CN109755537B - Doped coating modified nickel-rich ternary cathode material and preparation method thereof - Google Patents
Doped coating modified nickel-rich ternary cathode material and preparation method thereof Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 76
- 238000000576 coating method Methods 0.000 title claims abstract description 26
- 150000002815 nickel Chemical class 0.000 title claims abstract description 26
- 239000011248 coating agent Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 152
- 229910052759 nickel Inorganic materials 0.000 claims description 73
- 239000002243 precursor Substances 0.000 claims description 35
- 238000005245 sintering Methods 0.000 claims description 35
- 229910052744 lithium Inorganic materials 0.000 claims description 34
- 229910052736 halogen Inorganic materials 0.000 claims description 31
- 150000002367 halogens Chemical group 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 26
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 24
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 14
- -1 lithium halide Chemical class 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 6
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 6
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 6
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 6
- 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
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 description 20
- 239000007774 positive electrode material Substances 0.000 description 18
- 239000000306 component Substances 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical group [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- 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 2
- 238000000227 grinding Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910015639 LiNi0.815Co0.15Al0.035O2 Inorganic materials 0.000 description 1
- 229910016886 Ni0.815Co0.15Al0.035(OH)2 Inorganic materials 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 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
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- 239000007858 starting material Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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- 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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Abstract
The invention relates to a doped coating modified nickel-rich ternary cathode material and a preparation method thereof1‑x‑ yCoyAlxXzO2‑0.5z(X = F, Cl and Br), wherein X is more than or equal to 0.030 and less than or equal to 0.050, y is more than or equal to 0.100 and less than or equal to 0.150, and z is more than or equal to 0.001 and less than or equal to 0.008.
Description
Technical Field
The invention relates to a doped, coated and modified nickel-rich ternary cathode material and a preparation method thereof, belonging to the technical field of lithium ion battery cathode materials.
Background
In recent years, the application of lithium ion batteries in the fields of energy storage and electric automobiles is receiving wide attention. The lithium ion battery cathode material is used as a cathode material of an important component in a lithium ion battery, and plays a decisive role in important performances of the battery, such as working voltage, cycle life, high and low capacity, safety and the like. Therefore, research and development of high-capacity, long-life, and high-safety cathode materials are one of the major points in the research of lithium ion batteries.
The performance of the anode material in the lithium ion battery is very important for improving the performance of the lithium ion battery. At present, the anode material of the lithium ion battery mainly comprises lithium cobaltate, lithium manganate, lithium nickel manganese cobalt, lithium iron phosphate and the like. In recent years, nickel-rich ternary cathode materials (nickel cobalt lithium manganate) are attracting attention increasingly, and through data tests on the performances of the materials, such as volume specific capacity, gravimetric specific capacity, circulation, safety and the like, the nickel-rich ternary cathode materials are generally shown to have some excellent performances, such as high voltage platform, large reversible specific capacity, stable structure, good safety performance and the like, of the new lithium battery cathode materials. However, the nickel-rich ternary cathode material still has some problems to be solved urgently. Firstly, the phenomenon of bit occupation still exists in the nickel-rich ternary cathode material, so that the capacity of the material is lost in the charge and discharge process, and the cycle performance is reduced. Second, the heat and oxygen generated by oxidation in direct contact with the electrolyte in the charged state still pose safety concerns. Third, the highly alkaline nature of nickel-rich based positive electrode materials causes the materials to readily adsorb moisture and carbon dioxide, resulting in a dramatic decrease in electrochemical performance of the materials after storage.
In the prior art, the following reports have been made to solve the above problems: CN108899531A is a nickel-cobalt-aluminum ternary positive electrode material as a core, the surface of the core is coated with phosphate, and a chelating agent is added in the coating process, so that the phosphate is promoted to be coated on the surface of the nickel-cobalt-aluminum ternary positive electrode material. The phosphate-coated positive electrode material has higher ion migration capacity and electron transfer capacity, and the coated material inhibits side reaction between the positive electrode material and electrolyte. CN108933239A discloses a preparation method of a lithium manganate coated lithium nickel cobalt manganese oxide positive electrode material, which realizes the structure of lithium manganate coated lithium nickel cobalt manganese oxide, reduces the sintering difficulty, and simultaneously avoids the problems of high pH and water absorption of a certain high nickel material. Although some defects are solved to a certain extent by technical means in the prior art, the continuous improvement of the performance of the anode material for the lithium ion battery is a difficult problem which is continuously researched and overcome by technical personnel in the field, so that the invention and the creation of the material which has more excellent cycle stability and meets higher use requirements are particularly important.
Disclosure of Invention
The invention aims to solve the problems in the prior art, provides a doped coating modified nickel-rich ternary cathode material with excellent cycle performance and long service life, and also provides a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
subject of the technology 1
The invention provides a doped cladding modifiedThe nickel-rich ternary cathode material comprises a halogen-doped nickel-rich ternary nucleus body and a lithium halide amorphous coating structure, wherein the chemical composition of the halogen element-doped nickel-rich ternary nucleus body is LiNi1-x- yCoyAlxXzO2-0.5z(X = F, Cl, Br), wherein X is more than or equal to 0.030 and less than or equal to 0.050, y is more than or equal to 0.100 and less than or equal to 0.150, and z is more than or equal to 0.001 and less than or equal to 0.008.
Further, the ratio of the total amount of the material of the lithium halide amorphous coating structure to the amount of the material of the halogen element doped lithium nickel cobalt oxide core is (0.0005-0.0040): 1.
Subject matter two
The invention provides a preparation method of a doping coating modified nickel-rich ternary cathode material, which comprises the following steps:
(1) mixing the nickel-rich ternary precursor with a lithium source and a halogen source, and performing ball milling to obtain a ball-milled mixed material; the nickel-rich ternary precursor is Ni1-x-yCoyAlx(OH)2Wherein x is more than or equal to 0.030 and less than or equal to 0.050, y is more than or equal to 0.100 and less than or equal to 0.150, and the halogen source is selected from one or the combination of two or more of a fluorine source, a chlorine source and a bromine source;
(2) sequentially pre-sintering and re-sintering the ball-milling mixed material obtained in the step (2) in an oxygen atmosphere to obtain a coated doped anode material; the pre-sintering temperature is 400-500 ℃, and the pre-sintering time is 4-6 h; the temperature of the re-sintering is 700-800 ℃, and the time of the re-sintering is 11-13 h;
preferably, the pre-sintering temperature and the re-sintering temperature in the step (2) are both achieved in a temperature rise mode, and the temperature rise rate is independently 1-5 ℃/min.
Preferably, the lithium source in step (1) comprises one or more of lithium hydroxide monohydrate, lithium acetate and lithium carbonate.
Preferably, the fluorine source in step (1) comprises one or more of lithium fluoride, ammonium fluoride and tetrabutylammonium fluoride.
Preferably, the chlorine source in step (1) comprises one or more of lithium chloride, ammonium chloride and benzyltriethylammonium chloride.
Preferably, the bromine source in step (1) comprises one or more of lithium bromide, ammonium bromide and tetramethylammonium bromide.
Preferably, the mixing and ball milling time in the step (1) is 10-12 h, and the rotating speed of the mixing and ball milling is 100-150 r/min.
Preferably, the molar ratio of the lithium source in the step (1) to the nickel-rich ternary precursor in the step (1) is (1.03-1.08): 1;
the molar ratio of the halogen source in the step (1) to the nickel-rich ternary precursor in the step (1) is (0.10-0.40): 100.
adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
according to the invention, the nickel-rich ternary material is modified by a doping and coating means, part of halogen particles enter the particles through gaps to improve the crystal structure, and part of the halogen particles are left on the surfaces of the particles to form a lithium halide amorphous coating structure, so that the nickel-rich ternary cathode material is prevented from being directly contacted with an electrolyte, and the improvement of the overall performance of the nickel-rich ternary cathode material is facilitated.
The nickel-rich ternary precursor, the lithium source and the halogen source are mixed and ball-milled, fully dispersed, and uniformly doped and coated by controlling the sintering temperature and the sintering time.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is an SEM image of the positive electrode material obtained in comparative example 1;
fig. 2 is an SEM image of the cathode material obtained in example 2;
fig. 3 is an XRD spectrum of the positive electrode materials obtained in comparative example 1 and example 1.
Detailed Description
The doped coating modified nickel-rich ternary cathode material comprises a halogen-doped lithium nickel cobalt oxide core body and a lithium halide amorphous coating structure, wherein the chemical composition of the halogen element-doped nickel-rich ternary core body is LiNi1-x-yCoyAlxXzO2-0.5z(X = F, Cl, Br), wherein X is more than or equal to 0.030 and less than or equal to 0.050, y is more than or equal to 0.100 and less than or equal to 0.150, and z is more than or equal to 0.001 and less than or equal to 0.008.
The doped coating modified nickel-rich ternary cathode material provided by the invention comprises a halogen-doped nickel-rich ternary core body and a coating layer. In the invention, the chemical composition of the halogen element doped lithium nickel cobalt oxide core body is LiNi1-x-yCoyAlxXzO2-0.5z(X = F, Cl, Br), wherein:
x is more than or equal to 0.030 and less than or equal to 0.050, further, x is more than or equal to 0.035 and less than or equal to 0.045, and further, x = 0.40; y is more than or equal to 0.100 and less than or equal to 0.150, further, y is more than or equal to 0.135 and less than or equal to 0.145, and further, y = 0.130;
z is more than or equal to 0.001 and less than or equal to 0.008, further z is more than or equal to 0.0020 and less than or equal to 0.0070, and further z is more than or equal to 0.0035 and less than or equal to 0.0055; the coating layer comprises a lithium halide.
The invention also provides a preparation method of the doped coating modified nickel-rich ternary cathode material, which comprises the following steps:
(1) mixing and ball-milling the nickel-rich ternary precursor with a lithium source and a halogen source (one or more of a fluorine source, a chlorine source and a bromine source) to obtain a ball-milled mixed material; the nickel-rich ternary precursor is Ni1-x-yCoyAlx(OH)2Wherein x is more than or equal to 0.030 and less than or equal to 0.050, and y is more than or equal to 0.100 and less than or equal to 0.150;
(2) sequentially pre-sintering and re-sintering the ball-milling mixed material obtained in the step (2) in an oxygen atmosphere to obtain a coated doped anode material; the pre-sintering temperature is 400-500 ℃, and the pre-sintering time is 4-6 h; the temperature of the re-sintering is 700-800 ℃, and the time of the re-sintering is 11-13 h;
in the present invention, the starting materials used are commercially available products well known to those skilled in the art, unless otherwise specified.
The invention mixes and ball-mills the nickel-rich ternary precursor with lithium source and halogen source (one or more of fluorine source, chlorine source and bromine source) to obtain ball-milled mixture. In the present invention, the lithium source preferably includes one or more of lithium hydroxide monohydrate, lithium acetate, and lithium carbonate; the molar ratio of the lithium source to the nickel-cobalt-aluminum precursor is preferably (1.03-1.08): 1, and more preferably 1.05:1, in terms of lithium content.
In the invention, the nickel-rich ternary precursor component is Ni1-x-yCoyAlx(OH)2Wherein x is more than or equal to 0.030 and less than or equal to 0.050, further, x is more than or equal to 0.035 and less than or equal to 0.045, and further, x = 0.040; y is more than or equal to 0.100 and less than or equal to 0.150, further, y is more than or equal to 0.135 and less than or equal to 0.145, and further, y = 0.150; in the invention, the values of x and y in the nickel-rich ternary precursor component are consistent with those in the core component in the technical scheme of the doped coating modified nickel-rich ternary cathode material; in the examples of the present invention, specifically Ni0.82Co0.13Al0.05(OH)2Or Ni0.815Co0.15Al0.035(OH)2。
In the present invention, the fluorine source comprises one or more of lithium fluoride, ammonium fluoride and tetrabutylammonium fluoride; the chlorine source comprises one or more of lithium chloride, ammonium chloride and benzyltriethylammonium chloride; the bromine source preferably comprises one or more of lithium bromide, ammonium bromide and tetramethylammonium bromide; the molar ratio of the halogen source to the nickel-rich ternary precursor is preferably (0.10-0.40): 100, more preferably (0.20 to 0.30): 100.
the invention mixes and ball-mills the nickel-rich ternary precursor with lithium source and halogen source to obtain ball-milled mixed material. In the invention, the mixing and ball milling time is preferably 10-12 h, and more preferably 10.5-11 h; the rotation speed of the mixing ball milling is preferably 100-150 r/min, and more preferably 120-145 r/min. In the present invention, the mixing ball milling is performed in a ball mill; the ball mill of the invention has no special requirements on the type of the ball mill, and can be prepared by the method well known by the technical personnel in the field. In the process of mixing and ball milling, the raw materials are mixed to obtain a precursor of the mixed halogen source and the lithium source.
After the ball-milling mixed material is obtained, the ball-milling mixed material is sequentially subjected to presintering and resintering to obtain the primary coated doped anode material. In the invention, the pre-sintering temperature is 400-500 ℃, preferably 420-480 ℃, and further preferably 450-460 ℃; the pre-sintering time is 4-6 h, preferably 4.2-4.5 h, and more preferably 4.3-4.4 h. In the invention, the pre-sintering temperature is preferably reached in a temperature rise mode, and the temperature rise rate is preferably 1-5 ℃/min, and more preferably 4.5-4.8 ℃/min.
In the invention, the temperature of the re-sintering is 700-800 ℃, preferably 710-770 ℃, and more preferably 720-750 ℃; the time for the re-sintering is 11-13 hours, preferably 11.2-11.5 hours. In the present invention, the temperature of the re-sintering is preferably obtained by raising the temperature of the pre-sintering; the heating rate is preferably 1 to 5 ℃/min, and more preferably 1.2 to 2 ℃/min. In the presintering and resintering processes, a halogen source reacts with the nickel-rich ternary precursor to realize the doping of halogen, and the formed component is LiNi1-x-yCoyAlxXzO2-0.5z(X = F, Cl, Br) halogen doped nickel rich ternary nuclei; meanwhile, part of halogen is remained on the surface of the nickel-rich ternary precursor and reacts with lithium at high temperature to generate a lithium halide amorphous coating structure, so that the coated nickel-rich ternary doped anode material is obtained.
In the present invention, the pre-sintering and re-sintering are performed under an oxygen atmosphere; the formation of the layered structure is related to oxygen, and the formed layered structure can be firmer in a pure oxygen atmosphere. The oxygen atmosphere is preferably high-purity oxygen with the purity of more than or equal to 99.5 percent; the manner in which the oxygen atmosphere is provided in the present invention is not particularly limited and may be any manner known to those skilled in the art.
After the re-sintering is finished, the sintered product is preferably naturally cooled to obtain the coated nickel-rich ternary cathode material.
For further illustration of the present invention, the doped coated modified nickel-rich ternary cathode material and the preparation method thereof provided by the present invention are described in detail below with reference to the drawings and examples, but they should not be construed as limiting the scope of the present invention.
Comparative example 1
Undoped uncoated nickel-rich cathode material LiNi0.815Co0.15Al0.035O2The preparation scheme is as follows:
nickel-rich ternary precursor (Ni)0.815Co0.15Al0.035(OH)2) Uniformly mixing the lithium hydroxide monohydrate and the lithium hydroxide by a ball mill at the speed of 100r/min for 10h to obtain a mixture, gradually heating to 450 ℃ at the speed of 5 ℃/min under the oxygen atmosphere for calcining for 5h, then gradually heating to 750 ℃ at the speed of 1 ℃/min for calcining for 12h, and naturally cooling to obtain the pure nickel-rich ternary cathode material (LiNi)0.815Co0.15Al0.035O2）。
Example 1
Preparing a positive electrode material:
(1) uniformly mixing the nickel-rich ternary precursor, a lithium source (lithium hydroxide monohydrate), ammonium fluoride and ammonium chloride for 10 hours at the speed of 100r/min by using a ball mill to obtain a precursor mixed with fluorine-chlorine-lithium; wherein, the ammonium fluoride and the ammonium chloride respectively account for 0.10mol percent of the nickel-rich ternary precursor; the molar ratio of the lithium source to the nickel-rich ternary precursor is 1.08: 1.
(2) Placing the mixed fluorine-chlorine-doped lithium precursor obtained in the step (1) in an atmosphere furnace, gradually heating to 450 ℃ at a speed of 5 ℃/min under an oxygen atmosphere, calcining for 5h, then gradually heating to 750 ℃ at a speed of 1 ℃/min, calcining for 12h, and naturally cooling to obtain a core body LiNi0.815Co0.15Al0.035F0.001Cl0.001O1.999And the surface is coated with a lithium halide nickel-rich ternary cathode material. And grinding and sieving the sintered material to obtain a refined primary cathode material for later use.
The SEM examination of the positive electrode materials obtained in example 1 and comparative example 1 showed that the results are shown in fig. 2 and fig. 1, respectively, and it can be seen from a comparison of fig. 1 and fig. 2 that the material obtained in comparative example 1 without doping coating had a smooth surface. Example 1 the positive electrode material obtained by doping coating had an amorphous lithium halide coating on the surface. Therefore, the obtained cathode material is a doping coating modified nickel-rich ternary cathode material and comprises a halogen-doped nickel-rich ternary core body and a coating layer. Meanwhile, element analysis and detection show that the component of the halogen-doped nickel-rich ternary cathode material nucleus is LiNi0.815Co0.15Al0.035F0.001Cl0.00 1O1.999The components of the coating layer are lithium fluoride and lithium chloride, and the ratio of the total substance amount of the coating layer to the substance amount of the halogen element doped nickel-rich ternary nucleus body is 0.0005: 1.
Example 2
A cathode material was prepared in the manner of example 1, except that ammonium fluoride and ammonium chloride each accounted for 0.20mol% of the molar fraction of the nickel-rich ternary precursor.
And performing element analysis and detection on the obtained cathode material, wherein the obtained cathode material is a doping-coating-modified nickel-rich ternary cathode material and comprises a halogen-doped nickel-rich ternary core body core coating layer, and the component of the halogen-doped nickel-rich ternary cathode material core body is LiNi0.815Co0.15Al0.035F0.002Cl0.002O1.998The components of the coating layer are lithium fluoride and lithium chloride, and the ratio of the total substance amount of the coating layer to the substance amount of the halogen element doped nickel-rich ternary nucleus body is 0.0010: 1.
Example 3
Preparing a positive electrode material:
(1) uniformly mixing the nickel-rich ternary precursor, a lithium source (lithium hydroxide monohydrate), ammonium fluoride and ammonium bromide for 10 hours at the speed of 100r/min by using a ball mill to obtain a precursor mixed with fluorine-doped lithium bromide; wherein, the ammonium fluoride and the ammonium bromide respectively account for 0.10mol percent of the nickel-rich ternary precursor; the molar ratio of the lithium source to the nickel-rich ternary precursor is 1.08: 1.
(2) Placing the mixed fluorine-chlorine-doped lithium precursor obtained in the step (1) in an atmosphere furnace, gradually heating to 450 ℃ at a speed of 5 ℃/min under an oxygen atmosphere, calcining for 5h, then gradually heating to 750 ℃ at a speed of 1 ℃/min, calcining for 12h, and naturally cooling to obtain a core body LiNi0.815Co0.15Al0.035F0.001Br0.001O1.999The surface is coated with a nickel-rich ternary cathode material of lithium halide; and grinding and sieving the sintered material to obtain a refined primary cathode material for later use.
Therefore, the obtained cathode material is a doping coating modified nickel-rich ternary cathode material and comprises a halogen-doped nickel-rich ternary core body and a coating layer. Meanwhile, element analysis and detection show that the component of the halogen-doped nickel-rich ternary cathode material nucleus is LiNi0.815Co0.15Al0.035F0.001 Br0.001O1.999The components of the coating layer are lithium fluoride and lithium bromide, and the ratio of the total substance amount of the coating layer to the substance amount of the halogen element doped nickel-rich ternary nucleus body is 0.0005: 1.
Example 4
A cathode material was prepared in the manner of example 3, except that ammonium fluoride and ammonium bromide each accounted for 0.20mol% of the molar fraction of the nickel-rich ternary precursor.
And performing element analysis and detection on the obtained cathode material, wherein the obtained cathode material is a doping-coating-modified nickel-rich ternary cathode material and comprises a halogen-doped nickel-rich ternary cathode material core coating layer, and the component of the halogen-doped nickel-rich ternary core is LiNi0.815Co0.15Al0.035F0.002Br0.002O1.998The components of the coating layer are lithium fluoride and lithium bromide, and the ratio of the total substance amount of the coating layer to the substance amount of the halogen element doped nickel-rich ternary nucleus body is 0.0010: 1.
Example 5
A cathode material was prepared in the manner of example 1, except that ammonium fluoride and ammonium chloride each accounted for 0.40mol% of the molar fraction of the nickel-rich ternary precursor.
The obtained positive electrode material is also subjected toElement analysis and detection show that the obtained cathode material is a doping coating modified nickel-rich ternary cathode material, and comprises a halogen-doped nickel-rich ternary core body core coating layer, wherein the component of the halogen-doped nickel-rich ternary cathode material core body is LiNi0.815Co0.15Al0.035F0.004Cl0.004O1.996The components of the coating layer are lithium fluoride and lithium chloride, and the ratio of the total substance amount of the coating layer to the substance amount of the halogen element doped nickel-rich ternary nucleus body is 0.0020: 1.
Example 6
A cathode material was prepared in the manner of example 3, except that ammonium fluoride and ammonium bromide each accounted for 0.40mol% of the molar fraction of the nickel-rich ternary precursor.
And performing element analysis and detection on the obtained cathode material, wherein the obtained cathode material is a doping-coating-modified nickel-rich ternary cathode material and comprises a halogen-doped nickel-rich ternary cathode material core coating layer, and the component of the halogen-doped nickel-rich ternary core is LiNi0.815Co0.15Al0.035F0.004Br0.004O1.996The components of the coating layer are lithium fluoride and lithium bromide, and the ratio of the total substance amount of the coating layer to the substance amount of the halogen element doped nickel-rich ternary nucleus body is 0.0020: 1.
The positive electrode materials obtained in examples 1 to 6 and comparative example were subjected to constant current charge and discharge tests, and when the charge and discharge rate was 0.5C in a high temperature environment of 55C,
the first specific discharge capacity of the cathode material obtained in the embodiment 1 can reach 200.3mAh/g, and can still reach 160.7mAh/g after 100 times of circulation, and the capacity retention rate is as high as 80.2%;
the first specific discharge capacity of the cathode material obtained in the embodiment 2 can reach 202.5mAh/g, 169.29 mAh/g can still be reached after 100 times of circulation, and the capacity retention rate is as high as 83.6%;
the first discharge specific capacity of the cathode material obtained in the embodiment 3 can reach 208 mAh/g, 174.9 mAh/g can still be achieved after 100 times of circulation, and the capacity retention rate is as high as 84.1%;
the first specific discharge capacity of the cathode material obtained in the embodiment 4 can reach 201.3 mAh/g, the cathode material can still reach 170.2mAh/g after being cycled for 100 times, and the capacity retention rate is as high as 84.6%;
the first specific discharge capacity of the cathode material obtained in the embodiment 5 can reach 200.7 mAh/g, 167.2 mAh/g can still be reached after 100 times of circulation, and the capacity retention rate is as high as 83.3%;
the first specific discharge capacity of the cathode material obtained in the embodiment 6 can reach 200.1 mAh/g, still can reach 165.5 mAh/g after 100 times of circulation, and the capacity retention rate is as high as 82.7%;
the first specific discharge capacity of the cathode material obtained in the comparative example 1 is only 194.2 mAh/g, the first specific discharge capacity after 100 cycles is 121.6 mAh/g, and the capacity retention rate is only 62.6%.
Compared with the test results, the positive electrode material obtained by the embodiment of the invention has the advantages of higher specific discharge capacity, excellent cycling stability, high rate capability and high temperature performance. The rate performance of the positive electrode materials obtained in comparative example 1 and example 3 at a rate of 0.1C, 0.2C, 1C, 2C, 3C, 4C, 5C, respectively, is: the positive electrode material of comparative example 1 has rate performances at rates of 0.1C, 0.2C, 1C, 2C, 3C, 4C, and 5C of 188.2mAh/g, 180.3mAh/g, 178.9mAh/g, 173.5mAh/g, 166.7mAh/g, 161.3mAh/g, 155.1mAh/g, and 150.6mAh/g, respectively; the rate capability of the positive electrode material of example 3 at 0.1C, 0.2C, 1C, 2C, 3C, 4C, 5C rates were 199.1 mAh/g, 184.8mAh/g, 181.9mAh/g, 176.3mAh/g, 172.6mAh/g, 170.0mAh/g, 165.4mAh/g, 160.7mAh/g, respectively.
The embodiment shows that the cathode material provided by the invention has excellent cycling stability, the nickel-rich ternary material is modified by doping and coating means, the internal crystal structure is improved, the corrosion of side reaction of electrolyte is improved from the inside and the outside of the material, and the cycling stability of the material is effectively improved on the premise of not affecting the capacity of the nickel-rich ternary cathode material obviously.
The embodiment shows that the cathode material provided by the invention has excellent cycling stability, and meanwhile, the nickel-rich ternary material is modified by using a doping means, part of halogen particles enter the particle through gaps to improve the crystal structure, and part of the halogen particles are left on the surface of the particle to form a lithium halide amorphous coating structure.
The reaction raw materials used in the preparation process are rich in sources, low in price and low in production cost, and are easy to be applied to large-scale commercial application.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. The preparation method of the doped, coated and modified nickel-rich ternary cathode material is characterized in that the doped, coated and modified nickel-rich ternary cathode material comprises a halogen-doped nickel-rich ternary nucleus and a lithium halide amorphous coating structure, and the chemical composition of the halogen element-doped nickel-rich ternary nucleus is LiNi1-x-yCoyAlxXzO2-0.5z(X = F, Cl, Br), wherein X is more than or equal to 0.030 and less than or equal to 0.050, y is more than or equal to 0.100 and less than or equal to 0.150, and z is more than or equal to 0.001 and less than or equal to 0.008;
the method specifically comprises the following steps:
(1) mixing the nickel-rich ternary precursor with a lithium source and a halogen source, and performing ball milling to obtain a ball-milled mixed material; the nickel-rich ternary precursor is Ni1-x-yCoyAlx(OH)2Wherein x is more than or equal to 0.030 and less than or equal to 0.050, y is more than or equal to 0.100 and less than or equal to 0.150, and the halogen source is selected from one or the combination of two or more of a fluorine source, a chlorine source and a bromine source;
(2) sequentially pre-sintering and re-sintering the ball-milling mixed material obtained in the step (2) in an oxygen atmosphere to obtain a coated doped anode material; the pre-sintering temperature is 400-500 ℃, and the pre-sintering time is 4-6 h; the temperature of the re-sintering is 700-800 ℃, and the time of the re-sintering is 11-13 h.
2. The preparation method of the doped coated modified nickel-rich ternary cathode material as claimed in claim 1, wherein the pre-sintering temperature and the re-sintering temperature in step (2) are both achieved by raising the temperature, and the rate of temperature rise is independently 1-5 ℃/min.
3. The method for preparing the doping coated modified nickel-rich ternary cathode material as claimed in claim 1, wherein the lithium source in the step (1) comprises one or more of lithium hydroxide monohydrate, lithium acetate and lithium carbonate.
4. The method for preparing the doped cladding-modified nickel-rich ternary cathode material according to claim 3, wherein the fluorine source in the step (1) comprises one or more of lithium fluoride, ammonium fluoride and tetrabutylammonium fluoride.
5. The preparation method of the doped coated modified nickel-rich ternary cathode material as claimed in claim 3, wherein the chlorine source in the step (1) comprises one or more of lithium chloride, ammonium chloride and benzyltriethylammonium chloride.
6. The method for preparing the doping coating modified nickel-rich ternary cathode material as claimed in claim 3, wherein the bromine source in the step (1) comprises one or more of lithium bromide, ammonium bromide and tetramethylammonium bromide.
7. The preparation method of the doped coated modified nickel-rich ternary cathode material as claimed in claim 3, wherein the mixing and ball milling time in step (1) is 10-12 h, and the rotation speed of the mixing and ball milling is 100-150 r/min.
8. The preparation method of the doped coated modified nickel-rich ternary cathode material as claimed in claim 3, wherein the molar ratio of the lithium source in the step (1) to the nickel-rich ternary precursor in the step (1) is (1.03-1.08): 1;
the molar ratio of the halogen source in the step (1) to the nickel-rich ternary precursor in the step (1) is (0.10-0.40): 100.
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| CN112117452B (en) * | 2020-10-09 | 2023-07-28 | 中伟新材料股份有限公司 | Positive electrode material coating agent and preparation method thereof, lithium ion battery positive electrode material, lithium ion battery and electric equipment |
| CN112652771B (en) * | 2020-12-22 | 2021-12-14 | 北京理工大学重庆创新中心 | Polyanion-doped single-crystal high-nickel positive electrode material and preparation method thereof |
| CN113307309A (en) * | 2021-04-08 | 2021-08-27 | 桂林理工大学 | Method for improving cycle performance of ternary cathode material of lithium ion battery through conversion of lithium fluoride coating layer |
| CN114314693A (en) * | 2021-12-29 | 2022-04-12 | 合肥融捷能源材料有限公司 | Modified ternary cathode material, preparation method thereof and lithium ion battery |
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