CN113422046B - High-nickel single crystal nickel-cobalt-aluminum ternary cathode material and preparation method thereof - Google Patents
High-nickel single crystal nickel-cobalt-aluminum ternary cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material and a preparation method thereof, wherein the chemical formula of the high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material is LiaNixCoyAl1‑x‑yMbO2Wherein a is more than or equal to 1 and less than or equal to 1.2,0.8 and less than 1,0 and less than y and less than or equal to 0.15,0.001 and less than or equal to b and less than or equal to 0.01; the preparation method comprises the following steps of S1: uniformly mixing a ternary oxide precursor with high BET (BET), lithium hydroxide and a compound containing a doping element M, and sintering at high temperature for a short time and then at low temperature for a long time; s2: and cooling, crushing and sieving to obtain the high-nickel single crystal nickel-cobalt-aluminum ternary cathode material. According to the invention, the high BET oxide precursor is adopted for high and low temperature sintering, the stress of the high nickel single crystal nickel cobalt aluminum ternary positive electrode material is controlled within the range of 0.07-0.14, the distortion is not easy to occur in the charging and discharging processes, the cycle performance of the positive electrode material is good, and the capacity is higher.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode materials, and particularly relates to a high-nickel single-crystal nickel-cobalt-aluminum ternary anode material and a preparation method thereof.
Background
In order to solve the problem of too fast capacity attenuation of the lithium ion battery, many research institutes try to use a high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material to replace the traditional secondary ball ternary cathode material. Patent application No. US20200127280A1 mentions that single crystal lithium nickel cobalt aluminate positive electrode material LiNi obtained by a two-step lithiation process0.88Co0.09Al0.03O2And after the material is circulated for 100 circles at normal temperature, the capacity retention rate is higher than that of the secondary sphere anode material. Also, for example, liNi, a single crystal lithium nickel cobalt aluminate cathode material synthesized in Journal of Alloys and Compounds,2016,6950.80Co0.15Al0.05O2After 100 cycles, the capacity retention rate of 91.7% still exists, and the capacity retention rate of the corresponding secondary ball cathode material is only 74.9% left.
The reported patents and literature generally adopt high-temperature long-time burningAnd synthesizing the high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material in a junction mode. Although the above technical means can achieve the effect of improving the battery cycle, the solution has many disadvantages: such as high energy consumption, long time consumption, serious volatilization of lithium in the layered structure, high residual lithium in the sample, and impurity generation (such as Li)5AlO4NiO), etc.; therefore, the capacity of the existing high-nickel monocrystal nickel-cobalt-aluminum ternary positive electrode material battery is low, and the cycle performance still has a larger promotion space.
How to improve the service life of the battery while keeping the capacity of the battery not reduced to obtain a high-nickel single crystal nickel-cobalt-aluminum ternary cathode material with excellent cycle performance and provide a simpler and more convenient preparation method becomes a problem to be solved at present.
Disclosure of Invention
The invention aims to solve the technical problems that the capacity of the high-nickel single crystal nickel-cobalt-aluminum ternary cathode material is reduced by high-temperature sintering, the defects and shortcomings mentioned in the background technology are overcome, and the high-nickel single crystal nickel-cobalt-aluminum ternary cathode material which is high in capacity and can improve the cycle performance is provided; in addition, the invention also provides a method for preparing the high-nickel single crystal nickel-cobalt-aluminum ternary cathode material, so as to solve the defects and shortcomings caused by high-temperature long-time sintering in the background art, effectively shorten the high-temperature sintering time and reduce the residual lithium on the surface.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material has a chemical formula of LiaNixCoyAl1-x-yMbO2Wherein a is more than or equal to 1 and less than or equal to 1.2,0.8 and less than 1,0 and Y is more than or equal to 0.15,0.001 and less than or equal to 0.01, M is selected from one or more of Zr, al, ce, sr, mg, ti, mn, si, la, ba, sr, nb, cr, mo, ca, Y, in, sn and F, and the residual stress value range of the high-nickel single crystal nickel-cobalt-aluminum ternary positive electrode material is 0.08-0.14.
Preferably, the residual stress is obtained by XRD ray diffraction method test and refinement, wherein, the scanning range of XRD test is more than or equal to 10 degrees and less than or equal to 2 theta and less than or equal to 80 degrees, the scanning speed is 5 degrees/min, and Topas software is utilized to refine the obtained XRD spectrogram by Rietveld full-spectrum fitting refinement method.
The residual stress of the high-nickel single crystal nickel-cobalt-aluminum ternary cathode material is controlled to be 0.08-0.14, when the residual stress is large, distortion is easy to occur in the charge-discharge process, and the cycle performance is poor; when the residual stress is smaller, the capacity increase is affected, resulting in a lower capacity.
The median particle size D50 range of the high-nickel single crystal nickel-cobalt-aluminum ternary cathode material is 3.5-4.5 microns.
The invention controls the median particle diameter D50 to be 3.5-4.5 μm, and can simultaneously give consideration to capacity and circulation. The particle size is too large, the lithium ion conduction path is too long, and the capacity is not favorably exerted; the particle size is too small, most of the anode materials are agglomerated secondary spheres, the single crystal morphology is difficult to form, and in the later charging and discharging process, due to the intercalation and de-intercalation of lithium ions, the volume of the materials can change, and cracks can be formed among particles, so that the cycle performance is influenced.
Preferably, the molar ratio of Li/Me in the high-nickel single crystal nickel-cobalt-aluminum ternary cathode material is within the range of 0.990-1.100, wherein Me comprises Ni, co, al and a doping element M.
Preferably, the specific surface area of the high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material is 0.4 +/-0.2 m2G, the compacted density is more than or equal to 3.45g/cm3. Too high a specific surface area may result in too much contact between the material and the electrolyte, thereby increasing side reactions and aggravating material deterioration; the specific surface area is too low, which means that the particles are too large, and the exertion of the material capacity is not facilitated; the high compaction density can provide high energy density and improve the performance of the nickel single crystal nickel-cobalt-aluminum ternary cathode material.
Preferably, the unit cell parameters of the high-nickel single crystal nickel-cobalt-aluminum ternary positive electrode material are that a is more than or equal to 2.87 and less than or equal to 2.88, c is more than or equal to 14.18 and less than or equal to 14.20, and c/a is more than or equal to 4.9370. The high-nickel monocrystal nickel-cobalt-aluminum ternary cathode material disclosed by the invention is excellent in unit cell parameters and good in crystallinity.
Under the same technical concept, the application also provides a preparation method of the high-nickel monocrystal nickel-cobalt-aluminum ternary cathode material, which comprises the following steps of:
s1: uniformly mixing a ternary oxide precursor, lithium hydroxide and a compound containing a doping element M, and sintering at high temperature for a short time and then at low temperature for a long time;
s2: and cooling, crushing and sieving to obtain the high-nickel single crystal nickel-cobalt-aluminum ternary cathode material.
Preferably, the ternary oxide precursor has a chemical formula of NixCoyAl1-x-yO2BET range of 40m2/g～70m2The ternary hydroxide precursor is sintered at the temperature of 450-500 ℃ for 2-8 h.
Preferably, the two-stage sintering is carried out, wherein the temperature range of the first-stage sintering is 780-900 ℃, the sintering time is 1-4 h, the temperature range of the second-stage sintering is 600-780 ℃, the sintering time is 6-20 h, and the temperature difference of the two-stage sintering is more than or equal to 20 ℃;
preferably, the heating rate of the first-stage sintering and the second-stage sintering is 1-5 ℃/min, and the sintering atmosphere is an oxygen atmosphere.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the stress of the high-nickel single-crystal nickel-cobalt-aluminum ternary positive electrode material is controlled within the range of 0.08-0.14, so that the high-nickel single-crystal nickel-cobalt-aluminum ternary positive electrode material is not easy to distort in the charging and discharging processes, the cycle performance of the material is improved, and the capacity is higher.
(2) The preparation method provided by the invention has the advantages that the high-BET oxide precursor is used for replacing the low-BET hydroxide precursor, so that the contact area of the precursor and the lithium hydroxide is increased, and the reaction of the precursor and the lithium hydroxide is promoted; after the mixed precursor and lithium hydroxide are sintered at high temperature for a short time to obtain a single crystal shape, and then sintered at low temperature for a long time, the high BET precursor and the high temperature and low temperature sintering play a synergistic role to jointly promote the optimization of a crystal structure. The sintering mode is favorable for controlling the stress of the material to be in a lower level, not only can obtain NCA with single crystal morphology, but also can avoid lithium volatilization caused by the material being in a high-temperature state for a long time. The Li/Me obtained by testing is higher, so that the loss of lithium is reduced, more lithium is promoted to enter a layered structure to form a better crystal structure, and the better crystal structure is beneficial to more lithium ions to be extracted and inserted, so that the capacity performance of the material is improved, and meanwhile, the productivity can be improved by using the oxide precursor, and the production cost is reduced.
(3) The single crystal NCA material obtained by the invention has more excellent electrochemical performance, the discharge capacity of the first circle can reach 201.5mAh/g at 25 ℃ when the anode material is assembled into a button cell, 96.3% of capacity retention rate still exists after 50 circles of circulation, 93.2% of capacity retention rate still exists at 45 ℃, the material has excellent rate capability, and the rate of 2C/0.2C can reach 93.3%.
(4) The invention adopts a rapid sintering mode to prepare the single crystal NCA material for the first time, and the mode is simple and easy to implement, has lower energy consumption and saves the cost; by using the rapid sintering process provided by the invention, because lithium is more prone to enter a layered structure rather than being enriched on the surface of the material to be volatilized, the content of residual unreacted LiOH is lower, the content of the residual LiOH can be reduced by more than 0.3 percent, even the secondary sintering coating can be directly carried out without a water washing step, and the cost is saved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scanning electron microscope image of a high nickel single crystal nickel cobalt aluminum ternary positive electrode material prepared in example 1;
FIG. 2 is a scanning electron microscope image of the high nickel single crystal Ni-Co-Al ternary positive electrode material prepared in example 2;
FIG. 3 is a scanning electron microscope image of the high nickel single crystal Ni-Co-Al ternary positive electrode material prepared in example 3;
FIG. 4 is a scanning electron microscope image of the nickel-cobalt-aluminum ternary cathode material of high nickel single crystal prepared in example 4;
FIG. 5 is a scanning electron microscope image of the high-nickel single-crystal Ni-Co-Al ternary positive electrode material prepared in comparative example 1;
FIG. 6 is a scanning electron microscope image of the high-nickel single-crystal Ni-Co-Al ternary positive electrode material prepared in comparative example 2;
FIG. 7 is a scanning electron microscope image of the high-nickel single-crystal nickel-cobalt-aluminum ternary positive electrode material prepared in comparative example 3;
FIG. 8 is a graph of the residual LiOH of examples 1-4 and comparative examples 1-2 as wt% of the total mass of the sample;
FIG. 9 is a graph of actual Li/Me molar ratios for examples 1-4 and comparative examples 1-2;
FIG. 10 is a 1C capacity retention rate curve (room temperature) of examples 1-4 and comparative examples 1-2;
FIG. 11 is the 1C capacity retention (high temperature) of examples 1-4 and comparative examples 1-2.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a high-nickel single-crystal Ni-Co-Al ternary positive electrode material with molecular formula of Li1.01Ni0.90Co0.08Al0.02Zr0.003O2A median particle diameter D50 of 3.77 μm, a residual stress strain value of 0.117, a BET of 0.43m2(ii)/g, compacted density of 3.533g/cm3Compaction density of correspondingThe test pressure of (2) is 60MPa. FIG. 1 is a scanning electron microscope image of the high nickel single crystal nickel cobalt aluminum ternary positive electrode material of example 1.
The residual stress is obtained by testing and refining through an XRD ray diffraction method, wherein the scanning range of the XRD test is more than or equal to 10 degrees and less than or equal to 2 theta and less than or equal to 80 degrees, the scanning speed is 5 degrees/min, topas software is utilized, the obtained XRD spectrogram is refined through a Rietveld full-spectrum fitting refining method, and the Germany Bruker D8 ADVANCE is adopted in the XRD test.
The preparation method of the high-nickel monocrystal nickel-cobalt-aluminum ternary cathode material comprises the following steps of:
(1) The ternary precursor Ni0.9Co0.08Al0.02(OH)2Sintering for 5h at 450 ℃ in air atmosphere to obtain ternary oxide precursor Ni0.9Co0.08Al0.02O2BET of 60.70m2(iv) g; then, according to the molar ratio of transition metal to lithium being 1:1.01 weighing the sintered ternary oxide precursor, liOH and an additive ZrO2And fully mixing the three materials, sintering in an oxygen atmosphere at the heating rate of 3 ℃/min, heating to 790 ℃, keeping for 2h, cooling to 720 ℃, keeping for 13h, naturally cooling to below 100 ℃, taking out to obtain a positive electrode material sample, wherein the content of residual LiOH in the test accounts for 0.499wt% of the total mass of the sample.
(2) And (2) crushing the sample obtained in the step (1) for 2min, and then sieving the crushed sample by using a 300-mesh sieve to obtain the final high-nickel monocrystal nickel-cobalt-aluminum ternary cathode material.
Example 2:
a high-nickel single-crystal Ni-Co-Al ternary positive electrode material with molecular formula of Li1.04Ni0.90Co0.08Al0.02Zr0.003O2A median particle diameter D50 of 3.86 μm, a residual stress strain value of 0.112, a BET of 0.49m2(ii)/g, compacted density of 3.552g/cm3The test pressure corresponding to the compacted density is 60MPa. The residual stress test and the finishing method were the same as in example 1. FIG. 2 is a scanning electron microscope image of the nickel-cobalt-aluminum ternary cathode material of high nickel single crystal in example 2;
the preparation method of the high-nickel single crystal nickel-cobalt-aluminum ternary cathode material comprises the following steps of:
(1) The ternary precursor Ni0.9Co0.08Al0.02(OH)2Sintering for 5h at 450 ℃ in air atmosphere to obtain ternary oxide precursor Ni0.9Co0.08Al0.02O, BET of 60.70m2(ii)/g; then, according to the molar ratio of transition metal to lithium being 1:1.04 to weigh the sintered ternary oxide precursor, liOH and the additive ZrO2And fully mixing the three components, sintering in an oxygen atmosphere at the heating rate of 3 ℃/min, heating to 790 ℃, keeping for 2h, cooling to 720 ℃, keeping for 13h, naturally cooling to below 100 ℃, taking out to obtain an anode material sample, and testing the content of residual LiOH to be 1.001wt% of the total mass of the sample.
(2) And (2) crushing the sample obtained in the step (1) for 2min, and then sieving the crushed sample by using a 300-mesh sieve to obtain the final high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material.
Example 3:
a high-nickel single-crystal Ni-Co-Al ternary positive electrode material with molecular formula of Li1.01Ni0.90Co0.08Al0.02Zr0.003O2A median particle diameter D50 of 3.74 μm, a residual stress strain value of 0.104, a BET of 0.42m2(ii)/g, compacted density of 3.578g/cm3The test pressure corresponding to the compaction density was 60MPa. The residual stress test and the finishing method were the same as in example 1. FIG. 3 is a scanning electron microscope image of the nickel-cobalt-aluminum ternary cathode material of high nickel single crystal in example 3.
The preparation method of the high-nickel single crystal nickel-cobalt-aluminum ternary cathode material comprises the following steps of:
(1) The ternary precursor Ni0.9Co0.08Al0.02(OH)2Sintering for 5h at 450 ℃ in air atmosphere to prepare ternary oxide precursor Ni0.9Co0.08Al0.02O, BET of 60.70m2(ii)/g; then, according to the molar ratio of transition metal to lithium being 1:1.01 weighing the sintered ternary oxide precursor, liOH and an additive ZrO2And the three are fully mixed,sintering in an oxygen atmosphere, wherein the heating rate is 3 ℃/min, the temperature is raised to 790 ℃, the temperature is maintained for 2h, the temperature is reduced to 740 ℃, the temperature is maintained for 13h, then the temperature is naturally reduced to below 100 ℃, and the anode material is taken out to obtain an anode material sample, and the content of residual LiOH in the test accounts for 0.671wt% of the total mass of the sample.
(2) And (2) crushing the sample obtained in the step (1) for 2min, and then sieving the crushed sample by using a 300-mesh sieve to obtain the final high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material.
Example 4:
a high-nickel single-crystal Ni-Co-Al ternary positive electrode material with molecular formula of Li1.04Ni0.90Co0.08Al0.02Zr0.003O2A median particle diameter D50 of 3.71 μm, a residual stress strain value of 0.104, a BET of 0.46m2(ii)/g, compacted density of 3.596g/cm3The test pressure corresponding to the compaction density was 60MPa. The residual stress test and the finishing method were the same as in example 1. FIG. 4 is a scanning electron microscope image of the nickel-cobalt-aluminum ternary positive electrode material of the high nickel single crystal of example 4.
The preparation method of the high-nickel monocrystal nickel-cobalt-aluminum ternary cathode material comprises the following steps of:
(1) The ternary precursor Ni0.9Co0.08Al0.02(OH)2Sintering for 5h at 450 ℃ in air atmosphere to obtain ternary oxide precursor Ni0.9Co0.08Al0.02O, BET of 60.70m2(ii)/g; then, according to the molar ratio of transition metal to lithium being 1:1.04 to weigh the sintered ternary oxide precursor, liOH and the additive ZrO2And fully mixing the three components, sintering in an oxygen atmosphere at the heating rate of 3 ℃/min, heating to 790 ℃, keeping for 2h, cooling to 740 ℃, keeping for 13h, naturally cooling to below 100 ℃, taking out to obtain an anode material sample, and testing the content of residual LiOH to be 0.955wt% of the total mass of the sample.
(2) And (2) crushing the sample obtained in the step (1) for 2min, and then sieving the crushed sample by using a 300-mesh sieve to obtain the final high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material.
Comparative example 1:
a high-nickel single-crystal Ni-Co-Al ternary positive electrode material with molecular formula of Li1.01Ni0.90Co0.08Al0.02Zr0.003O2A median particle diameter D50 of 3.94 μm, a residual stress strain value of 0.119, a BET of 0.51m2(ii)/g, compacted density of 3.670g/cm3The test pressure corresponding to the compacted density is 60MPa. The residual stress test and the finishing method were the same as in example 1. FIG. 5 is a scanning electron microscope image of the nickel-high single crystal Ni-Co-Al ternary positive electrode material of comparative example 1.
(1) The ternary precursor Ni0.9Co0.08Al0.02(OH)2Sintering the mixture for 5 hours at 450 ℃ in an air atmosphere to obtain a ternary oxide precursor BET of 60.70m2(ii)/g; then, according to the molar ratio of transition metal to lithium being 1:1.01 weighing the sintered ternary oxide precursor, liOH and an additive ZrO2And fully mixing the three components, sintering in an oxygen atmosphere, heating to 790 ℃ at the heating rate of 3 ℃/min, keeping for 15h, naturally cooling to below 100 ℃, taking out to obtain an anode material sample, and testing that the content of residual LiOH accounts for 0.972wt% of the total mass of the sample.
(2) And (2) crushing the sample obtained in the step (1) for 2min, and then sieving the crushed sample by using a 300-mesh sieve to obtain the final high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material.
Comparative example 2:
a high-nickel single-crystal Ni-Co-Al ternary positive electrode material with molecular formula of Li1.04Ni0.90Co0.08Al0.02Zr0.003O2A median particle diameter D50 of 3.99 μm, a residual stress strain value of 0.118, a BET of 0.49m2(ii)/g, compacted density of 3.653g/cm3The test pressure corresponding to the compaction density was 60MPa. The residual stress test and the finishing method were the same as in example 1. FIG. 6 is a scanning electron microscope image of the high nickel single crystal nickel cobalt aluminum ternary positive electrode material of comparative example 2.
(1) The ternary precursor Ni0.9Co0.08Al0.02(OH)2Sintering for 5h at 450 ℃ in air atmosphere to obtain ternary oxide precursorBET of 60.70m2(ii)/g; then, according to the molar ratio of transition metal to lithium being 1:1.04 weighing sintered precursor, liOH and additive ZrO2And fully mixing the three components, sintering in an oxygen atmosphere, heating to 790 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 15h, naturally cooling to below 100 ℃, and taking out to obtain an anode material sample, wherein the content of residual LiOH in the test accounts for 1.353wt% of the total mass of the sample.
(2) And (2) crushing the sample obtained in the step (1) for 2min, and then sieving the crushed sample by using a 300-mesh sieve to obtain the final high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material.
Table 1 below is discharge capacity data at different rates for examples 1 to 4 and comparative examples 1 to 2.
Comparative example 3:
a high-nickel single-crystal Ni-Co-Al ternary positive electrode material with molecular formula of Li1.04Ni0.90Co0.08Al0.02Zr0.003O2The median particle diameter D50 was 4.01. Mu.m, the residual stress strain value was 0.122, and the compacted density was 3.513g/cm3The test pressure corresponding to the compacted density is 60MPa. The residual stress test and the finishing method were the same as in example 1. FIG. 7 is a scanning electron microscope image of the nickel-high single crystal Ni-Co-Al ternary positive electrode material of comparative example 3.
(1) According to the molar ratio of transition metal to lithium being 1:1.04 to weigh the hydroxide precursor Ni0.9Co0.08Al0.02(OH)2LiOH and an additive ZrO2And fully mixing the three components, sintering in an oxygen atmosphere, heating to 790 ℃ at the heating rate of 3 ℃/min, keeping for 15 hours, naturally cooling to below 100 ℃, taking out to obtain a positive electrode material sample, and testing the content of residual LiOH accounting for 1.320wt% of the total mass of the sample.
(2) And (2) crushing the sample obtained in the step (1) for 2min, and then sieving the crushed sample by using a 300-mesh sieve to obtain the final high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material.
Table 1 below is discharge capacity data at different rates for examples 1 to 4 and comparative examples 1 to 2.
TABLE 1
| Unit of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| 0.1C discharge capacity | mAh/g | 201.2 | 202.4 | 202.0 | 202.6 | 194.5 | 194.3 | 195.1 |
| 0.2C discharge capacity | mAh/g | 196.7 | 199.8 | 198.1 | 199.4 | 192.5 | 192.0 | 193.0 |
| 0.5C discharge capacity | mAh/g | 192.8 | 194.3 | 193.1 | 194.3 | 187.5 | 186.9 | 189.0 |
| 1.0C discharge capacity | mAh/g | 189.4 | 190.4 | 188.9 | 190.5 | 184.1 | 182.8 | 185.7 |
| 2.0C discharge capacity | mAh/g | 185.5 | 186.5 | 184.9 | 186.9 | 179.9 | 178.7 | 181.6 |
Through the examples and comparative examples, it can be seen that the stress of the material can be controlled at a relatively low level by using the technology mentioned in the present invention, which indicates that the material is not easy to be distorted during the circulation process; residual LiOH in the material is lower, so that the possibility of direct secondary-sintering coating without water washing is provided; as can be seen from fig. 8-11, the capacity retention rate is higher and the tested Li/Me is higher in this embodiment, which indicates that the technology can effectively reduce the volatilization of lithium, thereby promoting more lithium to enter the layered structure; in addition, the technology also saves energy consumption to a certain extent and reduces production cost; the materials synthesized by the technology are assembled into a buckle for electrochemical performance test, and the result shows that the materials are more excellent in capacity and cycle.
Claims (5)
1. The high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material is characterized in that the chemical formula of the high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material is LiaNixCoyAl1-x-yMbO2Wherein a is more than or equal to 1 and less than or equal to 1.2,0.8 and less than or equal to 1,0 and Y is more than or equal to 0.15,0.001 and less than or equal to 0.01, M is selected from one or more of Zr, al, ce, sr, mg, ti, mn, si, la, ba, nb, cr, mo, ca, Y, in, sn and F, the residual stress value range of the high-nickel single crystal nickel-cobalt-aluminum ternary positive electrode material is 0.08 to 0.14, the residual stress is obtained by XRD ray diffraction method test and fine modification, the scanning range of XRD test is more than or equal to 10 degrees and less than or equal to 2 theta and less than or equal to 80 degrees, the scanning speed is 5 degrees/min, and Topas software is utilized to carry out fine modification on the obtained XRD spectrogram by Rietveld full spectrum fitting fine modification method; the median particle diameter D50 range of the high-nickel single crystal nickel-cobalt-aluminum ternary positive electrode material is 3.5-4.5 mu m, and the specific surface area is 0.4 +/-0.2 m2G, the compacted density is more than or equal to 3.45g/cm3；
The preparation method of the high-nickel single crystal nickel-cobalt-aluminum ternary cathode material comprises the following steps of:
s1: with a BET range of 40m2/g~70m2Ternary oxide precursor/g, lithium hydroxide precursor containing dopantUniformly mixing the compounds of the heteroelement M, and sintering the mixture in two stages, wherein the temperature range of the first stage of sintering is 780-900 ℃, the sintering time is 1h-4h, the temperature range of the second stage of sintering is 600-780 ℃, the sintering time is 6-20h, and the temperature difference of the two stages of sintering is more than or equal to 20 ℃;
s2: and cooling, crushing and sieving to obtain the high-nickel monocrystal nickel-cobalt-aluminum ternary cathode material.
2. The high-nickel single-crystal nickel-cobalt-aluminum ternary positive electrode material according to claim 1, wherein the molar ratio of Li/Me in the high-nickel single-crystal nickel-cobalt-aluminum ternary positive electrode material is in the range of 0.990 or more Li/Me < 1.100, and Me contains Ni, co, al and a doping element M.
3. The nickel-cobalt-aluminum ternary positive electrode material as claimed in any one of claims 1-2, wherein the cell parameters of the nickel-cobalt-aluminum ternary positive electrode material are 2.87 ≤ a ≤ 2.88, 14.18 ≤ c ≤ 14.20, and c/a ≥ 4.9370.
4. The high-nickel single-crystal nickel-cobalt-aluminum ternary positive electrode material of claim 1, wherein the ternary oxide precursor has a chemical formula of NixCoyAl1-x-yO2The material is obtained by sintering a ternary hydroxide precursor, wherein the sintering temperature ranges from 450 ℃ to 500 ℃, and the sintering time ranges from 2 to 8 hours.
5. The high-nickel single-crystal nickel-cobalt-aluminum ternary cathode material as claimed in claim 1, wherein the temperature rise rates of the first stage sintering and the second stage sintering are 1~5 ℃/min, and the sintering atmosphere is oxygen atmosphere.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012252853A (en) * | 2011-06-02 | 2012-12-20 | Toyota Industries Corp | Method for manufacturing lithium-containing complex oxide, positive electrode active material, and secondary battery |
| CN109560276A (en) * | 2018-11-27 | 2019-04-02 | 宁波容百新能源科技股份有限公司 | A kind of monocrystalline tertiary cathode material and preparation method thereof and lithium ion battery with concentration gradient distribution primary particle oriented growth |
| CN110265657A (en) * | 2019-04-24 | 2019-09-20 | 河南科隆新能源股份有限公司 | One type monocrystalline lithium nickel cobalt manganese oxide material and preparation method thereof |
| CN111969200A (en) * | 2020-08-28 | 2020-11-20 | 湖南杉杉能源科技股份有限公司 | High-capacity long-cycle nickel-cobalt-manganese ternary cathode material and preparation method thereof |
| CN112151789A (en) * | 2019-06-28 | 2020-12-29 | 宁德时代新能源科技股份有限公司 | Positive electrode material and preparation method and application thereof |
| EP3817105A1 (en) * | 2019-10-31 | 2021-05-05 | Samsung SDI Co., Ltd. | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
-
2021
- 2021-06-30 CN CN202110738477.XA patent/CN113422046B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012252853A (en) * | 2011-06-02 | 2012-12-20 | Toyota Industries Corp | Method for manufacturing lithium-containing complex oxide, positive electrode active material, and secondary battery |
| CN109560276A (en) * | 2018-11-27 | 2019-04-02 | 宁波容百新能源科技股份有限公司 | A kind of monocrystalline tertiary cathode material and preparation method thereof and lithium ion battery with concentration gradient distribution primary particle oriented growth |
| CN110265657A (en) * | 2019-04-24 | 2019-09-20 | 河南科隆新能源股份有限公司 | One type monocrystalline lithium nickel cobalt manganese oxide material and preparation method thereof |
| CN112151789A (en) * | 2019-06-28 | 2020-12-29 | 宁德时代新能源科技股份有限公司 | Positive electrode material and preparation method and application thereof |
| EP3817105A1 (en) * | 2019-10-31 | 2021-05-05 | Samsung SDI Co., Ltd. | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN111969200A (en) * | 2020-08-28 | 2020-11-20 | 湖南杉杉能源科技股份有限公司 | High-capacity long-cycle nickel-cobalt-manganese ternary cathode material and preparation method thereof |
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