CN114335547A - High-rate ternary positive electrode material, and preparation method and application thereof - Google Patents
High-rate ternary positive electrode material, and preparation method and application thereof Download PDFInfo
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- CN114335547A CN114335547A CN202210217696.8A CN202210217696A CN114335547A CN 114335547 A CN114335547 A CN 114335547A CN 202210217696 A CN202210217696 A CN 202210217696A CN 114335547 A CN114335547 A CN 114335547A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 88
- 239000010406 cathode material Substances 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 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 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010937 tungsten Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 19
- HGHPQUIZVKPZEU-UHFFFAOYSA-N boranylidynezirconium Chemical compound [B].[Zr] HGHPQUIZVKPZEU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011164 primary particle Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 19
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 10
- 229940099596 manganese sulfate Drugs 0.000 claims description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims description 10
- 239000011702 manganese sulphate Substances 0.000 claims description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 10
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 10
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
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- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910001868 water Inorganic materials 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
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- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical group O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002345 surface coating layer Substances 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 5
- 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 5
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
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- 229910003176 Mn-O Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- BAEKJBILAYEFEI-UHFFFAOYSA-N lithium;oxotungsten Chemical compound [Li].[W]=O BAEKJBILAYEFEI-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a high-rate ternary cathode material, a preparation method and application thereof, and belongs to the technical field of lithium ion battery materials. The high-rate ternary cathode material comprises a base material and a coating layer on the surface of the base material, wherein the base material is zirconium-boron co-doped nickel-cobalt lithium manganate, and the coating layer contains tungsten and aluminum. The preparation method comprises the following steps: zr element homogeneous phase doping is adopted in a precursor coprecipitation stage, the hardness of the material is improved, B element doping is adopted in a primary sintering process to induce primary particles of the material to develop towards a thin strip shape, a large specific surface area is obtained, the rate capability is improved, W, Al is adopted for coating in the later stage to reduce the contact between the surface of the material and electrolyte, the cycle performance of the material is greatly improved, and the prepared ternary positive electrode material with high rate and high cycle performance can be widely applied as a lithium battery positive electrode material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a high-rate ternary cathode material and a preparation method and application thereof.
Background
The conventional micro-mixing system battery positive electrode material mainly comprises a small-particle ternary material and an LFP material, wherein the LFP compaction density is low, and the low-temperature performance is poor, a preparation method of a high-rate hollow sphere lithium nickelate positive electrode material is reported in patent CN109686972A, and a high-rate nickel cobalt lithium manganate positive electrode material and a preparation method thereof are reported in patent CN 109786695A.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a high-rate ternary cathode material, and a preparation method and application thereof.
The invention is realized by the following steps:
the invention provides a high-rate ternary cathode material which comprises a base material and a coating layer on the surface of the base material, wherein the base material is zirconium-boron co-doped nickel cobalt lithium manganate, and the coating layer contains tungsten and aluminum, wherein the doping amount of zirconium is 1000-3000 ppm of the mass of the nickel cobalt lithium manganate, the doping amount of boron is 1000-2000 ppm of the mass of the nickel cobalt lithium manganate, the coating amount of tungsten in the coating layer is 2000-4000 ppm of the mass of the nickel cobalt lithium manganate, and the coating amount of aluminum is 1000-2000 ppm of the mass of the nickel cobalt lithium manganate.
The invention also provides a preparation method of the high-rate ternary cathode material, which comprises the following steps: mixing a zirconium-doped nickel-cobalt-manganese precursor with a lithium source and a boron source, then sintering for the first time to obtain zirconium-boron-codoped nickel-cobalt lithium manganate, mixing the zirconium-boron-codoped nickel-cobalt lithium manganate with a tungsten source and an aluminum source, and then sintering for the second time to obtain the high-rate ternary cathode material.
The invention also provides application of the high-rate ternary cathode material as a lithium battery cathode material.
The invention has the following beneficial effects:
the invention provides a high-rate ternary cathode material, and a preparation method and application thereof. The high-rate ternary cathode material comprises a base material and a coating layer on the surface of the base material, wherein the base material is zirconium-boron-codoped nickel-cobalt lithium manganate, and the coating layer contains tungsten and aluminum. The preparation method comprises the following steps: zr element homogeneous phase doping is adopted in a precursor coprecipitation stage, the hardness of the material is improved, B element doping is adopted in a primary sintering process to induce primary particles of the material to develop towards a thin strip shape, a large specific surface area is obtained, the rate capability is improved, W, Al is adopted for coating in a later stage to reduce the contact between the surface of the material and electrolyte, and the cycle performance of the material is greatly improved, so that the prepared ternary cathode material with high rate and high cycle performance can be used as a lithium battery cathode material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a graph comparing XRD of examples and comparative examples;
FIG. 2 is a graph comparing the 003 peak at XRD for the examples and comparative examples;
fig. 3 is an SEM image of the zirconium-doped nickel cobalt manganese precursor provided in example 1;
fig. 4 is an SEM image of the ternary cathode material provided in example 1;
fig. 5 is an SEM image of the ternary cathode material provided in comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
One of the objectives of the present invention is to provide a high-rate ternary positive electrode material.
The second purpose of the invention is to provide a preparation method of the high-rate ternary cathode material.
The invention also aims to provide application of the high-rate ternary cathode material.
In order to achieve the above object, the technical solution of the present invention is as follows:
in a first aspect, an embodiment of the invention provides a high-rate ternary cathode material, which includes a substrate and a coating layer on the surface of the substrate, wherein the substrate is zirconium-boron co-doped lithium nickel cobalt manganese oxide, and the coating layer contains tungsten and aluminum, wherein the doping amount of zirconium is 1000ppm to 3000ppm of the mass of the lithium nickel cobalt manganese oxide, the doping amount of boron is 1000ppm to 2000ppm of the mass of the lithium nickel cobalt manganese oxide, the coating amount of tungsten in the coating layer is 2000ppm to 4000ppm of the mass of the lithium nickel cobalt manganese oxide, and the coating amount of aluminum is 1000ppm to 2000ppm of the mass of the lithium nickel cobalt manganese oxide.
The embodiment of the invention provides a high-rate ternary cathode material, wherein Zr is doped in nickel, cobalt and manganese, Zr element is adopted for homogeneous phase doping, the hardness of the material is improved, then B element doping is adopted, B reduces the surface energy of a (003) crystal face, the preferential growth of the (003) plane is maximized, a larger specific surface area is obtained, the rate performance is improved, W, Al is adopted for coating in the later period to reduce the contact between the surface of the material and electrolyte, and the cycle performance of the material is greatly improved.
In a second aspect, an embodiment of the present invention further provides a preparation method of the above high-rate ternary cathode material, including: mixing a zirconium-doped nickel-cobalt-manganese precursor with a lithium source and a boron source, then sintering for the first time to obtain zirconium-boron-codoped nickel-cobalt lithium manganate, mixing the zirconium-boron-codoped nickel-cobalt lithium manganate with a tungsten source and an aluminum source, and then sintering for the second time to obtain the high-rate ternary cathode material.
The embodiment of the invention also provides a preparation method of the high-rate ternary cathode material, which is characterized in that Zr is doped in nickel, cobalt and manganese firstly, so that the distribution of Zr of the sintered material is more uniform, and compared with Ni-O, Co-O and Mn-O bonds, the Zr-O bonds are more stable in a transition metal layer, and the crystal structure of the material can be stabilized. Introduction of Zr, resulting in Ni2+Orderly regulating and controlling the lithium layer and inhibiting H in the circulation process2-H3Harmful phase change, and effectively improves the charge and discharge performance and the cycle performance of the material.
Then, the zirconium-doped nickel-cobalt-manganese precursor is mixed with a lithium source and a boron source and then sintered for the first time, and B reduces the surface energy of the (003) crystal face, so that the preferential growth of the (003) face is maximized. Doping changes the microstructure (grain size and shape, crystal orientation) to relieve internal stress concentration caused by deep charge state phase transition. The primary particles which grow regularly obviously improve the specific surface area of the material and the rate capability of the material, and the 20C discharge retention rate is more than 95 percent. Simultaneously, the stability of the crystal structure is improved, and the O content is reduced2-: 2p can have potential, and a strong B-O bond (B-O: 809 kJ. mol) is introduced-1, Ni-O:382 kJ·mol-1) By enhancing the structural stability of oxygen, the air and thermal stability of the material is improved.
Then mixing the zirconium-boron co-doped nickel cobalt lithium manganate with a tungsten source and an aluminum source and then sintering for the second time, wherein WO is3The coating of the material can form lithium tungsten oxide on the surface layer of the primary particles, surface chemical modification is carried out, interface ion charge transfer is promoted, and the conductivity of the surface of the material is improved, so that the rate capability of the material is improved; the alumina coating layer inhibits the disappearance of oxygen vacancies at the later stage of the first charging, which leads to the reduction of the irreversible loss of the first discharge capacity, thereby improving the first efficiency and Al2O3Coating the surface of the ternary material to mechanically separate the material from the electrolyte, reducing the side reaction of the material and the electrolyte, inhibiting the dissolution of metal ions and Al2O3The coating of the oxide can prevent impedance from increasing in the charging and discharging processes, and the cycle stability of the material is improved.
In an alternative embodiment, the conditions for the first sintering are: uniformly mixing a zirconium-doped nickel-cobalt-manganese precursor, a lithium source and a boron source, heating to 750-790 ℃ at a heating rate of 2-3 ℃/min in an air atmosphere, preserving the temperature for 10-16 h, cooling, and sieving with a 400-mesh sieve to obtain the elongated spheroidal particles with the primary particles.
In an alternative embodiment, the molar ratio of the lithium source to the zirconium-doped nickel cobalt manganese precursor is from 1.07 to 1.12: 1, the lithium source is selected from one or more of lithium carbonate, lithium nitrate and lithium hydroxide; calculated by the content of boron element, the adding amount of the boron source is 0.05-0.3 percent of the mass of the zirconium-doped nickel-cobalt-manganese precursor, the boron source is selected from boric acid or boron oxide, and the particle size is less than or equal to 50 mu m.
In an alternative embodiment, the conditions for the second sintering are: uniformly mixing zirconium-boron-codoped nickel-cobalt lithium manganate, a tungsten source and an aluminum source, heating to 450-600 ℃ at the speed of 2-3 ℃/min in an air atmosphere, preserving the heat for 6-12 h, and sieving to obtain a high-rate ternary cathode material with a surface coating layer containing tungsten and aluminum.
In an optional embodiment, the addition amount of the tungsten source is 2000ppm to 4000ppm of the mass of the zirconium-boron co-doped nickel cobalt lithium manganate, the tungsten source is selected from tungsten oxide, and the particle size of particles is less than or equal to 300 nm; the adding amount of the aluminum source is 1000ppm-2000ppm of the mass of the zirconium-boron co-doped nickel cobalt lithium manganate, the aluminum source is selected from aluminum oxide, and the particle size of the particles is less than or equal to 40 nm.
In an alternative embodiment, the preparation of the zirconium doped nickel cobalt manganese precursor comprises the steps of: dissolving a nickel source, a cobalt source, a manganese source and a zirconium source in water according to a proportion to prepare a mixed solution with the total concentration of 2 mol/L, and mixing the mixed solution with the concentration of 2 mol/L and 2.5 mol/LNH3·H2Adding three materials of O and 8mol/L NaOH into a reaction container in a concurrent flow manner, controlling the stirring speed to be 600rpm-1000rpm, the temperature to be 53 ℃ and the pH value to be 11-12 in the atmosphere of inert atmosphere, reacting for 25h-35h, aging, filtering and washing the product until Na in the precursor+The content is 300 ppm-400ppm, vacuum drying is carried out for 10h-14h at 120 ℃, and then the spherical precursor is obtained after sieving by a standard 400-mesh sieve.
In an alternative embodiment, the composition of the zirconium-doped nickel cobalt manganese precursor is: (Ni)0.5 Co0.2Mn0.3)1-xZrx(OH)2Wherein x is more than or equal to 0.1 percent and less than or equal to 1 percent, D50 is approximately equal to 4 mu m, and the nickel source is selected from one or more of nickel sulfate, nickel acetate and nickel nitrate; the cobalt source is selected from one or more of cobalt sulfate, cobalt acetate and cobalt nitrate; the manganese source is selected from one or more of manganese sulfate, manganese acetate and manganese nitrate; the zirconium source is selected from one or more of zirconium nitrate and zirconium chloride.
In a third aspect, an embodiment of the present invention further provides an application of the above-mentioned high-rate ternary cathode material as a lithium battery cathode material.
The features and properties of the present invention are described in further detail below with reference to examples.
The following examples are intended to illustrate certain preferred embodiments of the invention and are not intended to limit the scope of the invention.
The specific surface area test methods for the following example and comparative example materials are referred to GB/T19587-2017.
And (3) electrochemical performance testing: the cathode material (the final product prepared in the example or the comparative example), acetylene black and polyvinylidene fluoride (PVDF) are prepared into slurry according to the mass ratio of 90:5:5 and coated on an aluminum foil, the aluminum foil loaded with the dried slurry is cut into small round pieces with the diameter of about 1cm by a cutting machine to be used as a cathode, a metal lithium piece is used as a cathode, Celgard2500 is used as a diaphragm, 1M carbonate solution is used as electrolyte (wherein, the solvent is a mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1:1, and the solute is LiPF6), and the small round pieces are assembled into a CR2025 button cell in an argon atmosphere glove box. The test is carried out on a charge and discharge tester at the temperature of 25 ℃ and the cut-off voltage within the range of 2.5-4.25 v.
Examples
Weighing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 50:20:30, dissolving the nickel sulfate, the cobalt sulfate and the manganese sulfate into deionized water to prepare a solution A with the concentration of 2.0mol/L, adding zirconium nitrate into the solution A, preparing a solution with the concentration of Zr ions of 0.004mol/L and the concentration of sodium hydroxide of 8mol/L, preparing a solution B, and preparing 2.5mol/L NH3·H2O aqueous solution as solution C;
three streams were separately metered in cocurrent flow into a 20L reaction vessel containing 4L of deionized water beforehandIt should be carried out under a nitrogen atmosphere. The stirring speed was controlled at 800rpm, and the temperature was maintained at 53 ℃. The pH value fluctuates around 12, when the reaction kettle is full of material liquid, clear liquid is pumped out of the reaction kettle by a precision filter, the liquid level in the kettle is kept stable and balanced, when material particles D50 in the reaction kettle grow to 3.5-4.0 mu m, the feeding is stopped, and the product is aged, filtered and washed until Na in the precursor+The content is 300 ppm, vacuum drying is carried out for 12h at 120 ℃, and a spherical precursor (Ni) is obtained after sieving by a standard 400-mesh sieve0.5Co0.2Mn0.3)0.998Zr0.002(OH)2，D50 3.7±0.2μm。
Will (Ni)0.5Co0.2Mn0.3)0.998Zr0.002(OH)2300g of precursor, 133.6g of lithium carbonate and a doping agent H3BO32.58g, uniformly mixing, heating to 770 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 12h, and obtaining the ternary material Li (Ni) after primary sintering0.5Co0.2Mn0.3)0.998Zr0.002O2And sieving with 400 mesh sieve.
Weighing sieved Li (Ni)0.5Co0.2Mn0.3)0.998Zr0.002O2300g of material, and coating agent WO3 1.14g，Al2O30.85g of the mixture is mixed and is subjected to heat preservation at 550 ℃ for 8 hours to finish secondary sintering, and the ternary cathode material with high multiplying power and high cycle performance is obtained.
Comparative example 1
Only the one-shot boron doping is reduced compared to the examples.
Weighing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 50:20:30, dissolving the nickel sulfate, the cobalt sulfate and the manganese sulfate into deionized water to prepare a solution A with the concentration of 2.0mol/L, adding zirconium nitrate into the solution A, preparing a solution with the concentration of Zr ions of 0.004mol/L and the concentration of sodium hydroxide of 8mol/L, preparing a solution B, and preparing 2.5mol/L NH3·H2O aqueous solution as solution C;
the three streams were each metered in co-currently into a 20L reaction vessel containing 4L of deionized water beforehand and the reaction was carried out under a nitrogen atmosphere. The stirring speed is controlled to be 800rpm, and the temperature is constantThe temperature was 53 ℃. The pH value fluctuates around 12, when the reaction kettle is full of material liquid, clear liquid is pumped out of the reaction kettle by a precision filter, the liquid level in the kettle is kept stable and balanced, when material particles D50 in the reaction kettle grow to 3.5-4.0 mu m, the feeding is stopped, and the product is aged, filtered and washed until Na in the precursor+The content is 300 ppm, vacuum drying is carried out for 12h at 120 ℃, and a spherical precursor (Ni) is obtained after sieving by a standard 400-mesh sieve0.5Co0.2Mn0.3)0.998Zr0.002(OH)2，D50 3.7±0.2μm。
Will (Ni)0.5Co0.2Mn0.3)0.998Zr0.002(OH)2Uniformly mixing 300g of precursor and 133.6g of lithium carbonate, heating to 770 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 12h, and obtaining the ternary material Li (Ni) after primary sintering0.5Co0.2Mn0.3)0.998Zr0.002O2And sieving with 400 mesh sieve.
Weighing sieved Li (Ni)0.5Co0.2Mn0.3)0.998Zr0.002O2300g of material, and coating agent WO3 1.14g，Al2O30.85g of the mixture was mixed and incubated at 550 ℃ for 8 hours to complete the second calcination.
Comparative example 2
Only the zirconium doping of the precursor synthesis process is reduced compared to the examples.
Weighing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 50:20:30, dissolving the nickel sulfate, the cobalt sulfate and the manganese sulfate into deionized water to prepare a solution A with the concentration of 2.0mol/L, preparing a solution B with the concentration of 8mol/L and preparing 2.5mol/L NH3·H2O aqueous solution as solution C;
the three streams were each metered in co-currently into a 20L reaction vessel containing 4L of deionized water beforehand and the reaction was carried out under a nitrogen atmosphere. The stirring speed was controlled at 800rpm, and the temperature was maintained at 53 ℃. The pH value fluctuates around 12, when the reaction kettle is full of material liquid, clear liquid is pumped out of the reaction kettle by using a precision filter, the liquid level in the kettle is kept stable and balanced, when the material particles D50 in the reaction kettle grow to 3.5-4.0 mu m, the feeding is stopped, and the product is agedFiltering and washing the solution until Na in the precursor+The content is 300 ppm, after vacuum drying for 12h at 120 ℃, the spherical precursor Ni is obtained after sieving by a standard 400-mesh sieve0.5Co0.2Mn0.3(OH)2，D50 3.7±0.2μm。
Mixing Ni0.5Co0.2Mn0.3(OH)2300g of precursor, 133.6g of lithium carbonate and a doping agent H3BO32.58g, uniformly mixing, heating to 770 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 12 hours, and obtaining the ternary material LiNi after primary sintering0.5Co0.2Mn0.3O2And sieving with 400 mesh sieve.
Weighing the screened LiNi0.5Co0.2Mn0.3O2300g of material, and coating agent WO3 1.14g，Al2O30.85g of the mixture was mixed and incubated at 550 ℃ for 8 hours to complete the second calcination.
Comparative example 3
Compared with the embodiment, only zirconium doping in the precursor synthesis process and boron doping in the sintering process are reduced.
Weighing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 50:20:30, dissolving the nickel sulfate, the cobalt sulfate and the manganese sulfate into deionized water to prepare a solution A with the concentration of 2.0mol/L, preparing a solution B with the concentration of 8mol/L and preparing 2.5mol/L NH3·H2O aqueous solution as solution C;
the three streams were each metered in co-currently into a 20L reaction vessel containing 4L of deionized water beforehand and the reaction was carried out under a nitrogen atmosphere. The stirring speed was controlled at 800rpm, and the temperature was maintained at 53 ℃. The pH value fluctuates around 12, when the reaction kettle is full of material liquid, clear liquid is pumped out of the reaction kettle by a precision filter, the liquid level in the kettle is kept stable and balanced, when material particles D50 in the reaction kettle grow to 3.5-4.0 mu m, the feeding is stopped, and the product is aged, filtered and washed until Na in the precursor+The content is 300 ppm, after vacuum drying for 12h at 120 ℃, the spherical precursor Ni is obtained after sieving by a standard 400-mesh sieve0.5Co0.2Mn0.3(OH)2，D50 3.7±0.2μm。
Mixing Ni0.5Co0.2Mn0.3(OH)2Uniformly mixing 300g of precursor and 133.6g of lithium carbonate, heating to 770 ℃ at the heating rate of 3 ℃/min, keeping the temperature for 12h, and obtaining the ternary material LiNi after primary burning0.5Co0.2Mn0.3O2And sieving with 400 mesh sieve.
Weighing the screened LiNi0.5Co0.2Mn0.3O2300g of material, and coating agent WO3 1.14g，Al2O30.85g of the mixture was mixed and incubated at 550 ℃ for 8 hours to complete the second calcination.
The composition morphology of the materials in the above examples and comparative examples is tested with reference to fig. 1, fig. 2, fig. 3, fig. 4 and fig. 5, it can be concluded from the figures that the above examples and comparative examples both synthesize layered ternary materials with perfect crystal form, and fig. 2 shows that the Zr doped and Zr + B doped samples 003 are shifted to small angles, the interlayer spacing of the surface material is increased, and the lithium ion migration during the charging and discharging process is facilitated. Fig. 3 shows that the synthesized precursor is well dispersed, primary grains are uniform, and no micro powder exists, and a comparison between fig. 4 and fig. 5 shows that B doping can induce primary grains of the material to grow to a long strip shape, so that the specific surface area of the material is increased, a diffusion channel of lithium ions in the material is shortened, and the performance of the material is effectively improved.
The materials in the above examples and comparative examples were tested for specific surface area and electrical properties, and the results are shown in table 1 below:
TABLE 1 BET and Electrical Performance results for ternary cathode materials prepared in examples and comparative examples
| Specific surface area (m2/g) | 0.1C specific volume (mAh/g) | 0.5C specific volume (mAh/g) | 1C specific capacity (mAh/g) | 3C specific capacity (mAh/g) | First effect (%) | 50th cycle capacity retention (%) | |
| Examples | 1.33 | 177.1 | 168.8 | 164.3 | 153.7 | 96.03 | 96.6 |
| Comparative example 1 | 1.02 | 172.8 | 162.7 | 157.4 | 147.4 | 94.81 | 95.4 |
| Comparative example 2 | 1.32 | 175.9 | 167.2 | 162.7 | 151.6 | 94.94 | 91.5 |
| Comparative example 3 | 1.03 | 169.4 | 158.9 | 152.8 | 141.5 | 93.70 | 90.3 |
From table 1 above, it can be derived: the capacity, multiplying power and cycle performance of the sample obtained in the embodiment are greatly improved compared with those of the comparative example. The Zr doping can improve the capacity of the material to a certain extent, obviously improve the cycle performance of the material, and the B doping can obviously improve the specific surface area and the capacity of the material.
Comparative example 4
Similar to the steps of example 1, except that the coating elements are different, the coating elements are Al and Ti, wherein the adding amount of Al is 1500 ppm of the mass of zirconium-boron co-doped nickel cobalt lithium manganate, the adding amount of Ti is 2000ppm of the mass of zirconium-boron co-doped nickel cobalt lithium manganate, the titanium source is selected from nano-scale titanium dioxide, and the particle size of the particles is less than or equal to 40 nm.
Comparative example 5
Similar to the procedure of example 1, except that: the coating amount of the coating element W was 5000 ppm.
Comparative example 6
Similar to the procedure of example 1, except that: the doping amount of Zr element is 4000 ppm.
Comparative example 7
Similar to the procedure of example 1, except that: the amount of the B element was 3000 ppm.
The materials in the above examples and comparative examples were tested for specific surface area and electrical properties, and the results are shown in table 2 below:
table 2 BET and electrical performance results for the ternary cathode material prepared in the comparative example
| Specific surface area (m2/g) | 0.1C specific volume (mAh/g) | 0.5C specific volume (mAh/g) | 1C specific capacity (mAh/g) | 3C specific capacity (mAh/g) | First effect (%) | 50th cycle capacity retention (%) | |
| Comparative example 4 | 1.32 | 174.5 | 165.5 | 161.0 | 148.7 | 95.03 | 94.1 |
| Comparative example 5 | 1.21 | 169.8 | 158.7 | 153.4 | 142.4 | 91.81 | 90.4 |
| Comparative example 6 | 1.02 | 165.4 | 157.8 | 152.4 | 141.3 | 88.94 | 84.5 |
| Comparative example 7 | 1.63 | 178.4 | 168.9 | 162.8 | 149.5 | 95.70 | 73.3 |
It can be seen from table 2 above that, after the coating element is changed, the change of the specific surface area of the material is small, and the capacity and the cycle performance are obviously reduced, probably because the W coating in the embodiment forms a fast ion conductor, which can effectively improve the conductivity of the material. However, when the coating amount of W is increased, the specific surface area of the material is reduced, the capacity is reduced more, and the coating amount is increased; the porous structure of the surface of the material is changed, and the contact between the electrolyte and the material particles is reduced, so that the internal resistance of the material is increased, and the electrical property is influenced; in the precursor stage, the doping amount of Zr is increased, so that the material result can be changed, the performance of the material is deteriorated, and the material can be mainly related to the lattice distortion caused by excessive doping amount; when the doping amount of B is further increased, the specific surface area of the material is remarkably increased, the discharge capacity of the material is increased, but the rate capability and the cycle performance are reduced, and B mainly induces primary particle refinement to cause overlarge specific surface area of the material, so that the side reaction with electrolyte is increased in the charging and discharging process, the surface structure of the material is damaged, and the capacity attenuation is serious in the cycle process.
The embodiment of the invention provides a high-rate ternary cathode material, and a preparation method and application thereof. The high-rate ternary cathode material comprises a base material and a coating layer on the surface of the base material, wherein the base material is zirconium-boron co-doped nickel-cobalt lithium manganate, and the coating layer contains tungsten and aluminum. The preparation method comprises the following steps: zr element homogeneous phase doping is adopted in a precursor coprecipitation stage, the hardness of the material is improved, B element doping is adopted in a primary sintering process to induce primary particles of the material to develop towards a thin strip shape, a large specific surface area is obtained, the rate capability is improved, W, Al is adopted for coating in a later stage to reduce the contact between the surface of the material and electrolyte, the cycle performance of the material is greatly improved, and the prepared ternary positive electrode material with high rate and high cycle performance can be widely used as a lithium battery positive electrode material.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The utility model provides a high magnification ternary cathode material, its characterized in that, high magnification ternary cathode material includes the coating on substrate and substrate surface, the substrate is the nickel cobalt lithium manganate that zirconium boron is codoped, the coating contains tungsten and aluminium, wherein, the doping amount of zirconium is 1000ppm-3000ppm of nickel cobalt lithium manganate quality, the doping amount of boron is 1000ppm-2000ppm of nickel cobalt lithium manganate quality, the cladding amount of tungsten is in the coating 2000ppm-4000ppm of nickel cobalt lithium manganate quality, the cladding amount of aluminium is in the coating 1000ppm-2000ppm of nickel cobalt lithium manganate quality.
2. A method for preparing a high-rate ternary positive electrode material according to claim 1, comprising: mixing a zirconium-doped nickel-cobalt-manganese precursor with a lithium source and a boron source, then sintering for the first time to obtain zirconium-boron-codoped nickel-cobalt lithium manganate, mixing the zirconium-boron-codoped nickel-cobalt lithium manganate with a tungsten source and an aluminum source, and then sintering for the second time to obtain the high-rate ternary cathode material.
3. The method according to claim 2, wherein the conditions for the first sintering are as follows: uniformly mixing the zirconium-doped nickel-cobalt-manganese precursor, the lithium source and the boron source, heating to 750-790 ℃ at a heating rate of 2-3 ℃/min in an air atmosphere, preserving the temperature for 10-16 h, cooling, and sieving with a 400-mesh sieve to obtain the elongated spheroidal particles with the primary particles.
4. The method of claim 3, wherein the molar ratio of the lithium source to the zirconium-doped nickel cobalt manganese precursor is from 1.07 to 1.12: 1, the lithium source is selected from one or more of lithium carbonate, lithium nitrate and lithium hydroxide; calculated by the content of boron element, the adding amount of the boron source is 0.05-0.3 percent of the mass of the zirconium-doped nickel-cobalt-manganese precursor, the boron source is selected from boric acid or boron oxide, and the particle size is less than or equal to 50 mu m.
5. The method according to claim 2, wherein the conditions for the second sintering are as follows: uniformly mixing the zirconium-boron-codoped nickel-cobalt lithium manganate, a tungsten source and an aluminum source, heating to 450-600 ℃ at the speed of 2-3 ℃/min in the air atmosphere, preserving the heat for 6-12 h, and sieving to obtain the high-rate ternary cathode material with the surface coating layer containing tungsten and aluminum.
6. The preparation method of claim 5, wherein the tungsten source is added in an amount of 2000ppm to 4000ppm based on the mass of the zirconium boron co-doped nickel cobalt lithium manganate, the tungsten source is selected from tungsten oxide, and the particle size of the tungsten source is less than or equal to 300 nm; the adding amount of the aluminum source is 1000ppm-2000ppm of the mass of the zirconium-boron co-doped nickel cobalt lithium manganate, the aluminum source is selected from aluminum oxide, and the particle size of the particles is less than or equal to 40 nm.
7. The method of claim 2, wherein the preparing of the zirconium doped nickel cobalt manganese precursor comprises the steps of: dissolving a nickel source, a cobalt source, a manganese source and a zirconium source in water according to a proportion to prepare a mixed solution with the total concentration of 2 mol/L, and mixing the mixed solution with the total concentration of 2 mol/L and 2.5mol/L NH3·H2Adding three materials of O and 8mol/L NaOH into a reaction container in a concurrent flow manner, controlling the stirring speed to be 600rpm-1000rpm, the temperature to be 53 ℃ and the pH value to be 11-12 in the atmosphere of inert atmosphere, reacting for 25h-35h, aging, filtering and washing the product until Na in the precursor+The content is 300 ppm-400ppm, vacuum drying is carried out for 10h-14h at 120 ℃, and then the spherical precursor is obtained after sieving by a standard 400-mesh sieve.
8. The method of claim 7, wherein the composition of the zirconium-doped nickel-cobalt-manganese precursor is: (Ni)0.5 Co0.2Mn0.3)1-xZrx(OH)2Wherein x is more than or equal to 0.1 percent and less than or equal to 1 percent, D50 is approximately equal to 4 mu m, and the nickel source is selected from one or more of nickel sulfate, nickel acetate and nickel nitrate; the cobalt source is selected from one or more of cobalt sulfate, cobalt acetate and cobalt nitrate; the manganese source is selected from one or more of manganese sulfate, manganese acetate and manganese nitrate; the zirconium source is selected from one or more of zirconium nitrate and zirconium chloride.
9. Use of the high-rate ternary cathode material according to claim 1 or the high-rate ternary cathode material prepared by the preparation method according to any one of claims 2 to 8 as a cathode material for a lithium battery.
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