CN119118222A - A medium-high nickel ternary positive electrode material powder and preparation method thereof, and a ternary positive electrode sheet - Google Patents
A medium-high nickel ternary positive electrode material powder and preparation method thereof, and a ternary positive electrode sheet Download PDFInfo
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Abstract
本申请属于锂离子电池领域，公开了一种中高镍三元正极材料粉末的制备方法，将镍钴锰前驱体、锂源、掺杂剂进行混合，得到混合物料；对混合物料进行烧结、冷却、破碎、过筛，得到烧结粉末；再将烧结粉末与磷源粉末、镧源粉末进行混合，煅烧、冷却、破碎、过筛，得到中高镍三元正极材料粉末；通过磷源粉末与镧源粉末进行低温熔融包覆，降低残留锂的同时提升正极材料性能。此外，还公开了一种通过上述方法制得的中高镍三元正极材料粉末及由上述中高镍三元正极材料粉末制得的中高镍三元正极片。The present application belongs to the field of lithium-ion batteries, and discloses a method for preparing a medium-high nickel ternary positive electrode material powder, wherein a nickel-cobalt-manganese precursor, a lithium source, and a dopant are mixed to obtain a mixed material; the mixed material is sintered, cooled, crushed, and sieved to obtain a sintered powder; the sintered powder is then mixed with a phosphorus source powder and a lanthanum source powder, calcined, cooled, crushed, and sieved to obtain a medium-high nickel ternary positive electrode material powder; the phosphorus source powder and the lanthanum source powder are low-temperature melt-coated to reduce residual lithium while improving the performance of the positive electrode material. In addition, a medium-high nickel ternary positive electrode material powder prepared by the above method and a medium-high nickel ternary positive electrode sheet prepared from the above medium-high nickel ternary positive electrode material powder are also disclosed.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a middle-high nickel ternary positive electrode material powder, a preparation method thereof and a ternary positive electrode plate.
Background
The nickel cobalt lithium manganate anode material is widely applied to power lithium batteries due to high energy density, long cycle life and high voltage platform, the anode material accounts for about 40% of the cost of a single battery core, the performance advantages and disadvantages of the anode material are directly related to the energy density, safety, service life and the like of the battery core and a system, the surface coating is a main way for modifying the nickel cobalt lithium manganate anode material, and the uniform and compact coating layer can greatly improve the comprehensive performance of the nickel cobalt lithium manganate.
In the prior art 1, chinese patent application 2015165733. X discloses a lithium manganese phosphate coated nickel cobalt lithium manganate positive electrode material and a preparation method thereof, wherein a complexing agent compound, a lithium source compound, a manganese source compound and a phosphorus source compound are sequentially dissolved in water to prepare a solution, the pH value is adjusted, then the nickel cobalt lithium manganate is added into the prepared solution, the obtained solution is stirred and evaporated until the solution is sticky, aged, dried and crushed to obtain solid powder, the obtained solid powder is roasted, and the temperature is naturally reduced to room temperature to obtain the lithium manganese phosphate coated nickel cobalt lithium manganate positive electrode material.
The lithium phosphate with stable structure is used as a coating material to promote the conduction of lithium ions on the surface of the nickel cobalt lithium manganate, so that the rate capability is improved. In addition, PO 4 3- in LiMnPO 4 can effectively inhibit dissolution of electrode materials in electrolyte, prevent corrosion of hydrofluoric acid in the electrolyte on the surface of active materials, and improve safety performance and cycle stability.
In the prior art 2, china patent application 201610462297.2 discloses a method for coating lithium ion battery anode material nickel cobalt lithium manganate with lanthanum phosphate, wherein ternary precursors, lithium salt, lanthanum salt and phosphate are added into a high-speed mixer, stirred for 1-4 hours at 500-2000 rpm, then the treated materials are heated for 5-20 hours in an oxygen-containing atmosphere at 750-1200 ℃, and kept for 4-10 hours, and the lanthanum phosphate-coated lithium ion battery anode material nickel cobalt lithium manganate is obtained after cooling.
In the coating process of the scheme, the P=O bond in the LaPO 4 can improve the chemical stability of the material, protect the electrode material from acid corrosion of electrolyte, and the combination of the composite material and lanthanum can improve the thermal stability. In addition, an amorphous LaPO 4 compound can be formed on the surface of the nickel cobalt lithium manganate ternary positive electrode material, and the amorphous LaPO 4 is coated on the surface of the nickel cobalt lithium manganate ternary positive electrode material, so that the content of impurity lithium can be effectively reduced, and the cycle performance and electrochemical performance of the lithium ion battery under high voltage can be effectively improved.
The technical scheme solves the problem of how to propose a novel preparation method for improving the electrochemical performance of the middle-high nickel ternary cathode material.
Disclosure of Invention
The invention aims to provide a middle-high nickel ternary positive electrode material powder and a preparation method thereof, wherein a shallow coating structure is formed on a ternary positive electrode material by using a doping agent, then a phosphorus source and a lanthanum source are added for calcination coating, so that a uniform coating layer is formed on the surface of the positive electrode material, and the electrochemical performance of the middle-high nickel ternary positive electrode material is improved under the protection of the two coating structures.
In order to achieve the above purpose, the application discloses a preparation method of a middle-high nickel ternary positive electrode material powder, which is characterized by comprising the following steps:
step 1, mixing a nickel cobalt manganese precursor, a lithium source and a doping agent to obtain a mixed material;
step 2, sintering, cooling, crushing and sieving the mixed material to obtain sintered powder;
step3, mixing the sintered powder with phosphorus source powder and lanthanum source powder, calcining, cooling, crushing and sieving to obtain middle-high nickel ternary anode material powder;
The phosphorus source powder is at least one selected from ammonium dihydrogen phosphate NH 4H2PO4, diammonium hydrogen phosphate (NH 4)2HPO4, lithium dihydrogen phosphate LiH 2PO4, lithium dihydrogen phosphate Li 2HPO4, sodium dihydrogen phosphate NaH 2PO4 and disodium hydrogen phosphate Na 2HPO4);
the lanthanum source powder is selected from at least one of lanthanum nitrate hexahydrate La (NO 3)3·6H2 O, lanthanum nitrate La (NO 3)3, lanthanum acetate C 6H9O6 La) and lanthanum isopropoxide (i-PrO) 3 La).
Preferably, the mass of the phosphorus element in the phosphorus source powder is 1500-5500 ppm of the mass of the sintered powder;
the mass of lanthanum element in the lanthanum source powder is 1500-5500 ppm of the mass of the sintered powder.
Preferably, the structural formula of the high nickel cobalt manganese precursor in the step 1 is Ni xCoyMnz(OH)2, wherein x is more than or equal to 0.50 and less than or equal to 0.92,0.03, y is more than or equal to 0.20,0.05 and less than or equal to z is more than or equal to 0.30, and x+y+z=1;
The lithium source is at least one of lithium carbonate Li 2CO3 or lithium hydroxide hydrate LiOH H 2 O;
further preferably, the lithium source is lithium carbonate;
the Li/Me ratio of the nickel cobalt manganese precursor and the lithium source is 1.02-1.06.
Preferably, the dopant is at least one selected from aluminum oxide Al 2O3, lanthanum oxide La 2O3, zirconium oxide ZrO 2, titanium oxide TiO 2, tungsten oxide WO 3 and niobium oxide Nb 2O5, and the addition amount of the dopant is 1000-5000 ppm of the total mass of the nickel cobalt manganese precursor and the lithium source.
The sintering process in the step 2 is preferably carried out by raising the temperature to 450-720 ℃ at a rate of 2-4 ℃ per minute, preserving heat for 1-5 hours, raising the temperature to 720-950 ℃ at a rate of 2-4 ℃ per minute, and preserving heat for 8-12 hours.
Preferably, the mixing operation in the step 3 is that the sintered powder, the phosphorus source powder and the lanthanum source powder are put into a planetary machine to be mixed and stirred for 1h at the rotating speed of 800rpm, so that the surfaces of the sintered powder are coated with the phosphorus source powder and the lanthanum source powder.
Preferably, the calcination temperature in the step3 is 300-600 ℃ and the calcination time is 6-12 min.
Preferably, the number of the sieving screens in the step 2 and the step 3 is 300 meshes.
In addition, the invention also discloses middle-high nickel ternary positive electrode material powder, which is prepared by the preparation method of the middle-high nickel ternary positive electrode material powder.
In addition, a middle-high nickel ternary positive plate is also disclosed, and the middle-high nickel ternary positive plate is prepared by coating the powder of the middle-high nickel ternary positive plate material on an aluminum foil.
The beneficial effects of the invention are as follows:
The invention provides a middle-high nickel ternary positive electrode material powder and a preparation method thereof, and a middle-high nickel ternary positive electrode plate, wherein after mixed sintering, a part of doping elements enter a shallow surface layer structure of a material at a high temperature after the doping agents added into the middle-high nickel ternary positive electrode material are mixed, so that structural phase change of the material at a high voltage is inhibited, cracking and pulverization of the material are slowed down, the cycle performance of the material is primarily improved, the other part of the doping elements can form lithium-containing substances Li xMyOz on the surfaces of primary particles and secondary particles formed by the primary particles in the ternary positive electrode material together with a lithium source in the sintering process, M is a metal element in the doping agents, and provides a lithium source for a subsequent coating layer.
Detailed Description
In the description of the present invention, it is to be noted that the specific conditions are not specified in the examples, and the description is performed under the conventional conditions or the conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Firstly, mixing nickel cobalt manganese precursor Ni 0.6Co0.1Mn0.3(OH)2 and lithium carbonate according to Li/Me=1.04, and then adding lanthanum oxide with the mass of 3000ppm of the total mass of the nickel cobalt manganese precursor and a lithium source to mix to obtain a mixed material;
step 2, raising the temperature of the mixed material to 580 ℃ at the speed of 3 ℃ per minute, preserving heat for 3 hours, raising the temperature to 830 ℃ at the speed of 3 ℃ per minute, preserving heat for 10 hours, completing sintering, cooling to room temperature, crushing, and sieving with a 300-mesh screen to obtain sintered powder;
And 3, placing the sintered powder, 3500ppm of lithium dihydrogen phosphate powder with the phosphorus content being the mass of the sintered powder and 3500ppm of lanthanum nitrate powder with the lanthanum content being the mass of the sintered powder into a planetary machine, mixing and stirring for 1h at the rotating speed of 800rpm, enabling the lithium dihydrogen phosphate powder and the lanthanum nitrate powder to be coated on the surface of the sintered powder, calcining for 9h at 450 ℃, cooling, crushing, and sieving by a 300-mesh screen to obtain the middle-high nickel ternary cathode material powder.
Example 2
Firstly, mixing nickel cobalt manganese precursor Ni 0.6Co0.1Mn0.3(OH)2 and lithium carbonate according to Li/Me=1.02, and then adding lanthanum oxide with the mass of 3000ppm of the total mass of the nickel cobalt manganese precursor and a lithium source to mix to obtain a mixed material;
Step 2, raising the temperature of the mixed material to 450 ℃ at the speed of 2 ℃ per minute, preserving heat for 5 hours, raising the temperature to 720 ℃ at the speed of 2 ℃ per minute, preserving heat for 12 hours, completing sintering, cooling to room temperature, crushing, and sieving with a 300-mesh screen to obtain sintered powder;
and 3, placing the sintered powder, 3500ppm of lithium dihydrogen phosphate powder with the phosphorus content being the mass of the sintered powder and 3500ppm of lanthanum nitrate powder with the lanthanum content being the mass of the sintered powder into a planetary machine, mixing and stirring for 1h at the rotating speed of 800rpm, enabling the lithium dihydrogen phosphate powder and the lanthanum nitrate powder to be coated on the surface of the sintered powder, calcining at 300 ℃ for 12h, cooling, crushing, and sieving by a 300-mesh screen to obtain the middle-high nickel ternary cathode material powder.
Example 3
Firstly, mixing nickel cobalt manganese precursor Ni 0.6Co0.1Mn0.3(OH)2 and lithium carbonate according to Li/Me=1.06, and then adding lanthanum oxide with the mass of 3000ppm of the total mass of the nickel cobalt manganese precursor and a lithium source to mix to obtain a mixed material;
step 2, raising the temperature of the mixed material to 720 ℃ at the speed of 4 ℃ per minute, preserving heat for 1h, raising the temperature to 950 ℃ at the speed of 4 ℃ per minute, preserving heat for 8h, completing sintering, cooling to room temperature, crushing, and sieving with a 300-mesh screen to obtain sintered powder;
and 3, placing the sintered powder, 3500ppm of lithium dihydrogen phosphate powder with the phosphorus content being the mass of the sintered powder and 3500ppm of lanthanum nitrate powder with the lanthanum content being the mass of the sintered powder into a planetary machine, mixing and stirring for 1h at the rotating speed of 800rpm, enabling the lithium dihydrogen phosphate powder and the lanthanum nitrate powder to be coated on the surface of the sintered powder, calcining at 600 ℃ for 6h, cooling, crushing, and sieving by a 300-mesh screen to obtain the middle-high nickel ternary cathode material powder.
Example 4
Substantially the same as in example 1, except that the mass of phosphorus element in the phosphorus source powder was 1500ppm of the mass of the sintered powder, and the mass of lanthanum element in the lanthanum source powder was 1500ppm of the mass of the sintered powder.
Example 5
Substantially the same as in example 1, except that the mass of the phosphorus element in the phosphorus source powder was 5500ppm of the mass of the sintered powder, and the mass of the lanthanum element in the lanthanum source powder was 5500ppm of the mass of the sintered powder.
Example 6
Substantially the same as in example 1, except that the mass of phosphorus element in the phosphorus source powder was 1000ppm of the mass of the sintered powder, and the mass of lanthanum element in the lanthanum source powder was 1000ppm of the mass of the sintered powder.
Example 7
Substantially the same as in example 1, except that the mass of the phosphorus element in the phosphorus source powder was 6000ppm of the mass of the sintered powder, and the mass of the lanthanum element in the lanthanum source powder was 6000ppm of the mass of the sintered powder.
Example 8
Substantially the same as in example 1, except that the phosphorus source was sodium dihydrogen phosphate.
Example 9
Substantially the same as in example 1, except that the lanthanum source was lanthanum nitrate hexahydrate.
Example 10
Substantially the same as in example 1, except that the mass of lanthanum oxide in the step 1 was 1000ppm of the total mass of the nickel cobalt manganese precursor and the lithium source.
Example 11
Substantially the same as in example 1, except that the lanthanum oxide in step 1 was 5000ppm of the total mass of the nickel cobalt manganese precursor and the lithium source.
Example 12
Substantially the same as in example 1, except that the lanthanum oxide in step 1 was 500ppm of the total mass of the nickel cobalt manganese precursor and the lithium source.
Example 13
Substantially the same as in example 1, except that the mass of lanthanum oxide in the step 1 was 6000ppm of the total mass of the nickel cobalt manganese precursor and the lithium source.
Comparative example 1
Substantially the same as in example 1, except that the coating was performed without using a phosphorus source and a lanthanum source in the step 3.
Comparative example 2
Substantially the same as in example 1, except that only lithium dihydrogen phosphate having a phosphorus element mass of 3500ppm based on the mass of the sintered powder was added for calcination in the above-mentioned step 3.
Comparative example 3
Substantially the same as in example 1, except that only lanthanum nitrate having a lanthanum element mass of 3500ppm of the sintered powder mass was added for calcination in the above-mentioned step 3.
Comparative example 4
Substantially the same as in example 1, except that lithium carbonate was used instead of lithium dihydrogen phosphate of step 3.
Comparative example 5
Substantially the same as in example 1, except that yttrium nitrate was used instead of lanthanum nitrate in step 3.
Comparative example 6
Substantially the same as in example 1, except that lanthanum oxide was not added in the above-mentioned step 1.
Comparative example 7
Substantially the same as in example 1, except that the nickel cobalt manganese precursor in step 1 is Ni 0.4Co0.2Mn0.4(OH)2.
Comparative example 8
Substantially the same as comparative example 7, except that the coating was not performed using the phosphorus source and the lanthanum source in the step 3.
Performance test:
Titration test of residual lithium
10G of the sample (accurate to 0.01 g) was weighed into a beaker and 100mL of distilled water was added.
The clean magnetic rotor was placed in a beaker, sealed with a sealing film, and then placed on a magnetic stirrer to stir at a rate of 500r/min for 15min.
And (5) filtering the sample solution by adopting a vacuum suction filtration device after standing.
Accurately transferring 1 mL-10 mL of filtrate to be measured into a 100mL beaker by adopting a pipette with corresponding specification, adding 50mL of distilled water, and placing the filtrate on a potentiometric titrator.
Starting the automatic potentiometric titrator, adjusting the magnetic stirring speed of the automatic potentiometric titrator to ensure that the test solution does not generate bubbles, and titrating by taking the pH value as an ordinate and the consumption volume of the hydrochloric acid titrating solution as an abscissa. Volumes V1 and V2 consumed by the hydrochloric acid titration solutions corresponding to the electrode potential jump points EP1 and EP2 are recorded.
Calculating the content of Li 2CO3 and lithium hydroxide in the sample according to the formulas 1 and 2, and calculating the content of free lithium in the sample according to the formulas 3, 4 and 5:
formula 1: ;
Formula 2: ;
Formula 3: ;
Formula 4: ;
Formula 5: ;
Wherein:
W X -the mass fraction of Li 2CO3 in the sample in parts per million;
W Y, the mass fraction of lithium hydroxide in a sample is in parts per million (ppm);
w X —the mass fraction of lithium in Li 2CO3 in ppm in parts per million in the sample;
w Y -the mass fraction of lithium in the sample, in parts per million (ppm);
w Z -the total content of free lithium in the sample in parts per million ppm;
V a -the volume of distilled water used in stirring the leached sample in milliliters mL;
V b -distilled water of the stirred leaching sample is filtered and used for measuring volume, and the unit is milliliter mL;
V 1 -the volume of hydrochloric acid titration solution consumed when titrating to the potential jump point EP1, in milliliters mL;
V 2 -the volume of hydrochloric acid titration solution consumed when titrating to the potential jump point EP2, in milliliters mL;
m-the mass of the sample is weighed, and the unit is g;
C, titrating the molar concentration of the solution by hydrochloric acid, wherein the unit is mol/L;
73.88-molar mass of Li 2CO3 in grams per mole g/mol;
23.94-molar mass of lithium hydroxide in grams per mole g/mol;
0.188-the mass ratio of lithium in Li 2CO3;
0.290-mass ratio of lithium in lithium hydroxide.
And (3) discharging capacity, namely after the materials are assembled into an R2016 button cell, testing the R2016 button cell on a new Wei cell testing integrated cabinet, setting a constant temperature of 25 ℃ in an incubator, setting the charging cut-off voltage to be 4.45V, setting the discharging voltage to be 3.0V, and obtaining the initial-circle discharging capacity of 0.1C after the charging and discharging are finished according to the multiplying power of 0.1C.
And (3) circulating the retention rate for hundred weeks, namely after the materials are assembled into the R2016 button cell, testing the R2016 button cell on a new-wire cell testing integrated cabinet, setting the constant temperature of the incubator to be 25 ℃, setting the charging cut-off voltage to be 4.45V, setting the discharging cut-off voltage to be 3.0V, firstly setting the multiplying power of 0.1C for activation, and then setting the 1C for 100 weeks to obtain the circulating retention rate for hundred weeks.
The performance test is shown in table 1:
TABLE 1
| Group of | Residual lithium content ppm | 0.1C first-turn discharge capacity mAh/g | Cycle hundred week retention% |
| Example 1 | 1162 | 196.60 | 95.95 |
| Example 2 | 1205 | 195.10 | 94.12 |
| Example 3 | 1248 | 195.21 | 94.59 |
| Example 4 | 1583 | 194.64 | 93.91 |
| Example 5 | 1088 | 194.29 | 94.22 |
| Example 6 | 3309 | 190.37 | 85.31 |
| Example 7 | 997 | 190.21 | 88.45 |
| Example 8 | 1335 | 194.11 | 93.18 |
| Example 9 | 1348 | 193.62 | 93.53 |
| Example 10 | 1833 | 192.78 | 91.31 |
| Example 11 | 1797 | 192.35 | 90.73 |
| Example 12 | 2910 | 189.48 | 81.42 |
| Example 13 | 2886 | 189.51 | 83.15 |
| Comparative example 1 | 4602 | 188.60 | 50.74 |
| Comparative example 2 | 3688 | 190.12 | 67.15 |
| Comparative example 3 | 4071 | 189.33 | 68.93 |
| Comparative example 4 | 2649 | 190.14 | 82.34 |
| Comparative example 5 | 3136 | 189.82 | 80.95 |
| Comparative example 6 | 3851 | 189.35 | 66.37 |
| Comparative example 7 | 2984 | 190.26 | 64.28 |
| Comparative example 8 | 4354 | 187.66 | 51.78 |
Conclusion analysis:
1. The results of the performance tests performed by examples 1 and 4-7 are shown in Table 2:
TABLE 2
| Group of | Residual lithium content ppm | 0.1C first-turn discharge capacity mAh/g | Cycle hundred week retention% |
| Example 1 | 1162 | 196.60 | 95.95 |
| Example 4 | 1583 | 194.64 | 93.91 |
| Example 5 | 1088 | 194.29 | 94.22 |
| Example 6 | 3309 | 190.37 | 85.31 |
| Example 7 | 997 | 190.21 | 88.45 |
As can be seen from the data in table 2, when the addition amount of the phosphorus source and the lanthanum source is 3500ppm of the mass of the sintered powder, the performance of the prepared ternary cathode material is best, and as the addition amount increases, more free lithium is combined in the coating process, so that the residual lithium amount is continuously reduced, but too much phosphorus source and lanthanum source are coated, the formed coating layer is too thick, the migration of lithium ions of the cathode material is affected, the performance is reduced, and as the addition amount decreases, the purpose of reducing residual lithium is not achieved, the coating is imperfect, and the performance of the cathode material is reduced.
2. The results of the performance tests of example 1, example 8 and comparative example 4 are shown in Table 3:
TABLE 3 Table 3
| Group of | Residual lithium content ppm | 0.1C first-turn discharge capacity mAh/g | Cycle hundred week retention% |
| Example 1 | 1162 | 196.60 | 95.95 |
| Example 8 | 1335 | 194.11 | 93.18 |
| Example 9 | 1348 | 193.62 | 93.53 |
| Comparative example 4 | 2649 | 190.14 | 82.34 |
| Comparative example 5 | 3136 | 189.82 | 80.95 |
It is understood from the data of Table 3 that, when lithium dihydrogen phosphate or lanthanum nitrate is used in place of lithium dihydrogen phosphate or yttrium nitrate in example 1, respectively, the bond effect between the carbonate and the lanthanum ion is not achieved, the carbonate structure is unstable, decomposition easily occurs under high temperature and acidic conditions, and a stable coating layer is formed after bonding with lanthanum element because the phosphate has a stronger coordination ability than that of the carbonate, and yttrium ion having a smaller ionic radius than that of lanthanum ion is replaced, and the bonding ability between yttrium ion and phosphate is stronger because the electronegativity of yttrium element is higher than that of lanthanum element, so that the coating layer formed by bonding between yttrium ion and phosphate should have a higher stability than that formed by lanthanum ion and phosphate, and the performance is better, but from the data of comparative example 5, the performance enhancing effect of yttrium nitrate is inferior to that of lanthanum nitrate.
3. The results of the performance tests performed by examples 1 and 10-13 are shown in Table 4:
TABLE 4 Table 4
| Group of | Residual lithium content ppm | 0.1C first-turn discharge capacity mAh/g | Cycle hundred week retention% |
| Example 1 | 1162 | 196.60 | 95.95 |
| Example 10 | 1833 | 192.78 | 91.31 |
| Example 11 | 1797 | 192.35 | 90.73 |
| Example 12 | 2910 | 189.48 | 81.42 |
| Example 13 | 2886 | 189.51 | 83.15 |
As can be seen from the data in table 4, when the dopant content is less than 1000ppm, the excessively low dopant element content cannot effectively stabilize the bulk structure of the material, and cannot form enough LiLaO 2 layers on the surfaces of the primary particles and the secondary particles of the material, which affects the subsequent coating effect, and thus the improvement of the material performance is limited.
When the content of the doping agent is higher than 5000ppm, besides doping a part of doping elements into the superficial structure of the material and forming a preliminary LiLaO 2 coating layer, a large amount of residual oxide remains on the surface of the material, and the residual oxide is an electrochemical inert substance, so that the performance of the material is affected.
4. The results of the performance tests of example 1, comparative examples 1-3 and comparative example 6 are shown in Table 5:
TABLE 5
| Group of | Residual lithium content ppm | 0.1C first-turn discharge capacity mAh/g | Cycle hundred week retention% |
| Example 1 | 1162 | 196.60 | 95.95 |
| Comparative example 1 | 4602 | 188.60 | 50.74 |
| Comparative example 2 | 3688 | 190.12 | 67.15 |
| Comparative example 3 | 4071 | 189.33 | 68.93 |
| Comparative example 6 | 3851 | 189.35 | 66.37 |
It is understood from the data in Table 5 that, in contrast to the coating of the comparative example 1 without using the phosphorus source and the lanthanum source, the improvement of the performance of the positive electrode material is not remarkable when the lanthanum source and the phosphorus source are used alone or without adding lanthanum oxide, whereas in the comparative example 1, when the lanthanum source, the phosphorus source and lanthanum oxide are used together, the lanthanum lithium oxide layer formed by lanthanum oxide provides a basis for the coating of the phosphorus source and the lanthanum source, so that the lanthanum source and the lanthanum source are coated on the positive electrode material core more firmly, and the combination of the lanthanum source and the lanthanum source can improve the absorption of free lithium, thereby further reducing the content of residual lithium.
5. The results of the performance tests of example 1 and comparative example 1, comparative examples 7 to 8 are shown in Table 6:
TABLE 6
| Group of | Residual lithium content ppm | 0.1C first-turn discharge capacity mAh/g | Cycle hundred week retention% |
| Example 1 | 1162 | 196.60 | 95.95 |
| Comparative example 1 | 4602 | 188.60 | 50.74 |
| Comparative example 7 | 2984 | 190.26 | 64.28 |
| Comparative example 8 | 4354 | 187.66 | 51.78 |
As can be seen from the data in table 6, when the same doping and coating process as in example 1 is used for the low-nickel ternary positive electrode material, there is a significant difference in the performance improvement effect of the positive electrode material, and thus, the doping and coating process of the present application is not suitable for the low-nickel ternary positive electrode material.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103456944A (en) * | 2013-09-04 | 2013-12-18 | 中国海洋石油总公司 | Modifying method of ternary anode material |
| CN105958054A (en) * | 2016-06-23 | 2016-09-21 | 中南大学 | Method for lanthanum phosphate coated lithium ion battery cathode material nickel cobalt lithium manganate |
| CN108134067A (en) * | 2017-12-25 | 2018-06-08 | 北京理工大学 | Adulterate La in a kind of surface layer3+NCM tertiary cathode materials preparation method |
| CN108878821A (en) * | 2018-06-19 | 2018-11-23 | 合肥国轩高科动力能源有限公司 | High-nickel ternary positive electrode material with lanthanum oxide coated surface and preparation method thereof |
| CN112002902A (en) * | 2020-08-12 | 2020-11-27 | 中南大学 | A kind of double modified lithium ion battery ternary positive electrode material and preparation method thereof |
| CN112002898A (en) * | 2020-08-12 | 2020-11-27 | 中南大学 | Titanium lanthanum lithium phosphate coated and modified ternary cathode material and preparation method thereof |
| CN115353155A (en) * | 2022-08-22 | 2022-11-18 | 长沙理工大学 | Preparation method of low-cobalt lithium-rich manganese-based lithium-ion battery cathode material co-modified by phosphorus and lanthanum |
| US20230322557A1 (en) * | 2022-04-01 | 2023-10-12 | Phylion Battery Co., Ltd. | Method for preparing lithium manganese iron phosphate, cathode material, and lithium-ion battery |
| CN117293399A (en) * | 2023-09-27 | 2023-12-26 | 苏州大学 | Integrated battery and preparation method thereof |
| CN117430171A (en) * | 2023-10-24 | 2024-01-23 | 荆门市格林美新材料有限公司 | Nickel-cobalt-manganese positive electrode precursor material doped with anions and cations as well as preparation method and application thereof |
-
2024
- 2024-11-08 CN CN202411586270.5A patent/CN119118222B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103456944A (en) * | 2013-09-04 | 2013-12-18 | 中国海洋石油总公司 | Modifying method of ternary anode material |
| CN105958054A (en) * | 2016-06-23 | 2016-09-21 | 中南大学 | Method for lanthanum phosphate coated lithium ion battery cathode material nickel cobalt lithium manganate |
| CN108134067A (en) * | 2017-12-25 | 2018-06-08 | 北京理工大学 | Adulterate La in a kind of surface layer3+NCM tertiary cathode materials preparation method |
| CN108878821A (en) * | 2018-06-19 | 2018-11-23 | 合肥国轩高科动力能源有限公司 | High-nickel ternary positive electrode material with lanthanum oxide coated surface and preparation method thereof |
| CN112002902A (en) * | 2020-08-12 | 2020-11-27 | 中南大学 | A kind of double modified lithium ion battery ternary positive electrode material and preparation method thereof |
| CN112002898A (en) * | 2020-08-12 | 2020-11-27 | 中南大学 | Titanium lanthanum lithium phosphate coated and modified ternary cathode material and preparation method thereof |
| US20230322557A1 (en) * | 2022-04-01 | 2023-10-12 | Phylion Battery Co., Ltd. | Method for preparing lithium manganese iron phosphate, cathode material, and lithium-ion battery |
| CN115353155A (en) * | 2022-08-22 | 2022-11-18 | 长沙理工大学 | Preparation method of low-cobalt lithium-rich manganese-based lithium-ion battery cathode material co-modified by phosphorus and lanthanum |
| CN117293399A (en) * | 2023-09-27 | 2023-12-26 | 苏州大学 | Integrated battery and preparation method thereof |
| CN117430171A (en) * | 2023-10-24 | 2024-01-23 | 荆门市格林美新材料有限公司 | Nickel-cobalt-manganese positive electrode precursor material doped with anions and cations as well as preparation method and application thereof |
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