has an outstanding energy density advantage, and particularly, a high-nickel ternary material with high theoretical specific capacity and low cobalt usage gradually becomes a mainstream positive electrode material for research in the field of power batteries. However, the high-nickel ternary nickel-cobalt-manganese positive electrode material has inherent stability defects, can generate side reactions with electrolyte, and is easy to have the problems of dissolution of transition metal elements, mixed arrangement of Li/Ni, irreversible change of a layered structure and the like, so that the cycle capacity of the battery is rapidly reduced, and potential safety hazards of the battery are caused.
In order to improve the stability of the high-nickel ternary cathode material, researchers generally modify the high-nickel ternary cathode material by adopting element doping and surface coating strategies. The element doping strategy can inhibit Li/Ni mixed discharge to a certain extent, slow down irreversible phase change of the high-nickel ternary cathode material and improve the structural stability of the high-nickel ternary cathode material, but can not effectively solve the problem of interface instability of the high-nickel ternary cathode material and electrolyte (Angew. chem. int. Ed.2015,54, 4440. acid 4457). The surface coating strategy is to coat and construct a layer of protective layer material on the surface of the high-nickel ternary cathode material, so that the direct contact between the high-nickel ternary cathode material and the electrolyte can be reduced while the structure of the high-nickel ternary cathode material is stabilized, the side reaction between the high-nickel ternary cathode material and the electrolyte can be effectively inhibited, and the problem of interface instability of the high-nickel ternary cathode material is relieved to a certain extent (adv. The coating materials that have been studied can be classified into inorganic coating materials (such as metal oxides, phosphides, fluorides, fast ion conductors, carbon materials, etc.) and organic polymer coating materials (such as polyethylene dioxythiophene (PEDOT), polypyrrole (PPy), polyethylene glycol (PEG), etc.). The coating of the inorganic compound often requires a post-treatment process of high-temperature calcination, which may not only affect the composition and structure of the ternary material, but also increase the production cost of the electrode material. In addition, the inorganic coating layer generally has the characteristics of strong rigidity and insufficient flexibility, and can crack or fall off to a certain extent along with the volume change of the electrode material in the charging and discharging processes, so that the stabilizing effect of the inorganic coating layer on the electrode material is reduced. In contrast, the organic high molecular polymer has good flexibility, the coating process is simple, and a high-temperature post-treatment step is not required. However, polymer coatings also suffer from low electrolyte stability, low voltage window and limited mechanical strength. Therefore, researchers usually adopt methods such as constructing a polymer blend coating layer (chinese invention CN110429269A) by using multiple polymers and adding an inorganic coating layer (chinese invention CN112758994A) to modify the polymer coating layer to improve the electrochemical performance of the polymer-coated high-nickel ternary cathode material, and to some extent, the process complexity of the polymer coating strategy is increased. How to develop a simple and effective coating strategy to improve the cycle stability and rate capability of the high-nickel ternary cathode material is still a problem to be solved urgently in application of a coated high-nickel ternary cathode material.
Disclosure of Invention
One of the purposes of the invention is to provide a polymer-coated high-nickel ternary cathode material, wherein a first polymer is coated outside the high-nickel ternary cathode material, and the first polymer is formed by polymerizing a transition metal oxygen cluster compound, a low molecular weight polyether precursor and isocyanate under the action of an initiator, wherein the molar ratio of the low molecular weight polyether precursor to the isocyanate is 1: 1-1: 1.5; the molar ratio of the transition metal oxygen cluster compound to the low molecular weight polyether precursor is 0.0005-0.01: 1.
further, the transition metal oxygen cluster compound includes, but is not limited to, one or more of surface hydroxyl-or amine-rich titanyl cluster, aluminoxy cluster, and zirconyl oxygen cluster.
Further, the transition metal oxygen cluster compound is Ti4O2(Oi Bu)10(ABZ)2(Oi Bu ═ tetra-isobutoxy; ABZ ═ p-aminobenzoic acid), Ti6O6(Oi Pr)6(9-AC)6(Oi Pr ═ tetraisopropoxy; 9-AC ═ 9-anthracenecarboxylic acid), Ti6O6(OCH3)6(AB)6(AB ═ benzoic acid) or Ti32(μ2-O)8(μ3-O)8(OCH2CH2O)32(RCOO)16(OCH2CH2OH)16(R ═ ethyl, propenyl, tert-butyl), Al8(OH)4(BA-mF)12-(OButn)8(BA-mF ═ 3-fluorobenzoic acid, OButn ═ n-butyric acid), Al16(OH)8 (BA-CH)3)24-(OPrn)16(BA-CH34-methylthiobenzoic acid, OPrn ═ isopropoxy), Al16(OH)8(BA-NH2)24-(OPrn)16(BA-NH24-aminobenzoic acid, OPrn ═ isopropoxy), [ Mg ═ Mg2Ti4(O)2(OH)4(TFA)8(THF)6]At least one of THF.
Further, the low molecular weight polyether precursor comprises a hydroxyl-terminated low molecular weight polyether precursor or an amino-terminated low molecular weight polyether precursor; the hydroxyl-terminated low molecular weight polyether precursor is at least one of polyethylene glycol (PEG), Polytetrahydrofuran (PTHF), polypropylene oxide (PPO), polycarbonate diol (PCDL), polylactic acid diol (PLA), butyl hydroxy adhesive and perfluoropolyether diol; the amine-terminated low molecular weight polyether precursor is at least one of polyetheramine, ethylenediamine and lithium diaminobenzene sulfonate.
Further, the isocyanate is at least one of Hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Toluene Diisocyanate (TDI), hydrogenated diphenylmethane diisocyanate (HMDI).
Further, the initiator is at least one of dibutyltin dilaurate and bismuth octoate. The addition proportion is that the initiator: and (3) setting the low molecular weight polyether precursor to be 0.00001-0.00005: 0.5 to 1.
Further, the mass ratio of the polymer 1 to the high-nickel ternary cathode material is 1: 5-1: 30.
Further, the Ni content of the high-nickel ternary positive electrode material is greater than or equal to 0.8. Further, the molecular formula of the high-nickel ternary cathode material is as follows: lizNixCoyMn1-x-yO2(0.8≤x≤0.9，0.075≤y≤0.125，1.0≤z≤1.1)。
The invention also aims to provide application of the polymer-coated high-nickel ternary cathode material in a lithium ion battery.
The invention further aims to provide a preparation method of the polymer-coated high-nickel ternary cathode material, which comprises the following steps:
the method comprises the following steps: weighing a low molecular weight polyether precursor, isocyanate and a small amount of initiator in a solvent according to a proportion, heating, stirring and reacting for a period of time, and adding a transition metal oxygen cluster compound to react to obtain a polymer solution;
step two: and heating and stirring the high-nickel ternary cathode material in the polymer-solution, centrifuging, washing, and finally drying in vacuum to obtain the coated high-nickel ternary cathode material.
Further, in the first step, the transition metal oxygen cluster compound is chemically synthesized by simple solution from the transition metal precursor and the hydroxyl or amino complex thereof.
Further, in the first step, the reaction molar ratio of the low molecular weight polyether precursor to the isocyanate is 1: 1.02-1: 1.3,
further, in the first step, the mass of the solvent is 5-10 times of that of the low molecular weight polyether precursor. The reaction temperature of the low molecular weight polyether precursor and isocyanate is 35-50 ℃, the reaction time is 1-6 h, and the magnetic stirring speed is 200-300 r/min;
in a preferred embodiment of the invention, the solvent is one or more of N-N dimethylformamide, N-N dimethylacetamide and N-methylpyrrolidone.
Further, in the first step, the reaction time after the transition metal oxygen cluster compound is added is 1-2 hours, the reaction temperature is 30-40 ℃, and the stirring speed is 300-400 r/min.
Further, in the second step, the mass ratio of the ternary cathode material to the solvent is 1: 5-1: 50, the heating temperature is 35-60 ℃, the heating time is 10-90 min, the stirring speed is 300-600 r/min, the centrifugal rotation speed is 6000-12000 r/min, the centrifugal time is 1-5min, the vacuum drying temperature is 60-120 ℃, and the drying time is 3-10 h.
Aiming at the defects of the existing coated high-nickel ternary cathode material in the aspects of synthesis and performance, the invention provides a novel high-performance cross-linked polymer coating layer, which can obviously improve the electrochemical performance of the high-nickel ternary cathode material. The invention takes transition metal oxygen cluster compound with rich hydroxyl or amino functional groups on the surface as a cross-linking agent to perform one-pot reaction with a polyether precursor with the capability of leading lithium ions to obtain an inorganic-organic hybrid cross-linked polymer with a highly cross-linked network structure, rich polar functional groups, good anti-electrolyte swelling property and excellent mechanical property, and the inorganic-organic hybrid cross-linked polymer is used for in-situ coating of the high-nickel ternary cathode material. The obtained inorganic-organic hybrid cross-linked polymer coated high-nickel ternary cathode material has obviously improved cycle performance and rate capability.
Compared with the prior art, the invention has the following outstanding advantages:
1. the polymer has the advantages of cheap raw materials, simple synthesis process and large-scale synthesis.
2. The process of the polymer coating anode material is simple and rapid, the polymer coating layer is uniform and compact, the equipment needed by the coating process is low in price, and the application prospect is good.
3. The polymer has the characteristics of inorganic-organic hybrid highly-crosslinked network structure, abundant polar functional groups, good swelling resistance, excellent mechanical property and the like.
4. The cycle stability and the rate capability of the coated high-nickel ternary cathode material battery are obviously improved.
Drawings
FIG. 1 is a chart of the infrared spectrum of the polymer prepared in example 1.
FIG. 2 is a stress-strain curve of the polymer prepared in example 1.
Fig. 3 is a scanning electron micrograph of an uncoated commercial high nickel ternary positive electrode material.
FIG. 4 is a scanning electron microscope image of the coating type high nickel ternary cathode material in example 1.
Fig. 5 shows the normal temperature cycle performance of the uncoated and coated high nickel ternary positive electrode material of example 1, with a test temperature of 25 ℃.
Fig. 6 shows the normal temperature rate performance of the uncoated and coated high nickel ternary positive electrode material of example 1, with a test temperature of 25 ℃.
Detailed Description
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
Firstly, the transition metal oxygen cluster compound is obtained by chemical synthesis based on the transition metal and the hydroxyl or amino complex thereof by using simple solution. Wherein, the "simple solution chemical synthesis" refers to solvothermal synthesis, the technology for synthesizing the transition metal oxygen cluster compound is the prior art, and the following documents Angew.chem.Int.Ed.2017,56, 16252-. This section is not central to the present invention.
Secondly, weighing a certain proportion of hydroxyl or amido terminated low molecular weight polyether precursor, isocyanate and a small amount of initiator, and carrying out magnetic stirring reaction in a solvent for 2-5 h at the reaction temperature of 35-50 ℃ and the magnetic stirring rotation speed of 200-300 r/min; wherein the mass ratio of the hydroxyl or amino terminated low molecular weight polyether precursor to the isocyanate is 1: 1.05-1.1.4, wherein the molar ratio of the initiator to the low molecular weight polyether precursor is 0.00001-0.00005: 0.5 to 1. Then adding a transition metal oxygen cluster (the mole ratio of the cluster to the low molecular weight polyether precursor is 0.00001-0.001: 1-2), reacting for 1-2h, and adding a high-nickel ternary cathode material LizNixCoyMn1-x-yO2(x is more than or equal to 0.8 and less than or equal to 0.9, y is more than or equal to 0.075 and less than or equal to 0.125, and z is more than or equal to 1.0 and less than or equal to 1.1) and stirring; wherein, the inorganic-organic hybridization cross-linking polymer based on cluster compound and the high nickel ternary anode materialThe mass ratio is 0.01-0.06, and the mass ratio of the high-nickel ternary cathode material to the solvent DMF is 0.01-0.1. The stirring temperature is 40-60 ℃, the stirring time is 10-120 min, and the stirring speed is 200-600 r/min. And finally, stirring, centrifuging (6000-12000 r/min for 1-5min), washing the centrifuged product for 1-3 times by using a DMF solution, and performing vacuum drying at 60-120 ℃ for 4-10 h to obtain the coated high-nickel ternary cathode material.
Example 1
Firstly, a transition metal oxygen cluster compound Ti is obtained by simple solution chemical synthesis based on transition metal titanium (Ti) and hydroxyl complexes thereof32(μ2-O)8(μ3-O)8(OCH2CH2O)32(RCOO)16(OCH2CH2OH)16(R ═ ethyl). Next, 1.01g of polytetrahydrofuran 2000(PTHF), 0.05g of diphenylmethane diisocyanate (MDI), 68. mu.L of Hexamethylene Diisocyanate (HDI) and 15. mu.L of dibutyltin dilaurate were weighed and added to 8mL of DMF solution, and the mixture was reacted for 3.5 hours with magnetic stirring at 42 ℃ and a magnetic stirring speed of 250 r/min. Then, 25mg of the transition metal oxygen cluster compound is added, the reaction temperature is 38 ℃, the magnetic stirring is carried out for 250r/min, and the polymer 1 is obtained after the reaction for 1 h. 0.5g of the polymer 1 is added into 1g of 10ml of the dispersion liquid of the high-nickel ternary cathode material NCM811, and the mixture is heated and stirred at the temperature of 40 ℃ for 1h and at the stirring speed of 300 r/min. And finally, stopping stirring, centrifuging at the rotating speed of 10000r/min for 3min, washing for 2 times by using a DMF (dimethyl formamide) solution, and carrying out vacuum drying at 100 ℃ for 8h to obtain the polymer 1-coated high-nickel ternary cathode material.
The related characteristics of the electrochemical properties of the polymer 1 and the coated ternary cathode material are shown in the attached drawings. FIG. 1 is an infrared spectrum of polymer 1, and the infrared spectrum shows that polymer 1 contains a large number of ether-oxygen bonds, indicating its strong ability to conduct lithium ions. In addition, the polymer 1 also contains rich polar functional groups, and the polar functional groups and oxygen species on the surface of the high-nickel ternary cathode material form hydrogen bond action and are firmly adsorbed and wrapped on the surface of ternary particles; fig. 2 is a stress-strain curve of the polymer 1, and as a result, the polymer 1 has good mechanical properties, which is helpful for inhibiting the generation of microcracks in the charging and discharging processes of the ternary cathode material. As a result, the surface polymer 1 had an extremely low swelling ratio in the electrolyte, indicating its excellent stability in the electrolyte. The comparison results of fig. 3 and fig. 4 show that the surface of the polymer 1-coated high-nickel ternary cathode material has a uniform and compact coating layer. Fig. 5 and 6 show the normal temperature battery cycle and rate performance of the polymer 1 coated high-nickel ternary positive electrode material, and the results show that the cycle and rate performance of the coated high-nickel ternary positive electrode material is significantly superior to those of a comparative sample, which indicates that the coating of the polymer 1 effectively blocks the direct contact of electrolyte to the ternary material, improves the interface stability of the ternary material, and improves the cycle stability and rate performance of the battery.
Example 2
Firstly, a transition metal oxygen cluster compound Ti is obtained by simple solution chemical synthesis based on transition metal titanium (Ti) and hydroxyl complexes thereof32(μ2-O)8(μ3-O)8(OCH2CH2O)32(RCOO)16(OCH2CH2OH)16(R ═ ethyl). Secondly, 2g of polytetrahydrofuran 4000, 0.05g of diphenylmethane diisocyanate (MDI), 68 muL of Hexamethylene Diisocyanate (HDI) and 10 muL of dibutyltin dilaurate are weighed and added into 7mL of DMF solution to be magnetically stirred and reacted for 3h, wherein the reaction temperature is 45 ℃, and the magnetic stirring speed is 230 r/min. Then, 29mg of the above-mentioned transition metal oxy cluster compound was added thereto, and the reaction was carried out for 1.5 hours to obtain polymer 2. 0.6g of the polymer 1 is added into 1.4g of 18ml DMMF dispersion liquid of a high-nickel ternary cathode material NCM811, and heating and stirring are carried out, wherein the heating temperature is 43 ℃, the stirring time is 70min, and the stirring speed is 250 r/min. And finally, stirring and centrifuging at the rotating speed of 10000r/min for 4min, washing for 1 time by using a DMF (dimethyl formamide) solution, and performing vacuum drying at 120 ℃ for 8h to obtain the polymer 2-coated high-nickel ternary cathode material.
Example 3
Firstly, a transition metal oxygen cluster compound Ti is obtained by simple solution chemical synthesis based on transition metal titanium (Ti) and hydroxyl complexes thereof4O2(Oi Bu)10(ABZ)2(Oi Bu ═ tetraisobutoxy; ABZ ═ p-aminobenzoic acid). Next, 0.25 is weighedPolyethylene glycol 400 g, 0.05g of diphenylmethane diisocyanate (MDI), 68 mu L of Hexamethylene Diisocyanate (HDI) and 5 mu L of dimethylaminocyclohexane are added into 8mL of DMF solution to be magnetically stirred and reacted for 3.5h, the reaction temperature is 43 ℃, and the magnetic stirring speed is 280 r/min. Then, 28mg of the above-mentioned transition metal oxy cluster compound was added thereto, and the reaction was carried out for 1.5 hours to obtain polymer 3. 0.5g of polymer 3 is added into 1.1g of 16ml DMMF dispersion liquid of a high-nickel ternary cathode material NCM811, and heating and stirring are carried out, wherein the heating temperature is 42 ℃, the stirring time is 30min, and the stirring speed is 330 r/min. And finally, stirring and centrifuging for 2min at the centrifugal rotation speed of 8000r/min, washing for 1 time by using a DMF (dimethyl formamide) solution, and carrying out vacuum drying for 10h at 110 ℃ to obtain the polymer 3-coated high-nickel ternary cathode material.
Example 4
Firstly, a transition metal oxygen cluster compound Ti is obtained by simple solution chemical synthesis based on transition metal titanium (Ti) and hydroxyl complexes thereof6O6(Oi Pr)6(9-AC)6(Oi Pr ═ tetraisopropoxy; 9-AC ═ 9-anthracenecarboxylic acid). Secondly, 1.03g of polyethylene glycol 2000, 0.05g of diphenylmethane diisocyanate (MDI), 88 muL of isophorone diisocyanate (IPDI) and 15 muL of dibutyltin dilaurate are weighed and added into 7mL of DMF solution to react for 3.5 hours by magnetic stirring at the temperature of 39 ℃ and the rotating speed of 230 r/min. Then, 24mg of the above-mentioned transition metal oxy cluster compound was added thereto, and the reaction was carried out for 2 hours to obtain polymer 4. 0.5g of the polymer 1 is added into 1.2g of 10ml of DMMF dispersion liquid of a high-nickel ternary cathode material NCM811, and heating and stirring are carried out, wherein the heating temperature is 44 ℃, the stirring time is 1h, and the stirring speed is 350 r/min. And finally, stirring and centrifuging at the rotating speed of 7000r/min for 4min, washing for 3 times by using a DMF (dimethyl formamide) solution, and carrying out vacuum drying at 90 ℃ for 10 hours to obtain the polymer 4-coated high-nickel ternary cathode material.
Example 5
Firstly, a transition metal oxygen cluster compound Ti is obtained by simple solution chemical synthesis based on transition metal titanium (Ti) and hydroxyl complexes thereof6O6(OCH3)6(AB)6(AB ═ benzoic acid). Next, 1.03g of polycarbonate diol 2000 and 0.03g of toluene diisocynate were weighed outAcid ester (TDI), 88 mu L of isophorone diisocyanate (IPDI) and 10 mu L of dibutyltin dilaurate are added into 7.5mL of DMF solution, and the mixture is magnetically stirred and reacted for 3 hours at the reaction temperature of 40 ℃ and the magnetic stirring speed of 230 r/min. Then, 20mg of the above-mentioned transition metal oxy cluster compound was added thereto, and the reaction was carried out for 1.5 hours to obtain polymer 5. 0.5g of the polymer 1 is added into 1.3g of 12ml DMMF dispersion liquid of a high-nickel ternary cathode material NCM811, and heating and stirring are carried out, wherein the heating temperature is 42 ℃, the stirring time is 1h, and the stirring speed is 320 r/min. And finally, stirring and centrifuging for 2min at 9000r/min, washing for 1 time by using a DMF (dimethyl formamide) solution, and performing vacuum drying at 100 ℃ for 12h to obtain the polymer 5-coated high-nickel ternary cathode material.
Example 6
Firstly, a transition metal oxygen cluster compound Ti is obtained by simple solution chemical synthesis based on transition metal titanium (Ti) and hydroxyl complexes thereof32(μ2-O)8(μ3-O)8(OCH2CH2O)32(RCOO)16(OCH2CH2OH)16(R ═ propenyl). Then, 1.01g of polytetrahydrofuran 2000(PTHF), 0.035g of Toluene Diisocyanate (TDI), 88. mu.L of isophorone diisocyanate (IPDI) and 15. mu.L of dibutyltin dilaurate were weighed and added to 8mL of DMF solution to react for 2 hours under magnetic stirring at 45 ℃ and 210 r/min. Then, 28mg of the above-mentioned transition metal oxy cluster compound was added thereto, and the reaction was carried out for 1.5 hours to obtain polymer 1. 0.3g of the polymer 1 is added into 1g of 16ml DMMF dispersion liquid of a high-nickel ternary cathode material NCM811, and heating and stirring are carried out, wherein the heating temperature is 45 ℃, the stirring time is 40min, and the stirring speed is 280 r/min. And finally, stirring and centrifuging for 5min at the rotating speed of 6000r/min, washing for 2 times by using a DMF (dimethyl formamide) solution, and carrying out vacuum drying for 12h at the temperature of 80 ℃ to obtain the polymer 6-coated high-nickel ternary cathode material.
Example 7
Firstly, a transition metal oxygen cluster compound Al is obtained by simple solution chemical synthesis based on transition metal aluminum (Al) and hydroxyl complexes thereof8(OH)4(BA-mF)12-(OButn)8(BA-mF ═ 3-fluorobenzoic acid. Next, 1.05g of the emulsion was weighedAcid diol 2000, 0.1g of diphenylmethane diisocyanate (MDI), 0.035g of Toluene Diisocyanate (TDI), and 8. mu.L of dibutyltin dilaurate were added into 7mL of DMF solution, and the mixture was magnetically stirred for reaction for 3 hours at 40 ℃ and at a magnetic stirring speed of 200 r/min. Then, 22mg of the above-mentioned transition metal oxy cluster compound was added thereto, and the reaction was carried out for 1.5 hours to obtain polymer 7. 0.4g of the polymer 1 is added into 1.2g of 20ml DMMF dispersion liquid of a high-nickel ternary cathode material NCM811, and heating and stirring are carried out, wherein the heating temperature is 45 ℃, the stirring time is 1h, and the stirring speed is 400 r/min. And finally, stirring and centrifuging for 2min at the centrifugal rotation speed of 10000r/min, washing for 1 time by using a DMF (dimethyl formamide) solution, and carrying out vacuum drying for 10h at 100 ℃ to obtain the polymer 7-coated high-nickel ternary cathode material.
Example 8
Firstly, a transition metal oxygen cluster compound Al16(OH)8 (BA-CH) is obtained by simple solution chemical synthesis based on transition metal aluminum (Al) and hydroxyl complexes thereof3)24-(OPrn)16(BA-CH34-methylthiobenzoic acid). Then, 0.5g of polytetrahydrofuran 4000(PTHF), 0.035g of Toluene Diisocyanate (TDI), 88. mu.L of isophorone diisocyanate (IPDI) and 10. mu.L of dibutyltin dilaurate were weighed and added to 5mL of DMF solution to react for 3 hours under magnetic stirring at 39 ℃ and 250 r/min. Then, 38mg of the above-mentioned transition metal oxy cluster compound was added thereto, and the reaction was carried out for 1 hour to obtain a polymer 8. 0.5g of polymer 8 is added into 1.2g of 9ml DMMF dispersion liquid of a high-nickel ternary cathode material NCM811, and heating and stirring are carried out, wherein the heating temperature is 45 ℃, the stirring time is 60min, and the stirring speed is 360 r/min. And finally, stirring and centrifuging for 5min at the centrifugal rotation speed of 8000r/min, washing for 1 time by using a DMF (dimethyl formamide) solution, and carrying out vacuum drying for 10h at the temperature of 80 ℃ to obtain the polymer 8-coated high-nickel ternary cathode material.
Example 9
Firstly, a transition metal oxygen cluster compound Al is obtained by simple solution chemical synthesis based on transition metal aluminum (Al) and amino group complex thereof16(OH)8(BA-NH2)24-(OPrn)16(BA-NH24-aminobenzoic acid)). Next, 1.01g of polycarbonate was weighedGlycol 2000, 0.05g of diphenylmethane diisocyanate (MDI), 90. mu.L of isophorone diisocyanate (IPDI) and 5. mu.L of dibutyltin dilaurate were added into 6mL of DMF solution, and the mixture was magnetically stirred for reaction for 3.2h at 41 ℃ and 230 r/min. Then, 20mg of the above-mentioned transition metal oxy cluster compound was added thereto, and the reaction was carried out for 1 hour to obtain a polymer 1. 0.6g of the polymer 1 is added into 1.3g of 14ml DMMF dispersion liquid of a high-nickel ternary cathode material NCM811, and heating and stirring are carried out, wherein the heating temperature is 42 ℃, the stirring time is 70min, and the stirring speed is 330 r/min. And finally, stirring and centrifuging at the rotating speed of 10000r/min for 1min, washing for 1 time by using a DMF (dimethyl formamide) solution, and carrying out vacuum drying at the temperature of 80 ℃ for 8h to obtain the polymer 9-coated high-nickel ternary cathode material.
Example 10
Firstly, a transition metal oxygen cluster compound Ti is obtained by simple solution chemical synthesis based on transition metal titanium (Ti) and hydroxyl complexes thereof32(μ2-O)8(μ3-O)8(OCH2CH2O)32(RCOO)16(OCH2CH2OH)16(R ═ t-butyl). Then, 0.52g of polytetrahydrofuran 4000(PTHF), 0.032g of Toluene Diisocyanate (TDI), 95. mu.L of isophoron diisocyanate (IPDI) and 13. mu.L of dibutyltin dilaurate were weighed and added into 6mL of DMF solution to react for 3 hours under magnetic stirring at 40 ℃ and the magnetic stirring speed of 220 r/min. Then, 27mg of the above-mentioned transition metal oxy cluster compound was added thereto, and the reaction was carried out for 1.5 hours to obtain a polymer 10. 0.5g of the polymer 10 is added into 1.1g of 15ml of DMDMF dispersion liquid of a high-nickel ternary cathode material NCM811, and heating and stirring are carried out, wherein the heating temperature is 42 ℃, the stirring time is 50min, and the stirring speed is 350 r/min. And finally, stirring and centrifuging at the rotating speed of 10000r/min for 4min, washing for 3 times by using a DMF (dimethyl formamide) solution, and carrying out vacuum drying at 120 ℃ for 5h to obtain the polymer 10-coated high-nickel ternary cathode material.
Example 11
Firstly, a transition metal oxygen cluster compound [ Mg ] is obtained by simple solution chemical synthesis based on transition metal magnesium (Mg) and hydroxyl complexes thereof2Ti4(O)2(OH)4(TFA)8(THF)6]THF. Secondly, 1.01g of polylactic acid diol 2000, 0.05g of diphenylmethane diisocyanate (MDI), 75 mu of isophorone diisocyanate (IPDI) and 6 mu of dibutyltin dilaurate are weighed and added into 8mL of DMF solution to be magnetically stirred and reacted for 3 hours, wherein the reaction temperature is 46 ℃, and the magnetic stirring rotation speed is 230 r/min. Then, 26mg of the above-mentioned transition metal oxy cluster compound was added thereto, and the reaction was carried out for 2 hours to obtain polymer 11. 0.4g of the polymer 11 was added to 1.1g of a 12ml DMMF dispersion of a high-nickel ternary positive electrode material NCM811, and the mixture was heated and stirred at 45 ℃ for 40min at a stirring speed of 300 r/min. And finally, stirring and centrifuging at 9000r/min for 5min, washing for 1 time by using a DMF (dimethyl formamide) solution, and performing vacuum drying at 100 ℃ for 10h to obtain the polymer 11-coated high-nickel ternary cathode material.
Example 12
Firstly, a transition metal oxygen cluster compound Ti is obtained by simple solution chemical synthesis based on transition metal titanium (Ti) and hydroxyl complexes thereof32(μ2-O)8(μ3-O)8(OCH2CH2O)32(RCOO)16(OCH2CH2OH)16(R ═ ethyl). Secondly, 1.01g of perfluoropolyether diol 2000, 0.03g of Toluene Diisocyanate (TDI), 75 muL of Hexamethylene Diisocyanate (HDI) and 8 muL of dibutyltin dilaurate are weighed and added into 8mL of DMF solution to be magnetically stirred and reacted for 4 hours, wherein the reaction temperature is 40 ℃, and the magnetic stirring rotation speed is 210 r/min. Then, 20mg of the above-mentioned transition metal oxy cluster compound was added thereto, and the reaction was carried out for 1.5 hours to obtain a polymer 12. 0.6g of the polymer 12 was added to 1.2g of a 15ml of a dispersion of a nickel-rich ternary positive electrode material NCM811, and the mixture was heated and stirred at a temperature of 43 ℃ for 50min at a rotation speed of 320 r/min. And finally, stirring and centrifuging for 2min at the centrifugal rotation speed of 10000r/min, washing for 1 time by using a DMF (dimethyl formamide) solution, and carrying out vacuum drying for 10h at 100 ℃ to obtain the polymer 12-coated high-nickel ternary cathode material.
Claims (10)
1. A polymer-coated high-nickel ternary cathode material is characterized in that: the high-nickel ternary cathode material is coated with a polymer I, the polymer I is formed by polymerizing a transition metal oxygen cluster compound, a low molecular weight polyether precursor and isocyanate under the action of an initiator, wherein the molar ratio of the low molecular weight polyether precursor to the isocyanate is 1: 1-1: 1.5; the molar ratio of the transition metal oxygen cluster compound to the low molecular weight polyether precursor is 0.0005-0.01: 1.
2. the polymer-coated high-nickel ternary positive electrode material of claim 1, wherein: the transition metal oxygen cluster compound comprises at least one of titanium oxygen cluster, aluminum oxygen cluster and zirconium oxygen cluster, wherein the surface of the titanium oxygen cluster is rich in hydroxyl or amine groups.
3. The polymer-coated high-nickel ternary positive electrode material of claim 2, wherein: the transition metal oxygen cluster compound is Ti4O2(Oi Bu)10(ABZ)2(Oi Bu ═ tetra-isobutoxy; ABZ ═ p-aminobenzoic acid), Ti6O6(Oi Pr)6(9-AC)6(Oi Pr ═ tetraisopropoxy; 9-AC ═ 9-anthracenecarboxylic acid), Ti6O6(OCH3)6(AB)6(AB ═ benzoic acid) or Ti32(μ2-O)8(μ3-O)8(OCH2CH2O)32(RCOO)16(OCH2CH2OH)16(R ═ ethyl, propenyl, tert-butyl), Al8(OH)4(BA-mF)12-(OButn)8(BA-mF ═ 3-fluorobenzoic acid, OButn ═ n-butyric acid), Al16(OH)8 (BA-CH)3)24-(OPrn)16(BA-CH34-methylthiobenzoic acid, OPrn ═ isopropoxy), Al16(OH)8(BA-NH2)24-(OPrn)16(BA-NH24-aminobenzoic acid, OPrn ═ isopropoxy), [ Mg ═ Mg2Ti4(O)2(OH)4(TFA)8(THF)6]At least one of THF.
4. The polymer-coated high-nickel ternary positive electrode material of claim 1, wherein: the low molecular weight polyether precursor comprises a hydroxyl-terminated low molecular weight polyether precursor or an amino-terminated low molecular weight polyether precursor; the hydroxyl-terminated low molecular weight polyether precursor is at least one of polyethylene glycol, polytetrahydrofuran, polypropylene oxide, polycarbonate diol, polylactic acid diol, butadiene-hydroxy glue and perfluoropolyether diol; the amine-terminated low molecular weight polyether precursor is at least one of polyetheramine, ethylenediamine and lithium diaminobenzene sulfonate.
5. The polymer-coated high-nickel ternary positive electrode material of claim 1, wherein: the isocyanate is at least one of hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, toluene diisocyanate and hydrogenated diphenylmethane diisocyanate.
6. The polymer-coated high-nickel ternary positive electrode material of claim 1, wherein: the initiator is at least one of dibutyltin dilaurate and bismuth octoate.
7. The polymer-coated high-nickel ternary positive electrode material of claim 1, wherein: the mass ratio of the polymer 1 to the high-nickel ternary cathode material is 1: 5-1: 30.
8. The polymer-coated high-nickel ternary positive electrode material of claim 1, wherein: the Ni content of the high-nickel ternary cathode material is greater than or equal to 0.8.
9. The use of a polymer-encapsulated high-nickel ternary positive electrode material of any one of claims 1-8 in a lithium ion battery.
10. The preparation method of the polymer-coated high-nickel ternary cathode material as claimed in any one of claims 1 to 8, comprising the steps of:
the method comprises the following steps: weighing a low molecular weight polyether precursor, isocyanate and a small amount of initiator in a solvent according to a proportion, heating, stirring and reacting for a period of time, and adding a transition metal oxygen cluster compound to react to obtain a polymer solution;
step two: and heating and stirring the high-nickel ternary cathode material in the polymer-solution, centrifuging, washing, and finally drying in vacuum to obtain the coated high-nickel ternary cathode material.
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