CN115947386A - Ternary cathode material with carbon-coated hollow structure and preparation method thereof - Google Patents
Ternary cathode material with carbon-coated hollow structure and preparation method thereof Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000007853 buffer solution Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 229960003638 dopamine Drugs 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000872 buffer Substances 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
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical group Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 claims description 3
- 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
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010405 anode material Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229960001149 dopamine hydrochloride Drugs 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a ternary cathode material with a carbon-coated hollow structure and a preparation method thereof, belonging to the technical field of lithium ion batteries. The problems of low specific surface area and poor conductivity of the ternary cathode material with the polycrystalline structure in the prior art are solved. The preparation method of the ternary cathode material with the carbon-coated hollow structure comprises the steps of uniformly mixing an NCM precursor and a lithium source, and sintering for two times to obtain the ternary cathode material; and then uniformly mixing the ternary cathode material, dopamine, a buffer solution and an ethanol solution, sequentially adding a calcium chloride solution and a sodium carbonate solution, stirring, standing, centrifugally washing, drying in vacuum, sintering under the protection of an inert atmosphere, placing in a hydrochloric acid solution, and stirring to obtain the ternary cathode material with the carbon-coated hollow structure. The ternary cathode material adopts a hollow structure, reduces the specific surface area of the ternary cathode material, improves the coulombic efficiency, and can isolate electrolyte and improve the conductivity of the ternary cathode material by adopting carbon coating.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a ternary cathode material with a carbon-coated hollow structure and a preparation method thereof.
Background
With the depletion of fossil energy, the demand for renewable, clean and pollution-free energy is increasing. Compared with fossil fuel and lead-acid batteries, lithium ion batteries have the characteristics of high energy density and high safety, and are increasingly favored by the market.
Compared with lithium iron phosphate, the lithium nickel cobalt manganese oxide ternary positive electrode material has higher and higher use ratio in a high-end electric vehicle due to high energy density in the existing lithium ion battery.
The ternary cathode material in the prior art is most commonly in a polycrystalline structure, but the ternary cathode material in the polycrystalline structure has low specific surface area and poor conductivity. In order to solve the problems of low specific surface area and poor conductivity of the ternary cathode material with the polycrystalline structure, researchers provide a new technical scheme. One is to mix a ternary precursor with a lithium source and sinter the mixture into single crystal particles at a higher temperature, and compared with a ternary cathode material with a polycrystalline structure, the ternary cathode material prepared by the method has more excellent cycle performance and rate capability. However, the single crystal particles have a large specific surface area due to small particles, so that the ternary cathode material has low coulombic efficiency for the first time. The other method is to mix the anode material with metal oxide or nonmetal oxide according to a proportion and then sinter the mixture at a lower temperature to prepare the oxide-coated ternary anode material. The oxide coating can isolate the material from the electrolyte, and can consume HF generated in the circulation process, thereby reducing gas generation. However, due to the solid-phase sintering method, the oxide coating is not uniform, the thickness is not controllable, and the oxide does not provide capacity, so that most of the oxide is non-conductive.
Disclosure of Invention
In view of the above, the invention provides a carbon-coated hollow ternary cathode material and a preparation method thereof, in order to solve the problems of low specific surface area and poor conductivity of a polycrystalline-structure ternary cathode material in the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows.
The invention provides a preparation method of a ternary cathode material with a carbon-coated hollow structure, which comprises the following steps:
step one, uniformly mixing an NCM precursor and a lithium source according to the mass ratio of 10-1000 by 1-500, heating to 400-500 ℃, preserving heat for 1-12h, then heating to 700-950 ℃, and preserving heat for 10-20h to obtain a ternary cathode material;
step two, uniformly mixing the ternary cathode material prepared in the step one, dopamine, buffer solution and ethanol solution, then adding calcium chloride solution, uniformly mixing, then dropwise adding sodium carbonate solution under stirring, stirring for 1-5h after dropwise adding is completed, standing for more than 12h, centrifugally washing, vacuum drying, and finally heating to 600-800 ℃ under the protection of inert atmosphere, and sintering for 1-5h to obtain a carbon-coated ternary cathode material;
the proportion of the ternary anode material, dopamine, buffer solution, ethanol solution, calcium chloride solution and sodium carbonate solution is (10-1000) g, (1-10) L, (5-20) L, (1-5) moL;
and step three, placing the carbon-coated ternary cathode material obtained in the step two in a hydrochloric acid solution, and stirring for 2-5 hours to obtain the carbon-coated hollow-structure ternary cathode material.
Preferably, in the first step, the NCM precursor is a mixture of one or more of NCM111, NCM523, NCM622, NCM712, and NCM 811.
Preferably, in the first step, the lithium source is one of lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate.
Preferably, in the first step, the temperature rise rate is 2-10 ℃/min, and then the temperature rise rate is 1-5 ℃/min.
Preferably, in the second step, the buffer is Tris-HCl buffer.
Preferably, in the second step, the ternary cathode material, dopamine, buffer solution and ethanol solution are mixed uniformly by ultrasound, and the ultrasound time is 1-10h.
Preferably, in the second step, the concentration of the calcium chloride solution is 1-5moL/L.
Preferably, in the second step, the concentration of the sodium carbonate solution is 1-5mol/L.
Preferably, in the second step, the drying is performed in vacuum for more than 12 hours.
Preferably, in the second step, the inert atmosphere is nitrogen.
Preferably, in the second step, the heating rate is 2-10 ℃/min.
Preferably, in the third step, the concentration of the hydrochloric acid solution is 1-10mol/L.
The invention also provides the ternary cathode material with the carbon-coated hollow structure, which is prepared by the preparation method of the ternary cathode material with the carbon-coated hollow structure.
Compared with the prior art, the invention has the following beneficial effects:
compared with the solid-phase oxide coating method of the traditional polycrystalline anode material, the ternary anode material with the carbon-coated hollow structure can provide excellent first coulombic efficiency, a better crystal structure, a lower specific surface and lower impedance.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention, but it is to be understood that the description is intended to illustrate further features and advantages of the invention, and not to limit the scope of the claims.
The preparation method of the ternary cathode material with the carbon-coated hollow structure comprises the following steps:
step one, uniformly mixing an NCM precursor and a lithium source according to the mass ratio of 10-1000 by 1-500, heating to 400-500 ℃, preserving heat for 1-12h, then heating to 700-950 ℃, and preserving heat for 10-20h to obtain a ternary cathode material;
step two, uniformly mixing the ternary cathode material prepared in the step one, dopamine, buffer solution and ethanol solution, then adding calcium chloride solution, uniformly mixing, then dropwise adding sodium carbonate solution under stirring, stirring for 1-5h after dropwise adding is completed, standing for more than 12h, centrifugally washing, vacuum drying, and finally heating to 600-800 ℃ under the protection of inert atmosphere, and sintering for 1-5h to obtain a carbon-coated ternary cathode material;
wherein the proportion of the ternary anode material, the dopamine, the buffer solution, the ethanol solution, the calcium chloride solution and the sodium carbonate solution is (10-1000 g), (1-10) L, (5-20) L, (1-5) moL;
and step three, placing the carbon-coated ternary cathode material obtained in the step two in a hydrochloric acid solution, and stirring for 2-5 hours to obtain the carbon-coated hollow ternary cathode material.
In the above technical solution, in the first step, the NCM precursor is preferably a mixture of one or more of NCM111, NCM523, NCM622, NCM712, and NCM 811. It is to be noted that NCM precursors known to those skilled in the art are all suitable for use in the present invention and are commercially available.
In the above technical solution, in the first step, the lithium source is preferably one of lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate. It is to be noted that lithium sources known to those skilled in the art are suitable for use in the present invention and are commercially available. .
In the technical scheme, in the first step, the heating rate of the first heating is preferably 2-10 ℃/min, and the heating rate of the second heating is preferably 1-5 ℃/min. It should be noted that the temperature raising rate is not particularly limited, and can be set by those skilled in the art according to actual needs.
In the above technical scheme, in the second step, the buffer solution is preferably Tris-HCl buffer solution. The buffer is not particularly limited, and one skilled in the art can select the buffer according to actual needs.
In the technical scheme, in the second step, the ternary cathode material, the dopamine, the buffer solution and the ethanol solution are ultrasonically mixed uniformly for 1-10 hours, and after the calcium chloride solution is added, the mixture is stirred and uniformly mixed. It should be noted that other mixing methods in the art that can achieve the effect of uniform mixing are also suitable for use in the present invention.
In the technical scheme, in the second step, the concentration of the calcium chloride solution is preferably 1-5moL/L; the concentration of the sodium carbonate solution is preferably 1-5mol/L; the invention manufactures the hollow structure by adding the calcium carbonate, reduces the specific surface area of the ternary anode material, and controls the amount of the hollow structure by controlling the dosage of the calcium carbonate.
In the above technical solution, in the second step, the time for vacuum drying is preferably 12 hours or more. It should be noted that the drying effect is achieved without any particular limitation.
In the above technical solution, in the second step, the preferable inert atmosphere is nitrogen. It is to be noted that the inert atmosphere in the present invention is not particularly limited, and other inert atmospheres can be applied to the present invention.
In the technical scheme, in the second step, the heating rate is preferably 2-10 ℃/min. It should be noted that the temperature raising rate is not particularly limited, and can be set by those skilled in the art according to actual needs.
In the technical scheme, in the third step, the concentration of the hydrochloric acid solution is preferably 1-10mol/L.
In the above technical scheme, in the third step, magnetic stirring is preferably adopted for stirring. Other stirring methods are also possible.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified. In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the following embodiments.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art. Materials, reagents, devices, apparatuses, instruments, apparatuses and the like used in the following examples are commercially available unless otherwise specified.
The present invention is further illustrated by the following examples.
Example 1
Step one, ball-milling and uniformly mixing 100g of NCM precursor and 48.64g of lithium hydroxide, putting the mixture into a tube furnace, heating to 500 ℃ at a heating rate of 8 ℃/min and keeping the temperature for 5 hours under the condition of liquid oxygen, and heating to 900 ℃ at a heating rate of 5 ℃/min and keeping the temperature for 12 hours to obtain a ternary cathode material;
step two, firstly adding 100g of the ternary cathode material prepared in the step one and 100g of dopamine hydrochloride into 15L of mixed solution (the volume ratio of the Tris-HCl solution to the ethanol solution is = 1; finally, placing the carbon-coated ternary cathode material in a tubular furnace under the nitrogen atmosphere, heating to 700 ℃ at the heating rate of 5 ℃/min, and preserving heat for 2 hours to obtain a carbon-coated ternary cathode material;
and step three, placing the carbon-coated ternary cathode material prepared in the step two in a 5mol/L hydrochloric acid solution, and magnetically stirring for 4 hours to obtain the carbon-coated ternary cathode material with a hollow structure, wherein the material is marked as NCM @ V @ C.
Comparative example 1
Step one, ball-milling and uniformly mixing 100g of NCM precursor and 48.64g of lithium hydroxide, putting the mixture in a tube furnace, keeping the temperature for 5h when the temperature is increased to 500 ℃ at the heating rate of 8 ℃/min under the condition of liquid oxygen, then increasing the temperature to 900 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 12h to obtain a ternary cathode material, and dividing the ternary cathode material into two parts, wherein one part of the ternary cathode material is marked as NCM-1;
and step two, uniformly mixing the other part of ternary cathode material with alumina according to the proportion of 1500ppm of the ternary cathode material, and then preserving the heat for 6 hours at 500 ℃ in an oxygen atmosphere to obtain the oxide-coated ternary cathode material which is recorded as NCM-2.
XRD was used to test the I of NCM @ Voids @ C of example 1, NCM-1 of comparative example 1, and NCM-2 of comparative example 1 (003)/I(104) Value of (I) (003)/I(104) The larger the value of (b) indicates the more complete the crystal form of the material), the test angle is 0-90 °, and the rotation speed per minute is 2 °. The specific surface area of NCM @ Voids @ C of example 1, NCM-1 of comparative example 1, and NCM-2 of comparative example 1 was measured using a specific surface area apparatus, the degassing temperature was 200 ℃, the temperature rise rate was 10 ℃/min, and the temperature was maintained at 200 ℃ for 90min. The test results are shown in table 1.
TABLE 1 results of Performance test of NCM @ Voids @ C of example 1, NCM-1 of comparative example 1, and NCM-2 of comparative example 1
| Name of Material | I (003)/I(104) | Specific surface area |
| NCM@Voids@C | 1.662256642 | 0.56 |
| NCM-1 | 1.545256256 | 1.21 |
| NCM-2 | 1.564879213 | 1.08 |
As can be seen from table 1, the value of the ternary cathode material with the carbon-coated hollow structure in example 1 is higher than that of the uncoated ternary cathode material and the oxide-coated ternary cathode material, which indicates that the hollow structure can effectively improve the integrity of the crystal form. The specific surface area of the ternary cathode material with the carbon-coated hollow structure is the smallest, and the specific surface area of the ternary cathode material coated with the oxide is slightly lower than that of the uncoated ternary cathode material, so that the specific surface area can be reduced by coating, but the effect is not better than that of the ternary cathode material with the hollow structure.
The NCM @ Voids @ C of example 1, the NCM-1 of comparative example 1 and the NCM-2 of comparative example 1 are uniformly mixed with SP and PVDF according to a mass ratio of 9.2: the charging and discharging voltage is 3.0-4.35V, and the testing temperature is 25 ℃. The results are shown in Table 2.
TABLE 2 performance test results for CR2032 button cell
As can be seen from Table 2, the button cell prepared from NCM @ Voids @ C has the highest initial specific discharge capacity and the highest initial coulombic efficiency, and the initial coulombic efficiency of the button cell prepared from the oxide-coated ternary cathode material is slightly higher than that of the button cell prepared from the uncoated ternary cathode material.
It should be understood that the above-described embodiments are merely examples for clearly illustrating the present invention and are not intended to limit the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. It need not be, and cannot be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A preparation method of a ternary cathode material with a carbon-coated hollow structure is characterized by comprising the following steps:
step one, uniformly mixing an NCM precursor and a lithium source according to the mass ratio of 10-1000, namely 1-500, heating to 400-500 ℃, preserving heat for 1-12h, then heating to 700-950 ℃, and preserving heat for 10-20h to obtain a ternary cathode material;
step two, uniformly mixing the ternary cathode material prepared in the step one, dopamine, buffer solution and ethanol solution, then adding calcium chloride solution, uniformly mixing, then dropwise adding sodium carbonate solution under stirring, stirring for 1-5h after dropwise adding is completed, standing for more than 12h, centrifugally washing, vacuum drying, and finally heating to 600-800 ℃ under the protection of inert atmosphere, and sintering for 1-5h to obtain a carbon-coated ternary cathode material;
the proportion of the ternary positive electrode material, dopamine, buffer solution, ethanol solution, calcium chloride solution and sodium carbonate solution is (10-1000) g, (1-10) L, (5-20) L, (1-5) moL;
and step three, placing the carbon-coated ternary cathode material obtained in the step two in a hydrochloric acid solution, and stirring for 2-5 hours to obtain the carbon-coated hollow-structure ternary cathode material.
2. The method for preparing a ternary cathode material with a carbon-coated hollow structure according to claim 1, wherein in the first step, the precursor of the NCM is a mixture of one or more of NCM111, NCM523, NCM622, NCM712 and NCM 811.
3. The method for preparing the ternary cathode material with the carbon-coated hollow structure according to claim 1, wherein in the first step, the lithium source is one of lithium carbonate, lithium hydroxide, lithium nitrate and lithium acetate.
4. The preparation method of the ternary cathode material with the carbon-coated hollow structure according to claim 1, wherein in the first step, the temperature rise rate of the first temperature rise is 2-10 ℃/min, and the temperature rise rate of the second temperature rise is 1-5 ℃/min.
5. The method for preparing a ternary cathode material with a carbon-coated hollow structure according to claim 1, wherein in the second step, the buffer is Tris-HCl buffer.
6. The preparation method of the ternary cathode material with the carbon-coated hollow structure according to claim 1, wherein in the second step, the ternary cathode material, dopamine, buffer solution and ethanol solution are uniformly mixed by ultrasound for 1-10 hours; after the calcium chloride solution is added, the mixture is stirred and mixed evenly.
7. The preparation method of the ternary cathode material with the carbon-coated hollow structure as claimed in claim 1, wherein the concentration of the calcium chloride solution is 1-5moL/L; the concentration of the sodium carbonate solution is 1-5mol/L.
8. The method for preparing the ternary cathode material with the carbon-coated hollow structure according to claim 1, wherein in the second step, the temperature rise rate is 2-10 ℃/min.
9. The method for preparing the ternary cathode material with the carbon-coated hollow structure according to claim 1, wherein the concentration of the hydrochloric acid solution in the third step is 1-10mol/L.
10. The carbon-coated hollow-structure ternary cathode material prepared by the method for preparing the carbon-coated hollow-structure ternary cathode material according to any one of claims 1 to 9.
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