CN114695876A - Method for in-situ solid-phase coating of lithium ion conductor by using ternary cathode material NCM - Google Patents
Method for in-situ solid-phase coating of lithium ion conductor by using ternary cathode material NCM Download PDFInfo
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- CN114695876A CN114695876A CN202210390495.8A CN202210390495A CN114695876A CN 114695876 A CN114695876 A CN 114695876A CN 202210390495 A CN202210390495 A CN 202210390495A CN 114695876 A CN114695876 A CN 114695876A
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- 239000010416 ion conductor Substances 0.000 title claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- 238000000576 coating method Methods 0.000 title claims abstract description 39
- 239000011248 coating agent Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 29
- 239000010406 cathode material Substances 0.000 title claims abstract description 26
- 239000007790 solid phase Substances 0.000 title claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 239000007774 positive electrode material Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000011247 coating layer Substances 0.000 claims abstract description 22
- 238000007873 sieving Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims abstract description 8
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 5
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 11
- 229910010092 LiAlO2 Inorganic materials 0.000 claims description 7
- 229910003327 LiNbO3 Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910007562 Li2SiO3 Inorganic materials 0.000 claims description 6
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 claims description 6
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical group O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims 3
- 229910052802 copper Inorganic materials 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 8
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 10
- 238000005457 optimization Methods 0.000 description 5
- 229910010093 LiAlO Inorganic materials 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 229910020489 SiO3 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910013457 LiZrO Inorganic materials 0.000 description 1
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 1
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 1
- 229910015150 Ni1/3Co1/3Mn1/3(OH)2 Inorganic materials 0.000 description 1
- 229910003618 NixCoyMn1-x-y(OH)2 Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method for in-situ solid-phase coating of a lithium ion conductor by a ternary cathode material NCM, which aims to solve the problem of difficult production by the existing method and comprises the following steps: (1) ni precursor after dryingxCoyMn1‑x‑y(OH)2Mixing with an excessive lithium source required by forming a lithium ion conductor on the surface in situ, and stirring and mixing by using a ball mill to obtain a uniformly mixed material; (2) the uniform mixed material is subjected to primary sintering by a high-temperature solid phase method to obtain a primary sintered product, namely a lithium compound coated positive electrode material LiNixCoyMn1‑x‑yO2Then sieving to obtain a product below a sieve; (3) adding a proper amount of metal oxide into the obtained product, carrying out secondary sintering, and then sieving to obtain a positive electrode material LiNi with a undersize material as a surface in-situ formed lithium ion conductor coating layerxCoyMn1‑x‑yO2And (3) powder lot. Has the advantages of simple operation, high efficiency, environmental protection, low cost, easy industrialized production and suitability for coating the surface of the ternary oxide anodeThe ion conductor is coated, and compared with an oxide coating layer, the prepared ion conductor coating layer has the advantage of higher ion conductivity.
Description
Technical Field
The invention relates to a method for coating a lithium ion conductor by a cathode material, in particular to a method for coating a lithium ion conductor by a ternary cathode material NCM in situ solid phase.
Background
In recent years, with the rise of the electric automobile industry and the field of large-scale energy storage, higher requirements are put on the performance of the lithium ion battery, and the lithium ion battery is required to have not only high energy density and power density, but also high safety performance, long service life and the like. The anode material is an important component of the lithium ion battery, and is not only a bottleneck for improving the capacity of the lithium ion battery, but also the most important factor for determining the price of the lithium ion battery. The method finds the positive electrode material with high discharge capacity and stability, produces the positive electrode material with excellent quality and low price, and becomes a hot spot of continuous attention of the industry. The safety, energy density, output performance, circulation and cost of the ternary material are relatively balanced, and the ternary material gradually becomes a development trend of power batteries. However, ternary materials still have major technical problems: firstly, the phase transformation of the particle surface is easy to cause the attenuation of the battery capacity and the cycle performance; secondly, after circulation, the particles are cracked, which causes the electrochemical performance to be attenuated, and leads the thermal stability and the safety performance to be reduced.
In order to improve the stability and electrochemical performance of the ternary material, metal ions are doped in a material crystal lattice or a coating layer is constructed on the surface of the positive electrode material, so that chemical/electrochemical side reactions of the positive electrode material interface can be effectively inhibited, and the interface resistance is reduced, which proves to be an effective measure. The coating materials reported so far mainly comprise conventional oxides (SiO)2，ZrO2，Al2O3Etc.) and lithium ion conductors (LiNbO)3，Li4Ti5O12，Li3PO4Etc.). Although the oxide material as a coating layer can effectively reduce the side reaction at the interface, it has no lithium ion conductivity and is not favorable for the transmission of lithium ions at the interface. Therefore, a lithium ion conductor having high ion conductivity is considered to be a more suitable cladding material than an oxide material. However, it is not limited toThe traditional method for coating the lithium ion conductor by the wet method uses a solvent, so that the process flow is long, and the early investment is large.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides the method for coating the lithium ion conductor on the surface of the ternary oxide anode by the NCM in-situ solid phase coating of the ternary anode material, which is simple to operate, efficient, environment-friendly, low in cost, easy for industrial production and suitable for coating the ion conductor on the surface of the ternary oxide anode.
In order to achieve the purpose, the method for in-situ solid-phase coating of the lithium ion conductor by the ternary cathode material NCM comprises the following steps: (1) ni precursor after dryingxCoyMn1-x-y(OH)2Mixing with an excessive lithium source required by forming a lithium ion conductor on the surface in situ, and stirring and mixing by using a ball mill to obtain a uniformly mixed material; (2) the uniform mixed material is subjected to primary sintering by a high-temperature solid phase method to obtain a primary sintered product, namely a lithium compound coated positive electrode material LiNixCoyMn1-x-yO2， x>0，y>0，1-x-y>0, then sieving to obtain a product under sieve; (3) adding a proper amount of metal oxide into the obtained product, carrying out secondary sintering, and then sieving to obtain a positive electrode material LiNi with a undersize material as a surface in-situ formed lithium ion conductor coating layerxCoyMn1-x-yO2And (3) powder lot. Experiments prove that the method has the advantages of simple operation, high efficiency, environmental friendliness, low cost, easiness in industrial production and suitability for coating the ion conductor on the surface of the ternary oxide anode, and the prepared ion conductor coating layer has higher ion conductivity compared with an oxide coating layer.
As optimization, the rotation speed of stirring and mixing by using a ball mill is 100-300r/h, and the stirring time is 1-3 h. The ball mill can ensure even mixing by stirring and mixing, and the next sintering is easy to be carried out.
Preferably, the lithium source is at least one of lithium hydroxide, lithium nitrate, lithium carbonate and lithium acetate. And various lithium sources are suitable.
As optimization, the primary sintering is two-stage sintering, the first-stage sintering temperature is 700 ℃, the sintering time is 4 hours, the second-stage sintering temperature is 750 ℃, and the sintering time is 12 hours; the secondary sintering temperature is 500-700 ℃, and the sintering time is 3-7 h. The first stage sintering is carried out in two stages with the time for increasing the high temperature, which is beneficial to ensuring and improving the sintering and sieving quality.
Preferably, the proper amount of the metal oxide is obtained according to the fact that the surface lithium ion conductor coating layer accounts for 1% -2% of the mass of the positive electrode material.
Preferably, the metal oxide is Nb2O5、SiO2、ZrO2Or Al2O3(ii) a The lithium ion conductor material is LiNbO3、Li2SiO3、LiZrO2Or LiAlO2。
Preferably, the sintering atmosphere is oxygen, and the lithium compound is Li2O。
As an optimization, NixCoyMn1-x-y(OH)2And LiNixCoyMn1-x-yO2And LiNixCoyMn1-x-yO2Wherein x is 1/3-0.8, and y is 0.1-1/3.
As optimization, the positive electrode material LiNixCoyMn1-x-yO2Is LiNbO3Coated LiNi1/3Co1/3Mn1/3O2And (3) a positive electrode material.
For optimization, the mass ratio of the positive electrode materials is as follows: LiAlO2Is LiNi0.6Co0.2Mn0.2O21-2% of the positive electrode material.
Compared with the prior art, the invention has the main beneficial effects that (1) the ion conductor coating layer prepared in the invention has obviously higher ion conductivity compared with an oxide coating layer; (2) the coating process can remove the impure phase on the surface of the ternary oxide anode and form a beneficial coating layer, thereby changing waste into valuable; (3) the coating layer preparation process is free from liquid use, does not need an evaporation process, is environment-friendly and is easy for industrial implementation.
After the technical scheme is adopted, the method for in-situ solid-phase coating of the lithium ion conductor by the ternary cathode material NCM has the advantages of simplicity in operation, high efficiency, environmental friendliness, low cost, easiness in industrial production and suitability for coating the ion conductor on the surface of the ternary oxide cathode, and the prepared ion conductor coating layer has higher ion conductivity compared with an oxide coating layer.
Drawings
FIGS. 1-2 are respectively Li obtained by the method of the invention of the ternary cathode material NCM in-situ solid-phase coating lithium ion conductor2SiO3Coated LiNi0.8Co0.1Mn0.1O2SEM image at 25 ℃ and Li obtained2SiO3Coated LiNi0.8Co0.1Mn0.1O2First cycle charge and discharge curves at 25 ℃. FIGS. 3 to 4 are respectively LiAlO obtained by the method of the invention for in-situ solid-phase coating of a ternary cathode material NCM on a lithium ion conductor2Coated LiNi0.8Co0.1Mn0.1O2SEM image at 25 ℃ and LiAlO obtained2Coated LiNi0.8Co0.1Mn0.1O2First cycle charge and discharge curves at 25 ℃. FIGS. 5 to 6 show LiNbO obtained by the method of the invention of the ternary cathode material NCM in-situ solid-phase coating of a lithium ion conductor3Coated LiNi0.8Co0.1Mn0.1O2SEM image at 25 ℃ and LiNbO obtained3Coated LiNi0.8Co0.1Mn0.1O2First cycle charge and discharge curves at 25 ℃.
Detailed Description
In the first embodiment, as shown in fig. 1-2, the method for coating lithium ion conductor with ternary cathode material NCM in situ solid phase is to coat dried 5g Ni0.8Co0.1Mn0.1(OH)2Precursor with 2.18g Li2CO3Mixing by using a ball mill at the rotating speed of 100r/h for 3h to obtain a uniformly mixed material; sintering the obtained material at 700 ℃ for 4h and at 750 ℃ for 12h to obtain a primary sintered product Li2O-coated positive electrode material LiNi0.8Co0.1Mn0.1O2Then sieving with 400 mesh sieve(ii) a The resulting product was added to 0.07g of SiO2Sintering at 700 ℃ for 3h, and then sieving with a 400-mesh sieve to obtain Li2SiO3Coated LiNi0.8Co0.1Mn0.1O2Positive electrode material of mass ratio Li2SiO3Is LiNi0.8Co0.1Mn0.1O22% of the positive electrode material. Li2SiO3The thickness of the coating layer is about 5.8 nm (figure 1), and Li is in the range of 3-4.3V charge-discharge voltage2SiO3Coated LiNi0.8Co0.1Mn0.1O2The specific discharge capacity of the anode can reach 207.6 mAh g-1(FIG. 2).
In the second embodiment, as shown in fig. 3-4, the method for coating lithium ion conductor with ternary cathode material NCM in situ solid phase is to coat dried 5g Ni0.6Co0.2Mn0.2(OH)2Precursor with 2.14g Li2CO3Mixing by using a ball mill at the rotating speed of 200r/h for 2h to obtain a uniformly mixed material; sintering the obtained material at 700 ℃ for 4h and at 750 ℃ for 12h to obtain a primary sintered product Li2O-coated positive electrode material LiNi0.6Co0.2Mn0.2O2Then sieving with a 400-mesh sieve; the resulting product was added with 0.06g of Al2O3Sintering at 600 ℃ for 5h, and then sieving with a 400-mesh sieve to obtain LiAlO2Coated LiNi0.6Co0.2Mn0.2O2Positive electrode material of LiAlO in mass ratio2Is LiNi0.6Co0.2Mn0.2O21.5% of the positive electrode material. LiAlO2The thickness of the coating layer is about 4.6 nm (figure 3), and LiAlO is in the range of 3-4.3V charge-discharge voltage2Coated LiNi0.6Co0.2Mn0.2O2The specific discharge capacity of the anode can reach 185.9 mAh g-1(FIG. 4).
In the third embodiment, as shown in fig. 5-6, the method for coating lithium ion conductor with ternary cathode material NCM in situ solid phase is to coat dried 5g Ni1/3Co1/3Mn1/3(OH)2Precursor and 1.37g LiOH utilization ballMixing by a mill at the rotating speed of 300r/h for 1h to obtain a uniformly mixed material; sintering the obtained material at 700 ℃ for 4h and at 750 ℃ for 12h to obtain a primary sintered product Li2O-coated positive electrode material LiNi1/3Co1/3Mn1/3O2Then sieving with a 400-mesh sieve; the resulting product was charged with 0.05g Nb2O5Sintering at 500 ℃ for 7h, and then sieving with a 400-mesh sieve to obtain LiNbO3Coated LiNi1/3Co1/3Mn1/3O2Positive electrode material of LiNbO in mass ratio3Is LiNi1/3Co1/3Mn1/3O21% of the positive electrode material. LiNbO3The thickness of the coating layer is about 3.5 nm (figure 5), and LiNbO is in the charge-discharge voltage range of 3-4.3V3Coated LiNi1/3Co1/3Mn1/3O2The specific discharge capacity of the anode can reach 174.2 mAh g-1(FIG. 6).
Note: in addition to the lithium hydroxide and lithium carbonate sources described above, the ion conductor coating made with lithium nitrate and lithium acetate also apparently has similarly higher ionic conductivity than the oxide coating. In addition to using Nb as described above2O5、SiO2、Al2O3Using ZrO other than metal oxides2The prepared ion conductor coating also has obviously similar higher ion conductivity compared with the oxide coating. Except for using the above LiNbO3、Li2SiO3、LiAlO2In addition to the lithium ion conductor, LiZrO is used2The ion conductor coating made of the lithium ion conductor also apparently has similarly higher ion conductivity than the oxide coating.
In a word, the method for in-situ solid-phase coating of the lithium ion conductor by the ternary cathode material NCM has the advantages of simple operation, high efficiency, environmental friendliness, low cost, easiness in industrial production and suitability for coating the ion conductor on the surface of the ternary oxide cathode, and the prepared ion conductor coating layer has higher ion conductivity compared with an oxide coating layer.
Claims (10)
1. A method for in-situ solid-phase coating of a lithium ion conductor by using a ternary cathode material NCM is characterized by comprising the following steps: (1) ni precursor after dryingxCoyMn1-x-y(OH)2Mixing with an excessive lithium source required by forming a lithium ion conductor on the surface in situ, and stirring and mixing by using a ball mill to obtain a uniformly mixed material; (2) the uniformly mixed material is sintered for one time by a high-temperature solid phase method to obtain a positive electrode material LiNi of which the primary sintered product is coated by a lithium compoundxCoyMn1-x-yO2， x>0，y>0，1-x-y>0, then sieving to obtain a product under sieve; (3) adding a proper amount of metal oxide into the obtained product, carrying out secondary sintering, and then sieving to obtain a positive electrode material LiNi with the undersize as a surface in-situ formed lithium ion conductor coating layerxCoyMn1-x-yO2And (3) powder lot.
2. The method for in-situ solid-phase coating of the ternary cathode material NCM on the lithium ion conductor as claimed in claim 1, wherein the rotation speed of stirring and mixing by the ball mill is 100-300r/h, and the stirring time is 1-3 h.
3. The method for in-situ solid-phase coating of the ternary cathode material NCM on the lithium ion conductor according to claim 1, wherein the lithium source is at least one of lithium hydroxide, lithium nitrate, lithium carbonate and lithium acetate.
4. The method for in-situ solid-phase coating of the ternary cathode material NCM on the lithium ion conductor according to claim 1, wherein the primary sintering is a two-stage sintering, the first-stage sintering temperature is 700 ℃, the sintering time is 4h, the second-stage sintering temperature is 750 ℃, and the sintering time is 12 h; the secondary sintering temperature is 500-700 ℃, and the sintering time is 3-7 h.
5. The method for in-situ solid-phase coating of the lithium ion conductor by the ternary cathode material NCM according to claim 1, wherein the proper amount of the metal oxide is obtained according to the condition that the coating layer of the surface lithium ion conductor accounts for 1% -2% of the mass of the cathode material.
6. The method for in-situ solid-phase coating of the ternary cathode material NCM on the lithium ion conductor according to claim 1, wherein the metal oxide is Nb2O5、SiO2、ZrO2Or Al2O3(ii) a The lithium ion conductor material is LiNbO3、Li2SiO3、LiZrO2Or LiAlO2。
7. The method of claim 1, wherein the atmosphere of sintering is oxygen, and the lithium compound is Li2O。
8. The method for in-situ solid-phase coating of the lithium ion conductor by the ternary cathode material NCM according to claim 1, wherein Ni is selected from the group consisting of Ni, Cu, Ni, and Co, and Ni, or a combination thereofxCoyMn1-x-y(OH)2And LiNixCoyMn1-x-yO2And LiNixCoyMn1-x-yO2Wherein x is 1/3-0.8, and y is 0.1-1/3.
9. The method for in-situ solid-phase coating of the lithium ion conductor by the ternary cathode material NCM according to claim 1, wherein the cathode material LiNi is LiNixCoyMn1-x-yO2Is LiNbO3Coated LiNi1/3Co1/3Mn1/3O2And (3) a positive electrode material.
10. The method for in-situ solid-phase coating of the lithium ion conductor by the ternary cathode material NCM according to claim 9, wherein the mass ratio of the cathode material is as follows: LiAlO2Is LiNi0.6Co0.2Mn0.2O21-2% of the positive electrode material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115133114A (en) * | 2022-07-29 | 2022-09-30 | 重庆太蓝新能源有限公司 | Solid electrolyte material, preparation method thereof and battery |
| CN115148997A (en) * | 2022-09-05 | 2022-10-04 | 宁德时代新能源科技股份有限公司 | Composite positive electrode active material, method for producing same, and electricity-using device comprising same |
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