CN111987313A - Scandium-titanium-lithium phosphate coated layered cobalt-free high-nickel cathode material and preparation method thereof - Google Patents

Scandium-titanium-lithium phosphate coated layered cobalt-free high-nickel cathode material and preparation method thereof Download PDF

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CN111987313A
CN111987313A CN202010866668.XA CN202010866668A CN111987313A CN 111987313 A CN111987313 A CN 111987313A CN 202010866668 A CN202010866668 A CN 202010866668A CN 111987313 A CN111987313 A CN 111987313A
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cobalt
free high
cathode material
lithium
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范鑫铭
胡国荣
姜怀
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Central South University
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Abstract

A scandium-titanium-lithium phosphate coated layered cobalt-free high-nickel cathode material and a preparation method thereof. The chemical formula of the cathode material is LiNixM1‑xO2·LiySczTin(PO4)3Wherein M is doping metal (Al, Mg, Mn, Ti, etc.), x, y, z, n, w are moleNumber, x is not less than 0.6<1，1<y≤1.8，0<z≤0.8，1<n≤1.9，LiySczTin(PO4)3The active lithium conducting layer is formed, and the thickness of the coating layer is 3-20 nm. The preparation method comprises the following steps: firstly, synthesizing a cobalt-free high-nickel precursor by adopting coprecipitation; mixing and sintering the cobalt-free high-nickel precursor with a lithium source to obtain the cobalt-free high-nickel anode material LiNixM1‑xO2Wherein M is doped metal (Al, Mg, Mn, Ti and other elements); then, scandium source, titanium source and cobalt-free high-nickel cathode material LiNixM1‑xO2Wherein M is doped metal (Al, Mg, Mn, Ti and other elements) which is uniformly dispersed in the organic solvent; stirring and evaporating most of the solvent to obtain black slurry; vacuum drying and grinding the black slurry to obtain pre-sintered powder; and sintering the mixture in an oxygen atmosphere to obtain the modified cobalt-free high-nickel cathode material. The material prepared by the invention has good cycling stability and excellent rate performance; the preparation method is simple and easy to operate, is suitable for large-scale industrial production, and has low cost.

Description

Scandium-titanium-lithium phosphate coated layered cobalt-free high-nickel cathode material and preparation method thereof
Technical Field
The invention relates to the field of battery materials, in particular to a lithium-conducting compound coated cobalt-free high-nickel positive electrode material and a preparation method thereof.
Background
Ternary positive electrode materials have been favored for high energy density lithium ion batteries, with nickel, cobalt, manganese and other elements playing their roles. The cobalt element is not only an active material, but also can effectively inhibit mixed arrangement of cations (Li/Ni) and stabilize the structure of the material, so that the cobalt-containing ternary material generally has good deep discharge characteristics and good rate performance. However, cobalt is highly disproportionately distributed throughout the world, and the factors of geopolitics and low reserves lead to a dramatic rise in cobalt prices, even exceeding $ 90000 per ton for one degree. With the gradual popularization of global electric transportation equipment, the reduction of cobalt in the use of positive electrode materials is becoming common knowledge in the industry, and in recent years, NMC (LiNi) has become common in the field1-x-yMnxCoyO2) The ternary material is undergoing the evolution process of NMC-532 → NMC-622 → NMC-721 → NMC-811, and the research of cobalt-free material is more concerned.
However, the cobalt-free high-nickel cathode material is usually mainly LiNiO2, and is doped with Mn, Al, Mg, Ti and other elements to form a high-nickel ternary material. However, the cobalt-free material is unsatisfactory in the aspects of rate cycle performance, element component regulation and control and the like, particularly, adverse effects are brought to the cycle performance and the thermal stability of the battery along with the increase of the nickel content, and the long cycle of the soft package battery meeting the commercial application standard is rarely reported, so that the application of the cobalt-free high-nickel cathode material is severely limited.
Therefore, aiming at the defects of the prior art, it is particularly important to provide a cobalt-free high-nickel positive electrode material of a lithium ion battery and a preparation method thereof, wherein the cobalt-free high-nickel positive electrode material can simultaneously improve the cycle and rate performance and the thermal stability performance of the cobalt-free high-nickel positive electrode material.
Disclosure of Invention
The invention aims to provide a scandium-titanium-lithium phosphate-coated layered cobalt-free high-nickel cathode material. The battery assembled by the anode material has good cycle performance and rate capability.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of the scandium-titanium-lithium phosphate coated layered cobalt-free high-nickel cathode material. The preparation method is simple and reasonable, and the cost is low.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a metal compound coated ternary anode material and a preparation method thereof. The chemical formula of the cathode material is LiNixM1-xO2·LiySczTin(PO4)3Wherein M is doping metal (Al, Mg, Mn, Ti, etc.), x, y, z, n, w are mole numbers, x is more than or equal to 0.6<1，1<y≤1.8，0<z≤0.8，1<n is less than or equal to 1.9, the particle size of the material is about 2-5 mu m, and the surface layer is provided with uniform LiySczTin(PO4)3A coating layer with a thickness of 3-20 nm.
The technical scheme adopted for further solving the technical problems is as follows:
a scandium-titanium-lithium phosphate coated layered cobalt-free high-nickel cathode material and a preparation method thereof are prepared by the following steps:
(1) in terms of molar ratio, firstly, 3-10 moL/L of NiSO4·6H2O、MSO4·H2O (M is doped metal (Al, Mg, Mn, Ti and other elements) is uniformly mixed, and simultaneously, 5-7 mol/L of NaOH solution and NH serving as a coordination agent are added3·H2And respectively adding the O solution (4-7 mol/L) into the reaction tanks. Adjusting the pH value to 10.5-11.0, and the concentration of ammonia water to 1.5-2 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor NixM1-x(OH)2。
(2) In terms of mole ratios, as per Li: weighing a lithium source according to the proportion of (Ni + M) ═ 1-1.2: 1, and mixing the precursor material Ni prepared in the step (1)xM1-x(OH)2Mixing the mixture with a lithium source uniformly, burning the mixture for 5 to 8 hours at the temperature of 400 to 600 ℃, and burning the mixture for 10 to 14 hours at the temperature of 800 to 1000 ℃ to obtain a cobalt-free high-nickel cathode material NixM1-x(OH)2。
(3) Uniformly dispersing a scandium source and a titanium source into an organic solvent according to a molar ratio, and slowly adding the cobalt-free high-nickel cathode material LiNi prepared in the step (2) into the organic solventxM1-xO2Stirring until the mixture is uniformly mixed, evaporating most of the solvent, and drying the obtained slurry in vacuum to obtain a presintered substance.
(4) Grinding the pre-sintered substance obtained in the step (3) according to a molar ratio and sintering the pre-sintered substance in an oxygen atmosphere to obtain the LiySczTin(PO4)3A coated cobalt-free high nickel positive electrode material;
wherein x is more than or equal to 0.6 and less than 1, y is more than 1 and less than or equal to 1.8, z is more than 0 and less than or equal to 0.8, and n is more than 1 and less than or equal to 1.9.
Preferably, in the step (3), the lithium source is one or more selected from lithium hydroxide, lithium carbonate and lithium nitrate.
Preferably, in the step (3), the cerium source is scandium nitrate or titanium nitrate.
Preferably, in the step (3), the solvent is one or more of methanol, ethanol and propanol
Preferably, in the step (3), the cobalt-free high nickel cathode material LiNixM1-xO2The solid-liquid ratio of the organic solvent to the organic solvent is 1-4 g-15 mL, and more preferably, the solid-liquid ratio is 2g:7 mL.
Preferably, in the step (3), the vacuum degree is-0.1 MPa.
Preferably, in the step (3), the temperature of vacuum drying is 60-120 ℃.
Preferably, in the step (3), the vacuum drying time is 8-14 h.
Preferably, in the step (3), the temperature of the evaporated solvent is 60-85 ℃, and the time is 2-8 hours; more preferably, the temperature of the evaporation solvent is 75-80 ℃ and the time is 3-4 h.
Preferably, in the step (4), the grinding time is 5-10 min.
Preferably, in the step (4), the sintering temperature is 600-900 ℃ and the time is 10-14 h.
The invention has the beneficial effects that:
(1) the scandium-titanium-lithium phosphate-coated layered cobalt-free high-nickel cathode material and the preparation method thereof are obtained through effective and feasible surface modification. The cobalt-free high-nickel cathode material has serious capacity reduction, and can play a great potential through the formed lithium-conducting coating layer, thereby improving the electrochemical performance of the high-nickel layered oxide. The lithium-conducting coating layer can resist corrosion of HF, and can rapidly transmit lithium ions to the surface of the cobalt-free high-nickel material, so that the lithium ion transmission rate on the surface of the material is remarkably improved, and the rate capability of the material is improved. Experimental data show that the coating layer can greatly improve the rate capability and the cycle performance of the material. In addition, the preparation method is simple, low in cost, simple to operate and suitable for industrial production.
(2) The cobalt-free high-nickel cathode material is of a single crystal structure and is uniformly coated with Li with the thickness of 3-20 nmySczTin(PO4)3The coating layer is a positive electrode material which has excellent rate capability and cycle performance, and tests show that the battery assembled by the positive electrode material has the first discharge capacity of 230.5mAh/g within the voltage range of 2.75-4.6V and the 1C rate, the capacity of 185.1mAh/g and the capacity retention rate of 80.3 percent after being cycled for 200 circles at 1C.
Drawings
FIG. 1 is an SEM image of a scandium-titanium-lithium phosphate-coated cobalt-free layered nickel-high-nickel cathode material obtained in example 1 of the present invention;
FIG. 2 is an XRD (X-ray diffraction) pattern of the scandium-titanium-lithium phosphate-coated layered cobalt-free high-nickel cathode material obtained in example 1 of the invention;
FIG. 3 is an SEM image of a cobalt-free layered nickel cathode material obtained in comparative example 1 of the present invention;
FIG. 4 is an XRD pattern of the cobalt-free laminated cathode material of the present invention obtained in comparative example 1.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Example 1
The preparation method of the scandium-titanium-lithium phosphate-coated layered cobalt-free high-nickel cathode material is described by combining specific examples, and is specifically prepared by the following steps:
(1) in terms of molar ratio, 3moL/L of 8.8moL of NiSO4·6H2O, 1.2moL MnSO4·H2O (Ni: Mn: 88:12) was uniformly mixed, and at the same time, a NaOH solution (5mol/L) and NH as a complexing agent were added3·H2O solution (6mol/L) was also added to the reaction tank separately. The pH was adjusted to 10.5 and the ammonia concentration was 1.5 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor Ni0.88Mn0.12(OH)2。
(2) In terms of mole ratios, as per Li: weighing 1.05mol of lithium nitrate according to the proportion of (Ni + Mn) ═ 1.05:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.88Mn0.12(OH)2Evenly mixing with lithium nitrate, burning for 6h at 500 ℃ and burning for 14h at 810 ℃ to obtain the ternary cathode material LiNi0.88Mn0.12O2。
(3) Uniformly dispersing 0.0012mol of lithium hydroxide, 0.00002mol of titanium nitrate and 0.0018mol of scandium nitrate into absolute ethyl alcohol in terms of molar ratio, and slowly adding 0.1mol of the cathode material LiNi prepared in the step (2) into the absolute ethyl alcohol0.88Mn0.12O2The solid-to-liquid ratio was adjusted to 1g:7 mL. Stirring until the mixture is uniformly mixed and evaporating for 3 hours at 80 ℃ to obtain black slurry; and (3) drying the black slurry at 100 ℃ for 10h under the vacuum degree of-0.1 MPa to obtain a presintered substance.
(4) Grinding the pre-sintered substance obtained in the step (3) for 5min in molar ratio, and sintering at 700 ℃ for 11h in an oxygen atmosphere to obtain the LiNi0.88Mn0.12O2·0.01Li1.2Sc0.2Ti1.8(PO4)3A positive electrode material;
the scandium-titanium-lithium phosphate coated layered cobalt-free high-nickel cathode material obtained in the embodiment is characterizedAnd detection consisting of LiNi0.88Mn0.12O2·0.01Li1.2Sc0.2Ti1.8(PO4)3The scanning image of the high-nickel cathode material is shown in figure 1, the particle size of the high-nickel cathode material is 2-5 mu m, and a coating layer with uniform thickness is arranged on the surface of the high-nickel cathode material. XRD results of the high-nickel cathode material are shown in figure 2, and LiNi exists0.88Mn0.12O2And Li1.2Sc0.2Ti1.8(PO4)3Two phases.
The button cell of CR2025 was assembled from the lithium titanium scandium phosphate coated cobalt-free high nickel positive electrode material obtained in this example. The battery is discharged for the first time within the voltage range of 2.75-4.6V and under the multiplying power of 1C, the gram capacity reaches 230.5mAh/g, the battery is circulated for 200 circles under the multiplying power of 1C, the capacity is 185.1mAh/g, and the capacity retention rate reaches 80.3%.
Example 2
The preparation method of the scandium-titanium-lithium phosphate-coated layered cobalt-free high-nickel cathode material is described by combining specific examples, and is specifically prepared by the following steps:
(1) in terms of molar ratio, 3moL/L of 8.8moL of NiSO4·6H2O, 1.2moL of MgSO 24·H2O (Ni: Mg: 88:12) was uniformly mixed, and at the same time, a NaOH solution (5mol/L) and NH as a complexing agent were added3·H2O solution (6mol/L) was also added to the reaction tank separately. The pH was adjusted to 10.5 and the ammonia concentration was 1.5 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor Ni0.88Mg0.12(OH)2。
(2) In terms of mole ratios, as per Li: weighing 1.05mol of lithium nitrate according to the proportion of (Ni + Mg) ═ 1.05:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.88Mg0.12(OH)2Evenly mixing with lithium nitrate, burning for 6h at 500 ℃ and burning for 14h at 810 ℃ to obtain the ternary cathode material LiNi0.88Mg0.12O2。
(3) Uniformly dispersing 0.0012mol of lithium hydroxide, 0.00002mol of titanium nitrate and 0.0018mol of scandium nitrate into absolute ethyl alcohol in a molar ratio, and slowly adding the prepared solution obtained in the step (2) into the absolute ethyl alcohol0.1mol of positive electrode material LiNi0.88Mg0.12O2The solid-to-liquid ratio was adjusted to 1g:7 mL. Stirring until the mixture is uniformly mixed and evaporating for 3 hours at 80 ℃ to obtain black slurry; and (3) drying the black slurry at 100 ℃ for 10h under the vacuum degree of-0.1 MPa to obtain a presintered substance.
(4) Grinding the pre-sintered substance obtained in the step (3) for 5min in molar ratio, and sintering at 700 ℃ for 11h in an oxygen atmosphere to obtain the LiNi0.88Mg0.12O2·0.01Li1.2Sc0.2Ti1.8(PO4)3A positive electrode material;
the scandium-titanium-lithium phosphate-coated layered cobalt-free high-nickel cathode material obtained in the embodiment is characterized and detected, and the composition of the scandium-titanium-lithium phosphate-coated layered cobalt-free high-nickel cathode material is LiNi0.88Mg0.12O2·0.01Li1.2Sc0.2Ti1.8(PO4)3The scanning image of the high-nickel cathode material is shown in figure 1, the particle size of the high-nickel cathode material is 2-5 mu m, and a coating layer with uniform thickness is arranged on the surface of the high-nickel cathode material. XRD results of the high-nickel cathode material are shown in figure 2, and LiNi exists0.88Mg0.12O2And Li1.2Sc0.2Ti1.8(PO4)3Two phases.
The button cell of CR2025 was assembled from the lithium titanium scandium phosphate coated cobalt-free high nickel positive electrode material obtained in this example. The first discharge gram capacity of the battery reaches 212.5mAh/g within the voltage range of 2.75-4.6V and under the multiplying power of 1C, the capacity is 165.3mAh/g after 200 cycles under the multiplying power of 1C, and the capacity retention rate reaches 78%.
Example 3
(1) In terms of molar ratio, firstly 5moL/L of 9moL of NiSO4·6H2O, 0.1moL MnSO4·H2O (Ni: Co: Mn: 90:10) was uniformly mixed, and at the same time, a NaOH solution (5.2mol/L) and NH as a complexing agent were added3·H2O solution (5.5mol/L) was also added to the reaction tank separately. The pH was adjusted to 10.5 and the ammonia concentration was 1.8 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor Ni0.9Mn0.1(OH)2。
(2) In terms of mole ratios, as per Li: (Ni + Mn) ═ 1.2:1 ratioExample 0.6mol of lithium carbonate was weighed, and 1mol of Ni as a precursor material prepared in step (1) was added0.88Co0.06Mn0.06(OH)2Uniformly mixing with lithium carbonate, burning for 6h at 600 ℃ and burning for 11h at 830 ℃ to obtain the ternary cathode material LiNi0.9Mn0.1O2。
(3) Uniformly dispersing 0.0012mol of lithium hydroxide, 0.00002mol of titanium nitrate and 0.0018mol of scandium nitrate into propanol in a molar ratio, and slowly adding 0.1mol of the positive electrode material LiNi prepared in the step (2) into the propanol0.9Mn0.1O2The solid-to-liquid ratio was adjusted to 1g:7 mL. Stirring until the mixture is uniformly mixed, and evaporating at 78 ℃ for 3.6h to obtain black slurry; and (3) drying the black slurry at 115 ℃ for 8.5h under the vacuum degree of-0.1 MPa to obtain a presintered substance.
(4) Grinding the pre-sintered substance obtained in the step (3) for 8min, and sintering at 710 ℃ for 10.5h in an oxygen atmosphere to obtain the LiNi0.9Mn0.1O2·0.01Li1.2Sc0.2Ti1.8(PO4)3A ternary positive electrode material;
the scandium-titanium-lithium phosphate coated ternary cathode material obtained in the embodiment was characterized and detected, and its composition was LiNi0.9Mn0.1O2·0.01Li1.2Sc0.2Ti1.8(PO4)3The particle size of the high-nickel anode material is 2-5 mu m, a coating layer with uniform thickness exists on the surface, and LiNi exists0.9Mn0.1O2And Li1.2Sc0.2Ti1.8(PO4)3Two phases.
The high-nickel cathode material obtained in the embodiment is adopted to assemble a button cell of CR 2025. When the battery is used in a voltage range of 2.75-4.3V and at a multiplying power of 1C, the first discharge gram capacity reaches 219.2mAh/g, the capacity is still 165.6mAh/g after 200 cycles at 1C, and the capacity retention rate reaches 75.58%.
Comparative example 1
(1) Firstly, 4moL/L of 8.8moL of NiSO4·6H2O, 1.2moL MnSO4·H2O (Ni: Co: Mn: 88:12) was uniformly mixed with NaOH solution (5.6mol/L)NH of complexing agent3·H2O solution (6.5mol/L) was also added to the reaction tank separately. The pH was adjusted to 10.8 and the ammonia concentration was 1.7 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor Ni0.88Mn0.12(OH)2。
(2) In terms of mole ratios, as per Li: weighing 1.1mol of lithium hydroxide according to the proportion of (Ni + Mn) ═ 1.1:1, and mixing 1mol of precursor material Ni prepared in the step (1)0.88Mn0.12(OH)2Mixing with lithium hydroxide uniformly, burning at 550 ℃ for 7h, and burning at 820 ℃ for 13h to obtain the ternary cathode material LiNi0.88Mn0.12O2。
(3) Grinding the pre-sintered substance obtained in the step (2) for 7min, and sintering at 680 ℃ for 12h in an oxygen atmosphere to obtain the LiNi0.88Mn0.12O2A cobalt-free high-nickel layered cathode material;
the cobalt-free high-nickel layered material obtained in this example was characterized and tested, and its composition was LiNi0.88Mn0.12O2The particle size of the high-nickel cathode material is 2-5 mu m, the surface is smooth and has no coating layer, and a scanning photo is shown in figure 3. Compared with the material coated with lithium scandium titanium phosphate, the diffraction peak (about 19 ℃) of the (003) crystal plane in XRD (as shown in figure 4) is stronger, which indicates that the material without the coating layer exposes more crystal planes of the cobalt-free high-nickel ternary material.
The high-nickel cathode material obtained in the embodiment is adopted to assemble a button cell of CR 2025. When the battery is used in a voltage range of 2.75-4.6V and at a multiplying power of 1C, the first discharge gram capacity reaches 190.0mAh/g, the battery is circulated for 200 circles at 1C, the capacity is 117.8mAh/g, and the capacity retention rate reaches 62% (specifically, see a curve shown in FIG. 4).
In conclusion, the cycle and rate performance of the ternary cathode material coated by the metal compound are greatly improved.

Claims (4)

1. A scandium-titanium-lithium phosphate coated layered cobalt-free high-nickel cathode material and a preparation method thereof. The chemical formula of the cathode material is LiNixM1-xO2·LiySczTin(PO4)3Wherein M is doping metal (Al, Mg, Mn, Ti, etc.), x, y, z, n, w are mole numbers, x is more than or equal to 0.6<1，1<y≤1.8，0<z≤0.8，1<n≤1.9。
2. The positive electrode material according to claim 1, wherein the positive electrode material is a single crystal particle having a particle size of about 2 to 8 μm, and the surface layer forms a uniform double coating layer having a thickness of 3 to 20 nm.
3. A scandium-titanium-lithium phosphate coated layered cobalt-free high-nickel cathode material and a preparation method thereof are prepared by the following steps:
(1) in terms of molar ratio, firstly, 3-10 moL/L of NiSO4·6H2O、MSO4·H2O (M is doped metal (Al, Mg, Mn, Ti and other elements) is uniformly mixed, and simultaneously, 5-7 mol/L of NaOH solution and NH serving as a coordination agent are added3·H2And respectively adding the O solution (4-7 mol/L) into the reaction tanks. Adjusting the pH value to 10.5-11.0, and the concentration of ammonia water to 1.5-2 mol/L. Carrying out coprecipitation reaction, washing and drying by pure water to obtain precursor NixM1-x(OH)2。
(2) In terms of mole ratios, as per Li: weighing a lithium source according to the proportion of (Ni + M) ═ 1-1.2: 1, and mixing the precursor material Ni prepared in the step (1)xM1-x(OH)2Mixing the mixture with a lithium source uniformly, burning the mixture for 5 to 8 hours at the temperature of 400 to 600 ℃, and burning the mixture for 10 to 14 hours at the temperature of 800 to 1000 ℃ to obtain a cobalt-free high-nickel cathode material NixM1-x(OH)2。
(3) Uniformly dispersing a scandium source and a titanium source into an organic solvent according to a molar ratio, and slowly adding the cobalt-free high-nickel cathode material LiNi prepared in the step (2) into the organic solventxM1-xO2Stirring until the mixture is uniformly mixed, evaporating most of the solvent, and drying the obtained slurry in vacuum to obtain a presintered substance.
(4) Grinding the pre-sintered substance obtained in the step (3) according to a molar ratio and sintering the pre-sintered substance in an oxygen atmosphere to obtain the LiySczTin(PO4)3A coated cobalt-free high nickel positive electrode material;
wherein x is more than or equal to 0.6 and less than 1, y is more than 1 and less than or equal to 1.8, z is more than 0 and less than or equal to 0.8, and n is more than 1 and less than or equal to 1.9.
4. The lithium-conducting scandium-titanium-lithium phosphate-coated cobalt-free high-nickel cathode material and the preparation method thereof according to claim 3, wherein in the step (3), the lithium source is selected from one or more of lithium hydroxide, lithium carbonate and lithium nitrate; the scandium source and the titanium source are scandium nitrate and titanium nitrate respectively; the solvent is one or more of methanol, ethanol and propanol; the positive electrode material LiNixM1-xO2The solid-liquid ratio of the organic solvent to the organic solvent is 1-4 g-15 mL, and more preferably, the solid-liquid ratio is 2g:7 mL; the vacuum degree of vacuum drying is-0.1 MPa, the temperature is 60-120 ℃, and the time is 8-14 h; the temperature of the evaporating solvent is 60-85 ℃, and the time is 2-8 h; more preferably, the temperature of the evaporation solvent is 75-80 ℃ and the time is 3-4 h. In the step (4), the grinding time is 5-10 min, the sintering temperature is 600-900 ℃, and the sintering time is 10-14 h.
CN202010866668.XA 2020-08-26 2020-08-26 Scandium-titanium-lithium phosphate coated layered cobalt-free high-nickel cathode material and preparation method thereof Pending CN111987313A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113363475A (en) * 2021-03-23 2021-09-07 万向一二三股份公司 Preparation method of cobalt-free high-nickel magnesium-doped layered positive electrode material
CN113517424A (en) * 2021-04-27 2021-10-19 湖南杉杉能源科技股份有限公司 Cobalt-free positive electrode material of high-voltage lithium ion battery and preparation method thereof
CN114335548A (en) * 2022-03-08 2022-04-12 宜宾锂宝新材料有限公司 Modified ternary positive electrode material and coating modification method thereof
CN114551839A (en) * 2022-02-25 2022-05-27 中南大学 Pre-lithiation of single crystal type cobalt-free high-nickel positive electrode material and preparation method thereof
CN114583168A (en) * 2020-12-01 2022-06-03 丰田自动车株式会社 Coated positive electrode active material, method for producing coated positive electrode active material, and all-solid-state battery
CN114784229A (en) * 2022-03-18 2022-07-22 蜂巢能源科技股份有限公司 Cobalt-free positive electrode material and preparation method and application thereof
CN114975983A (en) * 2022-05-06 2022-08-30 四川新锂想能源科技有限责任公司 High-nickel low-cobalt material, preparation method thereof and battery anode
CN115417461A (en) * 2022-08-30 2022-12-02 清华大学深圳国际研究生院 Cobalt-free high-nickel cathode material and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107591529A (en) * 2017-10-10 2018-01-16 中南大学 A kind of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof
CN109119621A (en) * 2018-09-11 2019-01-01 乳源东阳光磁性材料有限公司 Lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material and preparation method thereof
CN109879331A (en) * 2019-03-04 2019-06-14 浙江众泰汽车制造有限公司 The nickelic tertiary cathode material and preparation method of a kind of fast-ionic conductor cladding and its lithium ion battery being prepared
CN110112383A (en) * 2019-04-17 2019-08-09 湖北锂诺新能源科技有限公司 The nickelic tertiary cathode material and preparation method thereof of titanium phosphate aluminium lithium cladding

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107591529A (en) * 2017-10-10 2018-01-16 中南大学 A kind of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof
CN109119621A (en) * 2018-09-11 2019-01-01 乳源东阳光磁性材料有限公司 Lithium lanthanum titanate-lithium titanate coated nickel cobalt lithium aluminate anode material and preparation method thereof
CN109879331A (en) * 2019-03-04 2019-06-14 浙江众泰汽车制造有限公司 The nickelic tertiary cathode material and preparation method of a kind of fast-ionic conductor cladding and its lithium ion battery being prepared
CN110112383A (en) * 2019-04-17 2019-08-09 湖北锂诺新能源科技有限公司 The nickelic tertiary cathode material and preparation method thereof of titanium phosphate aluminium lithium cladding

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114583168A (en) * 2020-12-01 2022-06-03 丰田自动车株式会社 Coated positive electrode active material, method for producing coated positive electrode active material, and all-solid-state battery
US11990619B2 (en) 2020-12-01 2024-05-21 Toyota Jidosha Kabushiki Kaisha Coated cathode active material, method for producing coated cathode active material, and all solid state battery
EP4009401A1 (en) * 2020-12-01 2022-06-08 Toyota Jidosha Kabushiki Kaisha Coated cathode active material, method for producing coated cathode active material, and all solid state battery
CN113363475B (en) * 2021-03-23 2022-05-13 万向一二三股份公司 Preparation method of cobalt-free high-nickel magnesium-doped layered positive electrode material
CN113363475A (en) * 2021-03-23 2021-09-07 万向一二三股份公司 Preparation method of cobalt-free high-nickel magnesium-doped layered positive electrode material
CN113517424A (en) * 2021-04-27 2021-10-19 湖南杉杉能源科技股份有限公司 Cobalt-free positive electrode material of high-voltage lithium ion battery and preparation method thereof
CN114551839A (en) * 2022-02-25 2022-05-27 中南大学 Pre-lithiation of single crystal type cobalt-free high-nickel positive electrode material and preparation method thereof
CN114335548A (en) * 2022-03-08 2022-04-12 宜宾锂宝新材料有限公司 Modified ternary positive electrode material and coating modification method thereof
CN114784229A (en) * 2022-03-18 2022-07-22 蜂巢能源科技股份有限公司 Cobalt-free positive electrode material and preparation method and application thereof
CN114784229B (en) * 2022-03-18 2023-08-11 蜂巢能源科技股份有限公司 Cobalt-free positive electrode material and preparation method and application thereof
CN114975983A (en) * 2022-05-06 2022-08-30 四川新锂想能源科技有限责任公司 High-nickel low-cobalt material, preparation method thereof and battery anode
CN114975983B (en) * 2022-05-06 2024-06-18 四川新锂想能源科技有限责任公司 High-nickel low-cobalt material, preparation method thereof and battery anode
CN115417461A (en) * 2022-08-30 2022-12-02 清华大学深圳国际研究生院 Cobalt-free high-nickel cathode material and preparation method thereof

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