CN113896253A - Ternary cathode material and preparation method and application thereof - Google Patents
Ternary cathode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ternary cathode material and a preparation method and application thereof, wherein the preparation method comprises the steps of mixing a ternary precursor, a lithium source and a metal dopant, taking an organic solvent as a dispersion medium, carrying out mixing wet grinding, and drying to obtain a mixture; ultrasonically infiltrating the mixture by adopting a fluorine-containing organic solvent, and granulating and tabletting to obtain mixed particles; and carrying out high-temperature sintering, crushing and grading on the mixed particles by adopting three-stage temperature programming, so as to prepare the ternary cathode material, wherein the metal doping mode of the obtained ternary cathode material is changed, the fluorine-containing organic solvent is subjected to ultrasonic infiltration, and the three-stage temperature programming is matched, so that the obtained ternary cathode material is uniformly doped with metal elements, the doping effect is good, the residual alkali content on the surface of the material is effectively reduced, and the ternary cathode material has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a ternary cathode material, the ternary cathode material prepared by the preparation method, and application of the ternary cathode material as an active material in a lithium ion battery.
Background
The nickel-cobalt-manganese (NCM) ternary material of the lithium ion battery is a novel high-performance anode material and has the advantages of high capacity, good rate capability and the like. Against the background of the increasing energy density requirements of current power batteries, it is considered to be one of the most promising positive electrode materials for lithium ion batteries.
The traditional high-nickel ternary cathode material is prepared by adopting a mechanical high-mixing high-temperature solid phase method, the ternary cathode material prepared by adopting the method is usually accompanied by the problem of overhigh content of surface residual alkali, and except the excessive residual factors of a lithium source, another important reason is that the surface active oxygen ions of the cathode material can be mixed with CO in the air2And H2O reacts to generate carbonate radical, and lithium ions migrate from the bulk to the surface to form Li2CO3Thereby, the effect is achieved. Too high content of residual alkali on the surface can reduce the compatibility of the ternary material and the binder, so that a jelly shape is formed in the pulp mixing process; in addition, the excessive high residual alkali can cause the battery to absorb moisture reaction at high temperature, so that the cycle performance is deteriorated, the swelling and bulging occur, and the safety performance of the lithium battery is reduced.
Aiming at the problems, the current nickel-cobalt-manganese ternary positive electrode material is usually modified by doping metal cations to improve the cycle stability and discharge capacity of the material, wherein the commonly used doped metal is Al, Mg, Zr and the like, and the metal cations usually play a role in changing the valence state of transition metal ions, improving the electronic conductivity, reducing the concentration of surface Ni ions, inhibiting cation mixed arrangement, lattice distortion and the like to stabilize the material structure, and further improve the electrochemical performance of the ternary material.
In order to ensure the doping effect, the doping material needs to be uniformly distributed on the surface of the ternary material precursor, but the traditional doping mode is to use a high-speed mixer to mechanically and physically mix the doping material with the precursor and a lithium source, the doping amount is usually added according to the proportion of 200-10000ppm, and on one hand, the content of the doping metal is extremely low compared with that of the raw material; on the other hand, mechanical high mixing causes mixing unevenness, so that the doped metal cannot be uniformly distributed in the material. This results in insignificant improvement in properties of the ternary material.
Disclosure of Invention
In view of the above, the invention needs to provide a preparation method of a ternary cathode material, which is characterized in that a precursor is subjected to ultrasonic infiltration by mixing and wet milling in combination with a fluorine-containing organic solvent, so that the doping effect is improved, the residual alkali content on the surface of the ternary cathode material is effectively reduced, and the obtained ternary cathode material has excellent electrochemical performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a ternary cathode material, which comprises the following steps:
mixing a ternary precursor, a lithium source and a metal dopant, mixing, wet-grinding and drying by taking an organic solvent as a dispersion medium to obtain a mixture;
ultrasonically infiltrating the mixture by adopting a fluorine-containing organic solvent, and granulating and tabletting to obtain mixed particles;
and (3) sintering the mixed particles at a high temperature by adopting three-stage temperature programming, crushing and grading to prepare the ternary cathode material.
Further, the ternary precursor is selected from nickel cobalt manganese hydroxide, and the chemical general formula of the ternary precursor is NixCoyMn1-x-y(OH)2Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y is less than 1;
the lithium source is selected from lithium hydroxide or lithium carbonate.
Further, the metal dopant is selected from AlCl3、MgCl2、ZrCl4One or a mixture of two or more of them.
Further, the addition amount of the metal dopant is 600-1000 ppm.
Further, the organic solvent is selected from one or a mixture of more than two of methanol, ethanol and ether;
the process for mixing and wet grinding specifically comprises the following steps: ball material ratio 16-20: 1, the ball milling rotation speed is 300-.
Further, the adding amount of the fluorine-containing organic solvent is 3-5% of the mass of the mixture, wherein the fluorine-containing organic solvent is obtained by dissolving PVDF in a solvent, the solvent is selected from NMP, DMAc or DMF, and the mass ratio of PVDF to the solvent is 0.5-1: 1.
further, the ultrasonic frequency of the ultrasonic infiltration is not lower than 25kHz, and the time is 2-4 h;
the pressure of the granulation and tabletting is 0.2-0.4MPa, and the particle size of the mixed particles is 5-10 mm.
Further, the three steps of temperature programming specifically include: heating to 160-class 210 ℃ at a speed of 1-3 ℃/min, then preserving heat for 3-5h, heating to 300-class 350 ℃ at a heating rate of 1-3 ℃/min, preserving heat for 3-5h, heating to 850-class 920 ℃ at a heating rate of 3-5 ℃/min, and preserving heat for 10-12 h; cooling at the rate of 5-8 deg.C/min.
The invention further provides a ternary cathode material prepared by the preparation method of any one of the above materials.
The invention further provides the application of the ternary cathode material in the preparation of the ternary lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the ternary precursor, the lithium source, the metal dopant and the organic solvent are mixed and wet-milled, so that the problem of uneven mixing of the traditional solid phase is effectively solved, the doped metal elements are more uniformly distributed on the surface of the ternary precursor, and the doping effect is improved. Meanwhile, the mixture is fully infiltrated by the fluorine-containing organic solvent under the action of ultrasonic infiltration, so that the doping uniformity of metal elements is improved, and the doping effect is improved; and the fluorine-containing organic solvent can provide fluorine element, so that the granulated secondary particles can effectively reduce the residual alkali content on the surface of the material.
In addition, the preparation method adopts three stages of temperature programming for high-temperature sintering, wherein the first heat preservation area effectively removes redundant organic solvent, the second heat preservation area releases HF which fully reacts with the mixed particles to ensure that fluorine ions enter material lattices, and the third heat preservation area enables the mixed particle grains to be molded, so that the ternary cathode material with excellent electrochemical performance is prepared.
Drawings
FIG. 1 is a block diagram of a process for preparing a ternary cathode material in accordance with a preferred embodiment of the present invention;
FIG. 2 is an XRD pattern of the ternary cathode material prepared in example 4 of the present invention;
fig. 3 is an SEM image of the ternary cathode material prepared in example 4 of the present invention.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention discloses a preparation method of a ternary cathode material, as shown in figure 1, comprising the following steps:
mixing a ternary precursor, a lithium source and a metal dopant, mixing, wet-grinding and drying by taking an organic solvent as a dispersion medium to obtain a mixture;
ultrasonically infiltrating the mixture by adopting a fluorine-containing organic solvent, and granulating and tabletting to obtain mixed particles;
and (3) sintering the mixed particles at a high temperature by adopting three-stage temperature programming, crushing and grading to prepare the ternary cathode material.
The preparation method comprises the steps of mixing a ternary precursor, a lithium source and a metal dopant, taking an organic solvent as a dispersion medium, carrying out mixing wet grinding, drying to uniformly distribute metal elements on the surface of the mixture, and drying by distillation, wherein the organic solvent is not particularly limited as long as the metal dopant can be dissolved, but the ternary precursor and the lithium source are not dissolved and do not react with the ternary precursor and the lithium source. The method has the advantages that the uniformity degree of metal doping can be improved by ultrasonically infiltrating the mixed powder with the fluorine-containing organic solvent, the doping effect is improved, and meanwhile, the fluorine-containing organic solvent can provide fluorine elements for the ternary material, so that residual alkali on the surface of the ternary anode material is reduced, three-section temperature programmed sintering is combined, wherein redundant organic solvent is effectively removed in the first heat preservation area, HF is released in the second heat preservation area, the first heat preservation area fully reacts with mixed particles, fluorine ions are ensured to enter material lattices, the mixed particle grains are formed in the third heat preservation area, and the ternary anode material with excellent electrochemical performance is prepared.
Further, the ternary precursor, the lithium source, and the like described herein are all raw materials conventionally used in the art for preparing ternary cathode materials, and are not particularly limited, and in one or more embodiments of the present invention, the ternary precursor is selected from nickel-cobalt-manganese hydroxide having a chemical formula of NixCoyMn1-x-y(OH)2Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y is less than 1;
the lithium source is selected from lithium hydroxide or lithium carbonate.
Further, the metal dopant described herein may be a metal dopant compound conventionally used in the art for the preparation of ternary cathode materials, it being noted that the metal dopant is selected to be soluble in organic solvents, and thus in one or more embodiments of the present invention, the metal dopant is selected from AlCl3、MgCl2、ZrCl4One or a mixture of two or more of them.
In a further scheme, due to the fact that the doping effect is improved in the preparation method, the doping amount of the metal dopant can be obviously improved, in one or more embodiments of the invention, the mass of the ternary cathode material is taken as a measurement standard, and the addition amount of the metal dopant is 600-1000 ppm.
Further, the organic solvent is not particularly limited as long as it can dissolve the metal dopant as a dispersion medium in the preparation method, and may be adjusted according to the selection of the metal dopant, and in one or more embodiments of the present invention, the organic solvent is one or a mixture of two or more selected from methanol, ethanol, and diethyl ether;
further, the process of wet mixing and milling is not particularly limited, and the ball-to-material ratio, the rotation speed, the time, etc. may be adjusted as needed as long as the purpose of uniform mixing can be achieved, and in one or more embodiments of the present invention, the process of wet mixing and milling specifically includes: ball material ratio 16-20: 1, the ball milling rotation speed is 300-.
In a further scheme, the adding amount of the fluorine-containing organic solvent is 3-5% of the mass of the mixture, wherein the fluorine-containing organic solvent is obtained by dissolving PVDF in a solvent, the solvent is selected from NMP, DMAc or DMF, and the mass ratio of PVDF to the solvent is 0.5-1: 1. the mixture is subjected to ultrasonic infiltration by using the fluorine-containing organic solvent, so that the uniformity of metal doping is improved, the doping effect is improved, the PVDF-containing organic solvent is fully infiltrated into the mixture to provide fluorine, and then granulation is carried out to form secondary particles by bonding the PVDF, so that the residual alkali content on the surface of the ternary cathode material is effectively reduced.
Further, the ultrasonic infiltration and granulation tabletting processes are not particularly limited herein, and may be adjusted as required, and in one or more embodiments of the present invention, the ultrasonic frequency of the ultrasonic infiltration is not lower than 25KHz, and the time is 2-4 h;
the pressure of the granulating and tabletting is 0.2-0.4MPa, the particle size of the mixed particles is 5-10mm, and the large particles are adopted for sintering to enlarge the gaps between the materials and ensure the sufficient circulation of oxygen, so that the materials are fully reacted.
According to a further scheme, redundant organic solvent in the fluorine-containing organic solvent is removed through a first heat preservation area by three-section temperature programming sintering; the second heat preservation area decomposes fluorine-containing substances to release HF, so that the HF is fully contacted and reacted with the mixed particles to ensure that fluorine ions successfully enter material lattices; the third heat preservation area ensures the mixed particle crystal grain to be formed, thereby obtaining the ternary anode material with excellent electrochemical performance. In one or more embodiments of the present invention, the three steps of temperature programming specifically include: heating to 160-210 ℃ at a speed of 1-3 ℃/min, then preserving heat for 3-5h, heating to 300-320 ℃ at a heating rate of 1-3 ℃/min, preserving heat for 3-5h, heating to 850-920 ℃ at a heating rate of 3-5 ℃/min, and preserving heat for 10-12 h; cooling to 60 ℃ at the speed of 5-8 ℃/min.
The second aspect of the invention provides a ternary cathode material prepared by the preparation method of the first aspect of the invention. The ternary cathode material prepared by the preparation method has the advantages of uniform metal element doping, increased doping amount, low surface residual alkali content and excellent electrochemical performance.
In a third aspect, the invention provides the use of a ternary cathode material according to the second aspect of the invention in the preparation of a ternary lithium ion battery. The ternary cathode material is used as a cathode active substance to prepare a cathode, the cathode, a diaphragm and electrolyte are assembled to obtain the ternary lithium ion battery, the cathode and the ternary lithium ion battery are conventional preparation means in the field, and the lithium ion battery obtained by the preparation means is not specifically explained here, and has excellent performance.
Example 1
50g of Ni are taken0.5Co0.20Mn0.3(OH)220.86g of Li2CO3And 0.0425g of MgCl2Adding the mixture into ball milling equipment, and ball milling for 1h at the rotating speed of 300r/min by taking 100mL of anhydrous methanol and 100mL of anhydrous ethanol as ball milling media at a ball-to-material ratio of 20:1 to obtain ball milling slurry;
drying the ball-milling slurry at 120 ℃ for 6h to obtain a mixture;
mixing the obtained mixture with 2.1270g of fluorine-containing organic solvent, and carrying out ultrasonic infiltration for 4h at the ultrasonic frequency of 30KHz, wherein the mass ratio of the fluorine-containing organic solvent to PVDF: NMAc ═ 1: 1 with an organic solvent;
adding the ultrasonically infiltrated material into a granulator, and granulating into granules with the particle size of 10mm, wherein the granulating pressure is 0.2 MPa;
placing the prepared particles in a box furnace, heating to 170 ℃ at a speed of 1 ℃/min, preserving heat for 3h, heating to 350 ℃ at a heating rate of 3 ℃/min, preserving heat for 5h, heating to 920 ℃ at a heating rate of 5 ℃/min, and preserving heat for 10 h; cooling to 60 ℃ at the speed of 8 ℃/min to obtain a calcined substance;
and (3) carrying out jet milling on the calcined substance to obtain the NCM523 ternary cathode material, wherein in the jet milling, the gas pressure is controlled to be 0.6MPa, the rotation frequency of a grading wheel is 50Hz, and the feeding speed is 100 g/s.
Example 2
50g of Ni are taken0.6Co0.20Mn0.2(OH)223.60g of LiOH. H2O and 0.0425g of MgCl20.0434g of AlCl3And 0.0312g of ZrCl4Adding the mixture into ball milling equipment, and ball milling for 2 hours at a rotating speed of 500r/min by taking 200mL of diethyl ether as a ball milling medium at a ball-to-material ratio of 20:1 to obtain ball milling slurry;
drying the ball-milling slurry at 120 ℃ for 8h to obtain a mixture;
mixing the obtained mixture with 3.6858g of fluorine-containing organic solvent, and carrying out ultrasonic infiltration for 2h at 35KHz ultrasonic frequency, wherein the mass ratio of the fluorine-containing organic solvent to PVDF: DMF ═ 1: 1 with an organic solvent;
adding the ultrasonically infiltrated material into a granulator, and granulating into granules with the particle size of 5mm, wherein the granulating pressure is 0.4 MPa;
placing the prepared particles in a box furnace, heating to 160 ℃ at a rate of 3 ℃/min, preserving heat for 5h, heating to 320 ℃ at a heating rate of 1 ℃/min, preserving heat for 3h, heating to 890 ℃ at a heating rate of 3 ℃/min, and preserving heat for 11 h; cooling to 60 ℃ at the speed of 8 ℃/min to obtain a calcined substance;
and (3) carrying out jet milling on the calcined substance to obtain the NCM622 ternary cathode material, wherein in the jet milling, the gas pressure is controlled to be 0.8MPa, the rotation frequency of a grading wheel is 50Hz, and the feeding speed is 150 g/s.
Example 3
50g of Ni are taken0.75Co0.10Mn0.15(OH)223.55g of LiOH. H2O and 0.0723g AlCl30.0312g of ZrCl4Adding the mixture into ball milling equipment, and ball milling for 2 hours at the rotating speed of 400r/min by using 180mL of anhydrous ether and 20mL of ethanol as ball milling media at a ball-to-material ratio of 20:1 to obtain ball milling slurry;
drying the ball-milling slurry at 120 ℃ for 10h to obtain a mixture;
mixing the obtained mixture with 2.2096g of fluorine-containing organic solvent, and carrying out ultrasonic infiltration for 3h at 28KHz ultrasonic frequency, wherein the mass ratio of the fluorine-containing organic solvent to PVDF: NMP 1: 1 with an organic solvent;
adding the ultrasonically infiltrated material into a granulator, and granulating into granules with the particle size of 5mm, wherein the granulating pressure is 0.4 MPa;
placing the prepared particles in a box furnace, heating to 210 ℃ at the speed of 2 ℃/min, preserving heat for 5h, heating to 320 ℃ at the heating rate of 1 ℃/min, preserving heat for 5h, heating to 850 ℃ at the heating rate of 3 ℃/min, and preserving heat for 12 h; cooling to 60 ℃ at the speed of 5 ℃/min to obtain a calcined substance;
and (3) carrying out jet milling on the calcined substance to obtain the NCM751015 ternary cathode material, wherein in the jet milling, the gas pressure is controlled to be 0.8MPa, the rotation frequency of a grading wheel is 30Hz, and the feeding speed is 100 g/s.
Example 4
50g of Ni are taken0.75Co0.10Mn0.15(OH)223.55g of LiOH. H2O and 0.0723g AlCl3Adding the mixture into ball milling equipment, and ball milling for 2 hours at a rotating speed of 500r/min by using 200mL of anhydrous ether as a ball milling medium at a ball-to-material ratio of 20:1 to obtain ball milling slurry;
drying the ball-milling slurry at 120 ℃ for 10h to obtain a mixture;
mixing the obtained mixture with 3.6811g of fluorine-containing organic solvent, and carrying out ultrasonic infiltration for 44h at the ultrasonic frequency of 30KHz, wherein the mass ratio of the fluorine-containing organic solvent to PVDF: NMP 1: 1 with an organic solvent;
adding the ultrasonically infiltrated material into a granulator, and granulating into granules with the particle size of 8mm, wherein the granulating pressure is 0.3 MPa;
placing the prepared particles in a box furnace, heating to 210 ℃ at the speed of 2 ℃/min, preserving heat for 5h, heating to 320 ℃ at the heating rate of 2 ℃/min, preserving heat for 5h, heating to 850 ℃ at the heating rate of 3 ℃/min, and preserving heat for 10 h; cooling to 60 ℃ at the speed of 5 ℃/min to obtain a calcined substance;
and (3) carrying out jet milling on the calcined substance to obtain the NCM751015 ternary cathode material, wherein in the jet milling, the gas pressure is controlled to be 0.8MPa, the rotation frequency of a grading wheel is 50Hz, and the feeding speed is 120 g/s.
Example 5
The same embodiment as in example 1 was used except that the metal dopant was ZrCl4The doping amount is 600 ppm.
Example 6
The same embodiment as in example 1 was used except that the metal dopant was AlCl4The doping amount is 1000 ppm.
Example 7
The same embodiment as in example 2 was used except that the amount of the fluorine-containing organic solvent added was 3% by mass of the blend, and the fluorine-containing organic solvent was a mixture of PVDF: NMP 0.5: 1, mixing and preparing.
Example 8
The present example adopts the same embodiment as example 2, except that the amount of the fluorine-containing organic solvent added is 5% by mass of the mix, and the fluorine-containing organic solvent is a mixture of PVDF: DMAc ═ 0.7: 1, mixing and preparing.
Comparative example 1
50g of Ni were weighed0.75Co0.10Mn0.15(OH)223.55g of LiOH. H2O and 0.0723g AlCl3Mixing in high-speed mixer, heating to 210 deg.C at 2 deg.C/min in box furnace, and maintainingHeating for 5h, heating to 320 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 5h, heating to 850 ℃ at the heating rate of 3 ℃/min, and keeping the temperature for 10 h; cooling to 60 deg.C at a rate of 5 deg.C/min; in the jet milling, the gas pressure is controlled to be 0.8MPa, and the rotation frequency of the grading wheel is 50 Hz; the feeding speed is 120g/s, and the NCM751015 ternary cathode material is obtained by classification.
Comparative example 2
50g of Ni were weighed0.75Co0.10Mn0.15(OH)223.55g of LiOH. H2O, after being mixed by a high-speed mixer, the mixture is put into a box-type furnace, the temperature is raised to 210 ℃ at the speed of 2 ℃/min, then the heat is preserved for 5h, the temperature is raised to 320 ℃ at the speed of 2 ℃/min, the heat is preserved for 5h, and then the temperature is raised to 850 ℃ at the speed of 3 ℃/min and the heat is preserved for 10 h; cooling to 60 deg.C at a rate of 5 deg.C/min; in the jet milling, the gas pressure is controlled to be 0.8MPa, and the rotation frequency of the grading wheel is 50 Hz; the feeding speed is 120g/s, and the NCM751015 ternary cathode material is obtained by classification.
Comparative example 3
The same embodiment as in example 4 was used except that: 50g of Ni0.75Co0.10Mn0.15(OH)223.55g of LiOH. H2O and 0.0723g AlCl3And mixing by a high-speed mixer to obtain mixed powder.
Comparative example 4
The same embodiment as in example 4 was used except that: ultrasonic infiltration of fluorine-containing organic solvent is not carried out, namely, powder obtained after mixing, wet grinding and drying is directly sintered by three-stage programmed heating.
Comparative example 5
The same embodiment as in example 4 was used except that: heating to 850 ℃ at the heating rate of 3 ℃/min without three-stage temperature programmed sintering, and keeping the temperature for 10 h; the temperature is reduced to 60 ℃ at the speed of 5 ℃/min to obtain a calcined substance.
Test example
The ternary positive electrode materials in examples 1-4 and comparative examples 1-5 are respectively assembled into a 2032 type button battery, metal lithium is taken as a negative electrode to ensure that sufficient lithium ions are provided, and the positive electrode is composed of the ternary materials: conductive carbon black: binder 8: 1: 1 (mass ratio), the test voltage range is 3.0-4.2V, and the test results are shown in Table 1.
Table 1 lithium ion battery performance test results
As can be seen from comparative example 2 and comparative example 1 in Table 1, the first discharge capacity and the cycling stability of the material can be effectively improved by metal doping, but the performance improvement is not obvious by the traditional process, and the residual alkali content of the material is high. From comparative example 1 and example 4, it can be seen that the ternary material preparation method of the present invention can effectively reduce the surface residual alkali content, and the metal cation doping effect is more obvious by the preparation method of the present invention under the condition of the same doping element and doping amount, and the first capacity and the cycle retention rate are improved higher than those of the conventional ternary material preparation process. As can be seen from the comparison of example 4 with comparative examples 3 to 5, the surface residual alkali content and the electrochemical performance of the material are inferior to those of example 4.
Further, as can be seen from fig. 2, the ternary cathode material is successfully prepared, and the peak intensity of crystal plane I (003): i (104) >1.2 shows that the lithium-nickel mixed-disclination degree is low, and (111) and (012) are not overlapped, which shows that the crystal growth is good, and the SEM image in figure 3 shows that the polycrystalline ternary material is generated, the particle surface has no obvious foreign matter, the residual alkali is low, the particle uniformity is good, the growth is uniform, and the particle dispersibility is good. And practical test representation shows that the structures of the comparative example 4 and the comparative example 4 show that the metal doping effect can be obviously improved through ultrasonic infiltration of the fluorine-containing organic solvent, so that the metal doping effect is more uniform, and the electrochemical performance of the anode material is improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the ternary cathode material is characterized by comprising the following steps of:
mixing a ternary precursor, a lithium source and a metal dopant, mixing, wet-grinding and drying by taking an organic solvent as a dispersion medium to obtain a mixture;
ultrasonically infiltrating the mixture by adopting a fluorine-containing organic solvent, and granulating and tabletting to obtain mixed particles;
and (3) sintering the mixed particles at a high temperature by adopting three-stage temperature programming, crushing and grading to prepare the ternary cathode material.
2. The method of claim 1, wherein the ternary precursor is selected from the group consisting of nickel cobalt manganese hydroxides having the general chemical formula NixCoyMn1-x-y(OH)2Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, and x + y is less than 1;
the lithium source is selected from lithium hydroxide or lithium carbonate.
3. The method of claim 1, wherein the metal dopant is selected from the group consisting of AlCl3、MgCl2、ZrCl4One or a mixture of two or more of them.
4. The method according to claim 1, wherein the metal dopant is added in an amount of 600-1000 ppm.
5. The method according to claim 1, wherein the organic solvent is one or a mixture of two or more selected from methanol, ethanol, and diethyl ether;
the process for mixing and wet grinding specifically comprises the following steps: ball material ratio 16-20: 1, the ball milling rotation speed is 300-.
6. The preparation method according to claim 1, wherein the fluorine-containing organic solvent is added in an amount of 3-5% by mass of the mixture, wherein the fluorine-containing organic solvent is obtained by dissolving PVDF in a solvent selected from NMP, DMAc or DMF, and the mass ratio of PVDF to solvent is 0.5-1: 1.
7. the preparation method of claim 1, wherein the ultrasonic infiltration is performed at an ultrasonic frequency of not less than 25kHz for 2-4 hours;
the pressure of the granulation and tabletting is 0.2-0.4MPa, and the particle size of the mixed particles is 5-10 mm.
8. The preparation method according to claim 1, wherein the three temperature programming steps are specifically: heating to 160-class 210 ℃ at a speed of 1-3 ℃/min, then preserving heat for 3-5h, heating to 300-class 350 ℃ at a heating rate of 1-3 ℃/min, preserving heat for 3-5h, heating to 850-class 920 ℃ at a heating rate of 3-5 ℃/min, and preserving heat for 10-12 h; cooling at the rate of 5-8 deg.C/min.
9. A ternary positive electrode material, characterized by being produced by the production method according to any one of claims 1 to 8.
10. Use of the ternary cathode material of claim 9 in the preparation of a ternary lithium ion battery.
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