CN113809320A - Quaternary polycrystalline positive electrode material, and preparation method and application thereof - Google Patents
Quaternary polycrystalline positive electrode material, and preparation method and application thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 38
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 33
- 239000010941 cobalt Substances 0.000 claims abstract description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 32
- -1 nickel-cobalt-manganese-aluminum Chemical compound 0.000 claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 28
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910013716 LiNi Inorganic materials 0.000 claims abstract 2
- 239000011248 coating agent Substances 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 23
- 229910052796 boron Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 239000010406 cathode material Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 15
- 238000007873 sieving Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 238000007580 dry-mixing Methods 0.000 claims description 9
- FYWUVDVZWURZJH-UHFFFAOYSA-E [OH-].[Al+3].[Mn+2].[Co+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Al+3].[Mn+2].[Co+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-] FYWUVDVZWURZJH-UHFFFAOYSA-E 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims 2
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 76
- 229910052759 nickel Inorganic materials 0.000 abstract description 46
- 239000000463 material Substances 0.000 abstract description 37
- 239000013078 crystal Substances 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 description 50
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000011164 primary particle Substances 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 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 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910014758 LiNiaCobMnc Inorganic materials 0.000 description 1
- 229910013172 LiNixCoy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
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- 230000002427 irreversible effect Effects 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01—ELECTRIC ELEMENTS
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- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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Abstract
本发明提供了一种四元多晶正极材料、其制备方法和用途，所述四元多晶正极材料的化学式为LiNiaCobMncAldTa(1‑a‑b‑c‑d)O2，其中，0.9≤a＜1，0＜b＜0.07，0＜c＜0.03，0＜d≤0.002，所述制备方法包括：镍钴锰铝四元前驱体、锂源、钽源和钴源混合得到混合物，对混合物煅烧后制备得到所述四元多晶正极材料。本发明通过Co/Ta共掺杂，对超高镍正极材料进行晶体微结构的调节来稳定材料结构，减少锂镍混排程度，提高超高镍正极材料的容量及循环寿命，具有制备工艺简单、稳定性高和电性能优异等特点。
The invention provides a quaternary polycrystalline positive electrode material, a preparation method and application thereof, and the chemical formula of the quaternary polycrystalline positive electrode material is LiNi a Co b Mn c Al d Ta (1‑a‑b‑c‑d) O 2 , wherein, 0.9≤a<1, 0<b<0.07, 0<c<0.03, 0<d≤0.002, and the preparation method includes: nickel-cobalt-manganese-aluminum quaternary precursor, lithium source, tantalum source and The cobalt source is mixed to obtain a mixture, and the quaternary polycrystalline positive electrode material is prepared by calcining the mixture. The invention adjusts the crystal microstructure of the ultra-high nickel positive electrode material through Co/Ta co-doping to stabilize the material structure, reduces the degree of mixing of lithium and nickel, improves the capacity and cycle life of the ultra-high nickel positive electrode material, and has the advantages of simple preparation process. , high stability and excellent electrical properties.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a quaternary polycrystalline positive electrode material, and a preparation method and application thereof.
Background
Lithium ion batteries have become the most widely used electrochemical power source at present, and the most representative of such batteries is lithium secondary batteries (LIBs) which generate electric energy by the change of chemical potential when lithium ions in a positive electrode and a negative electrode are intercalated and deintercalated. The positive electrode material has a direct leading effect on the performance of LIBs, and therefore, many researchers are dedicated to realizing a positive electrode material which has a large capacity, a fast charge/discharge speed and a long cycle life and can reversibly intercalate and deintercalate lithium ions. Currently, ultra-high nickel materials are considered to be the most promising candidate materials because they can increase the specific capacity of lithium ion batteries by increasing the nickel content. However, the resulting poor cycling stability of lithium ion batteries may hinder the success of this approach.
In addition, the quaternary polycrystalline material in the ultra-high nickel material has more advantages in safety than the ternary cathode material, and is one of the most promising materials at present. However, the poor cycle stability of the ultra-high nickel layered cathode material is mainly attributed to that the lithium-nickel mixing and discharging is more serious with the increase of the nickel content, the conductivity of the material is poor, the irreversible loss of lithium ion intercalation and deintercalation is more serious, and the generation of particle cracks and the release of oxygen are accelerated, which is also considered to be a main reason for the performance degradation of the ultra-high nickel layered cathode material.
CN109704413A discloses a high nickel cathode material and a method for improving storage performance of the high nickel cathode material. The high nickel anode material is prepared fromChemical formula LiNixCoyMnzAl1-x-y-zO2Represents; wherein x is more than or equal to 0.5 and less than 1, y is more than 0 and less than 0.5, z is more than 0 and less than 0.5, and 1-x-y-z is more than 0. Mixing inorganic salt containing manganese, inorganic salt containing aluminum, LiOH. H2O and a high-nickel precursor, adding ethanol, and grinding uniformly to obtain a solid powder mixture; and pre-calcining the obtained solid powder mixture, and then heating to calcine to obtain the high-nickel cathode material. The method effectively inhibits the side reaction of the high-nickel anode material with moisture and carbon dioxide in the air, and improves the surface stability of the material, thereby improving the storage performance of the material and being beneficial to the commercial application of the high-nickel anode material.
CN111606363A discloses a preparation method of a modified high-nickel anode material, which comprises the steps of uniformly mixing a high-nickel anode material precursor, an additive and a lithium source, carrying out primary sintering in an oxygen atmosphere, crushing and sieving to obtain a primary sintered high-nickel anode material; washing and drying the primary sintered high-nickel anode material to obtain a washed and dried primary sintered high-nickel anode material; carrying out primary surface treatment on the washed and dried primary sintered high-nickel anode material to obtain a primary surface-treated high-nickel anode material; and uniformly mixing the modifier with the primary surface-treated high-nickel anode material, and then carrying out secondary surface treatment to obtain the modified high-nickel anode material. The invention reduces the residual alkali amount on the surface of the material and the specific surface area of the final product, obviously reduces the impedance on the surface of the material, obviously relieves the gas generation phenomenon of the battery, improves the structural stability and the circulation stability of the material, can improve the processing performance of the anode material in the preparation process, has easily controlled preparation conditions and can be produced in large batch.
CN109950497A discloses a high nickel cathode material with a uniform coating layer and a preparation method thereof, the preparation method comprises the following steps: (1) adding deionized water and a high-nickel anode material into a container, and uniformly stirring to obtain a suspension; (2) slowly adding metal soluble salt into the suspension liquid obtained in the step (1), uniformly stirring, carrying out vacuum filtration, washing with absolute ethyl alcohol, pumping, and drying in an oven to obtain a dry material; (3) and (3) placing the dried material obtained in the step (2) in a sagger, sintering at high temperature in a preheated muffle furnace oxygen atmosphere, cooling, crushing, and sieving to obtain the high-nickel anode material with a uniform coating layer. The high-nickel anode material has high specific capacity, long circulation, better thermal stability and structural stability, and simultaneously, because of the operation of water washing, the amounts of lithium hydroxide and lithium carbonate on the surface of the high-nickel anode material are greatly reduced, the powder resistance of the material is reduced, the first effect is improved, the specific capacity is increased, and the pH value of the high-nickel anode material is reduced.
The existing positive electrode material has the problems of poor stability, poor electrical property, complex preparation method and the like, so that the problem that how to ensure the excellent stability and electrical property of the positive electrode material under the condition of simple preparation process becomes the problem which needs to be solved urgently at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a quaternary polycrystalline anode material, a preparation method and application thereof, wherein the crystal microstructure of the ultrahigh nickel anode material is adjusted by Co/Ta Co-doping to stabilize the material structure, reduce the mixed arrangement degree of lithium and nickel, improve the capacity and cycle life of the ultrahigh nickel anode material, and the quaternary polycrystalline anode material has the characteristics of simple preparation process, high stability, excellent electrical property and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a quaternary polycrystalline cathode material, which is prepared by the preparation method of the first aspect.
As a preferable technical scheme of the invention, the chemical formula of the quaternary polycrystalline positive electrode material is LiNiaCobMncAldTa(1-a-b-c-d)O2Where 0.9. ltoreq. a < 1, 0. ltoreq. b < 0.07, 0. ltoreq. c < 0.03, 0. ltoreq. d < 0.002, where 0.9. ltoreq. a < 1, for example a is 0.90, 0.91, 0.92, 0.93, 0.94, 0.95, 0.96, 0.97, 0.98 or 0.99, 0. ltoreq. b < 0.07, for example b is 0.01, 0.02, 0.03, 0.04, 0.05, 0.06 or 0.07, 0. ltoreq. c < 0.03, for example c is 0.005, 0.010, 0.015, 0.020, 0.025 or 0.030, 0. ltoreq. d.002, for example d is 0.0005, 0.0010, 0.0015 or 0.0020.
According to the invention, the crystal microstructure of the quaternary polycrystalline anode material is adjusted by Co-doping Co/Ta, so that the lattice structure is stabilized, wherein cobalt doping mainly inhibits divalent nickel from entering a lithium position, the lithium-nickel mixed-discharging degree is reduced, and then the electronic conductivity of the material is improved by gradient doping on the surface; the tantalum doping can improve the interlayer spacing of the transition metal layer, thereby improving the diffusion rate of lithium ions and further improving the cycle life of the ultra-high nickel cathode material. Furthermore, the Co/Ta Co-doping adjusts the microstructure of the anode material, stabilizes the crystal lattice, reduces the mixed arrangement degree of lithium and nickel, and improves the electronic conductivity and the lithium ion diffusion rate of the material, thereby improving the capacity and the cycling stability of the material.
In a preferred embodiment of the present invention, the quaternary polycrystalline positive electrode material is coated with a boron coating layer.
In a second aspect, the present invention provides a method for preparing a quaternary polycrystalline positive electrode material, the method comprising: and mixing the nickel-cobalt-manganese-aluminum quaternary precursor, a lithium source, a tantalum source and a cobalt source to obtain a mixture, and calcining the mixture to obtain the quaternary polycrystalline positive electrode material.
In a preferred embodiment of the present invention, the molar ratio of the lithium element in the lithium source to the total of the non-lithium metal elements in the mixture is (1-1.05): 1, for example, 1.005:1, 1.010:1, 1.015:1, 1.020:1, 1.025:1, 1.030:1, 1.035:1, 1.040:1, 1.045:1 or 1.050: 1.
Note that, the non-lithium metal elements in the mixture, that is, all other metal elements except lithium in the mixture, are represented by nickel, cobalt, manganese, aluminum, tantalum, and cobalt in the present invention.
Preferably, the molar ratio of the tantalum source to the nickel-cobalt-manganese-aluminum quaternary precursor is (0.0005-0.0015): 1, for example, 0.0005:1, 0.0006:1, 0.0007:1, 0.0008:1, 0.0009:1, 0.0010:1, 0.0011:1, 0.0012:1, 0.0013:1, 0.0014:1, or 0.0015: 1.
According to the invention, the molar ratio of the tantalum source to the nickel-cobalt-manganese-aluminum quaternary precursor is controlled to be (0.0005-0.00015): 1, so that the growth of primary particles in the preparation process is ensured, the spacing of transition metal layers is increased, and if the molar ratio is lower than 0.0005:1, the effect of increasing the spacing of the transition metal layers is not achieved; if the molar ratio is higher than 0.0015:1, the growth of primary particles is inhibited.
Preferably, the molar ratio of the cobalt source to the nickel-cobalt-manganese-aluminum quaternary precursor is (0.006-0.01): 1, such as 0.0060, 0.0065, 0.0070, 0.0075, 0.0080, 0.0085, 0.0090, 0.0095 or 0.0100.
According to the invention, the molar ratio of the cobalt source to the nickel-cobalt-manganese-aluminum quaternary precursor is controlled to be (0.006-0.01): 1, so that the stability is effectively enhanced, and if the molar ratio is lower than 0.006:1, the material has poor stability effect; if the molar ratio is higher than 0.010:1, the cost is high.
Preferably, in the nickel-cobalt-manganese-aluminum quaternary precursor, the molar ratio of the elements Ni, Co, Mn and Al is (85-95): (5-9): 1-3): 0.5-1.5, such as 85:9:1:1.5, 95:9:3:1.5, 85:3:1:0.5 or 90:7:2:1, preferably 90:7:2: 1.
Preferably, the nickel-cobalt-manganese-aluminum quaternary precursor comprises nickel-cobalt-manganese-aluminum hydroxide.
Illustratively, there is provided a preparation method of the above nickel cobalt manganese aluminum hydroxide, the preparation method comprising: respectively weighing a nickel source, a cobalt source, a manganese source and an aluminum source according to the molar ratio of metal elements, and preparing the nickel-cobalt-manganese-aluminum hydroxide by adopting a coprecipitation method, wherein preparation parameters can be reasonably selected by a person skilled in the art according to the requirements of products.
As a preferred embodiment of the present invention, the lithium source includes one or a combination of at least two of lithium hydroxide, lithium carbonate, and lithium nitrate.
Preferably, the tantalum source comprises Ta2O5And/or TaC.
Preferably, the cobalt source comprises Co3O4And/or Co (OH)2。
In a preferred embodiment of the present invention, the calcination temperature is 700 to 800 ℃, for example 700 ℃, 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃ or 800 ℃.
According to the invention, the calcination temperature is controlled to be 700-800 ℃, the particle size and morphology of the particles are ensured, the material capacity is improved, and if the temperature is lower than 700 ℃, the primary particles are not large in length and the gas generation is serious; if the temperature is higher than 800 ℃, the problem of overburning exists, and the capacity exertion of the material is influenced.
Preferably, the calcination time is 7-9 h, such as 7.0h, 7.2h, 7.4h, 7.6h, 7.8h, 8.0h, 8.2h, 8.4h, 8.6h, 8.8h or 9.0 h.
Preferably, the calcination is carried out under an oxygen atmosphere.
Preferably, the mixing is performed by dry mixing.
Preferably, the calcination is followed by cooling, crushing and sieving in that order.
As a preferred technical solution of the present invention, the quaternary polycrystalline positive electrode material is subjected to coating treatment.
Preferably, the coating treatment is boron coating.
According to the invention, the quaternary polycrystalline anode material is further coated with boron, the coating can be carried out at a lower temperature by adopting the boron coating, and a uniform protective film can be formed, so that the capacity and the cycle stability of the material are further enhanced.
Preferably, the boron cladding comprises: and stirring and mixing the quaternary polycrystalline anode material with distilled water, drying, mixing with a boron coating agent, and coating and calcining to obtain the coated quaternary polycrystalline anode material.
It should be noted that the coating calcination should be followed by cooling and sieving treatment according to the particle size of the material.
Preferably, the volume ratio of the quaternary polycrystalline positive electrode material to distilled water is 1: (1-2) is, for example, 1:1.0, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1: 2.0.
Preferably, the stirring speed is 200-400 r/min, such as 200r/min, 220r/min, 240r/min, 260r/min, 280r/min, 300r/min, 320r/min, 340r/min, 360r/min, 380r/min or 400 r/min.
Preferably, the stirring time is 5-15 min, such as 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15 min.
Preferably, the drying temperature is 100-200 ℃, such as 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃.
Preferably, the drying time is 5-10 h, such as 5.0h, 5.5h, 6.0h, 6.5h, 7.0h, 7.5h, 8.0h, 8.5h, 9.0h, 9.5h or 10.0 h.
Preferably, the drying is performed in a vacuum drying oven.
In a preferred embodiment of the present invention, the molar ratio of the boron capping agent to the quaternary polycrystalline positive electrode material is (0.01 to 0.03):1, and is, for example, 0.010:1, 0.012:1, 0.014:1, 0.016:1, 0.018:1, 0.020:1, 0.022:1, 0.024:1, 0.026:1, 0.028:1, or 0.030: 1.
Preferably, the boron capping agent comprises boric acid and/or boron oxide.
Preferably, the temperature of the coating calcination is 250 to 350 ℃, for example, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃ or 350 ℃.
Preferably, the coating calcination time is 7-9 h, such as 7.0h, 7.2h, 7.4h, 7.6h, 7.8h, 8.0h, 8.2h, 8.4h, 8.6h, 8.8h or 9.0 h.
Preferably, the mixing mode of the boron coating agent and the quaternary polycrystalline positive electrode material is dry mixing.
As a preferred technical scheme of the invention, the preparation method specifically comprises the following steps:
the method comprises the following steps of (I) mixing a nickel-cobalt-manganese-aluminum quaternary precursor, a lithium source, a tantalum source and a cobalt source in a dry method to obtain a mixture, wherein the molar ratio of lithium elements in the lithium source to the sum of non-lithium metal elements in the mixture is (1-1.05): 1, the molar ratio of the tantalum source to the nickel-cobalt-manganese-aluminum quaternary precursor is (0.0005-0.0015): 1, and the molar ratio of the cobalt source to the nickel-cobalt-manganese-aluminum quaternary precursor is (0.006-0.01): 1;
calcining the mixture obtained in the step (I) for 7-9 hours at 700-800 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the quaternary polycrystalline anode material;
and (III) stirring and mixing the quaternary polycrystalline anode material obtained in the step (II) with distilled water according to the ratio of (1) - (2) to (200-400 r/min for 5-15 min, drying at 100-200 ℃ for 5-10 h, drying, mixing with a boron coating agent in a dry method, wherein the molar ratio of the boron coating agent to the quaternary polycrystalline anode material is (0.01-0.03): 1, and coating and calcining at 250-350 ℃ for 7-9 h to obtain the coated quaternary polycrystalline anode material.
In a third aspect, the present invention provides a battery comprising a positive electrode, a negative electrode and a separator, wherein the positive electrode material in the positive electrode comprises the quaternary polycrystalline positive electrode material of the second aspect.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the crystal microstructure of the quaternary polycrystalline anode material is adjusted by Co-doping Co/Ta, so that the lattice structure is stabilized, wherein cobalt doping mainly inhibits divalent nickel from entering a lithium position, the lithium-nickel mixed-discharging degree is reduced, and then the electronic conductivity of the material is improved by gradient doping on the surface; the tantalum doping can improve the interlayer spacing of the transition metal layer, thereby improving the diffusion rate of lithium ions and further improving the cycle life of the ultra-high nickel cathode material. Furthermore, the Co/Ta Co-doping is adopted to adjust the microstructure of the anode material, stabilize the crystal lattice, reduce the lithium-nickel mixed discharge degree and improve the electronic conductivity and the lithium ion diffusion rate of the material, so that the capacity and the cycle stability of the material are improved, the first effect is more than 86.2%, the 50-turn cycle retention rate is more than 90.5%, and further, in the preferred range, the first effect is more than 93.1%, and the 50-turn cycle retention rate is more than 96.5%.
Drawings
FIG. 1 is a graph showing the first charge and discharge curves of example 1;
fig. 2 is a first charge and discharge graph of comparative example 1.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
Example 1
The embodiment provides a preparation method of a quaternary polycrystalline positive electrode material, which specifically comprises the following steps:
(I) Nickel-cobalt-manganese-aluminum hydroxide (molar ratio of Ni: Co: Mn: Al elements is 90:7:2:1), lithium hydroxide, Ta2O5And Co3O4Performing dry mixing to obtain a mixture, wherein the molar ratio of lithium elements in a lithium source to the sum of non-lithium metal elements in the mixture is 1.025:1, the molar ratio of a tantalum source to a nickel-cobalt-manganese-aluminum quaternary precursor is 0.0001:1, and the molar ratio of a cobalt source to the nickel-cobalt-manganese-aluminum quaternary precursor is 0.008: 1;
calcining the mixture obtained in the step (I) for 8 hours at 750 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the quaternary polycrystalline anode material;
and (III) stirring and mixing the quaternary polycrystalline anode material obtained in the step (II) with distilled water according to a ratio of 1:1, stirring at a speed of 300r/min for 10min, drying at 150 ℃ for 10h, drying, mixing with boric acid in a dry method, coating and calcining at 300 ℃ for 8h, cooling and sieving to obtain the coated quaternary polycrystalline anode material, wherein the molar ratio of the boric acid to the quaternary polycrystalline anode material is 0.01: 1.
The chemical formula of the prepared quaternary polycrystalline anode material is LiNi0.891Co0.078Mn0.02Al0.011Ta0.001O2。
Example 2
The embodiment provides a preparation method of a quaternary polycrystalline positive electrode material, which specifically comprises the following steps:
(I) Nickel-cobalt-manganese-aluminum hydroxide (Ni: Co: Mn: Al element molar ratio is 90:7:2:1), hydroxideLithium, Ta2O5And Co3O4Performing dry mixing to obtain a mixture, wherein the molar ratio of lithium elements in a lithium source to the sum of non-lithium metal elements in the mixture is 1:1, the molar ratio of a tantalum source to a nickel-cobalt-manganese-aluminum quaternary precursor is 0.0005:1, and the molar ratio of a cobalt source to the nickel-cobalt-manganese-aluminum quaternary precursor is 0.006: 1;
calcining the mixture obtained in the step (I) for 9 hours at 700 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the quaternary polycrystalline anode material;
and (III) stirring and mixing the quaternary polycrystalline anode material obtained in the step (II) with distilled water according to a ratio of 1:2, stirring at a speed of 200r/min for 15min, drying at 100 ℃ for 10h, drying, mixing with boric acid in a dry method, coating and calcining at 250 ℃ for 9h, cooling and sieving to obtain the coated quaternary polycrystalline anode material, wherein the molar ratio of the boric acid to the quaternary polycrystalline anode material is 0.02: 1.
The chemical formula of the prepared quaternary polycrystalline anode material is LiNi0.8935Co0.076Mn0.02Al0.01Ta0.0005O2。
Example 3
The embodiment provides a preparation method of a quaternary polycrystalline positive electrode material, which specifically comprises the following steps:
(I) Nickel-cobalt-manganese-aluminum hydroxide (molar ratio of Ni: Co: Mn: Al elements is 90:7:2:1), lithium hydroxide, Ta2O5And Co3O4Performing dry mixing to obtain a mixture, wherein the molar ratio of lithium elements in a lithium source to the sum of non-lithium metal elements in the mixture is 1.05:1, the molar ratio of a tantalum source to a nickel-cobalt-manganese-aluminum quaternary precursor is 0.0015:1, and the molar ratio of a cobalt source to the nickel-cobalt-manganese-aluminum quaternary precursor is 0.01: 1;
calcining the mixture obtained in the step (I) for 7 hours at 800 ℃ in an oxygen atmosphere, cooling, crushing and sieving to obtain the quaternary polycrystalline anode material;
and (III) stirring and mixing the quaternary polycrystalline anode material obtained in the step (II) with distilled water according to a ratio of 1:1.5, stirring at a speed of 400r/min for 5min, drying at 200 ℃ for 5h, drying, mixing with boric acid in a dry method, coating and calcining at 350 ℃ for 7h, cooling and sieving to obtain the coated quaternary polycrystalline anode material, wherein the molar ratio of the boric acid to the quaternary polycrystalline anode material is 0.03: 1.
The chemical formula of the prepared quaternary polycrystalline anode material is LiNi0.8885Co0.08Mn0.02Al0.01Ta0.0015O2。
Example 4
This example provides a method for preparing a quaternary polycrystalline positive electrode material, which is different from example 1 in that the molar ratio of the tantalum source to the nickel-cobalt-manganese-aluminum quaternary precursor is 0.0003:1, and the rest steps and parameters are completely the same as those in example 1.
Example 5
The embodiment provides a preparation method of a quaternary polycrystalline cathode material, compared with the embodiment 1, the difference is that the molar ratio of a tantalum source to a nickel-cobalt-manganese-aluminum quaternary precursor is 0.0020:1, and the rest steps and parameters are completely the same as those of the embodiment 1.
Example 6
This example provides a method for preparing a quaternary polycrystalline positive electrode material, which is different from example 1 in that the molar ratio of the cobalt source to the nickel-cobalt-manganese-aluminum quaternary precursor is 0.003:1, and the rest steps and parameters are completely the same as those in example 1.
Example 7
The embodiment provides a preparation method of a quaternary polycrystalline cathode material, compared with the embodiment 1, the difference is that the molar ratio of a cobalt source to a nickel-cobalt-manganese-aluminum quaternary precursor is 0.012:1, and the rest steps and parameters are completely the same as the embodiment 1.
Example 8
This example provides a method for preparing a quaternary polycrystalline positive electrode material, which is different from example 1 in that the calcination temperature in step (ii) is 600 ℃, and the rest of the steps and parameters are exactly the same as those in example 1.
Example 9
This example provides a method for preparing a quaternary polycrystalline positive electrode material, which is different from example 1 in that the calcination temperature in step (ii) is 900 ℃, and the remaining steps and parameters are exactly the same as those in example 1.
Example 10
This example provides a method for preparing a quaternary polycrystalline positive electrode material, which is different from example 1 in that boron coating, i.e., step (iii), is not performed, and the remaining steps and parameters are exactly the same as those of example 1.
Example 11
Compared with the embodiment 1, the difference of the preparation method of the quaternary polycrystalline anode material is that the cobalt doping is not carried out, the content of the cobalt element in the nickel-cobalt-manganese-aluminum hydroxide is adjusted, the element composition of the finally prepared material is completely the same as that of the embodiment 1, and the rest steps and parameters are completely the same as those of the embodiment 1.
Comparative example 1
This comparative example provides a method for preparing a quaternary polycrystalline positive electrode material, which is different from example 1 in that cobalt doping and tantalum doping are not performed, i.e., a cobalt source and a tantalum source are not added, and the remaining steps and parameters are completely the same as those of example 1.
Comparative example 2
This comparative example provides a method of making a quaternary polycrystalline positive electrode material, which differs from example 1 in that no tantalum doping, i.e., no tantalum source, is added, and the remaining steps and parameters are exactly the same as in example 1.
Comparative example 3
This comparative example provides a method of preparing a quaternary polycrystalline positive electrode material, which, compared to example 1, differs in that no cobalt doping, i.e. no cobalt source, is added, and the remaining steps and parameters are exactly the same as in example 1.
The invention also provides a battery, which comprises a positive electrode, a negative electrode and a diaphragm, wherein the positive electrode material in the positive electrode is the quaternary polycrystalline positive electrode material in the embodiment.
The cathode materials prepared in the above examples and comparative examples were assembled into button cells, and the assembly method included:
weighing the quaternary polycrystalline positive electrode material, the carbon black conductive agent, the binder PVDF and the NMP according to the mass ratio of 90:2.5:2.5:5, and uniformly mixing to prepare the battery positive electrode slurry. Coating the slurry on an aluminum foil with the thickness of 30um, preparing a positive electrode plate by vacuum drying and rolling, taking a lithium metal plate as a negative electrode, and assembling the positive electrode plate and the negative electrode plate to obtain the button cell, wherein the electrolyte ratio is 1.15M LiPF6EC: DMC (1:1 vol%).
And (3) carrying out an electrical property test on the assembled battery, wherein the test method comprises the following steps:
testing at 45 ℃ by adopting a blue battery testing system, wherein the testing voltage range is 3-4.3V; capacity and capacity retention was tested for 1 week, 20 weeks and 50 weeks.
The test results are shown in table 1, fig. 1 is a graph showing the first charge and discharge of example 1, and fig. 2 is a graph showing the first charge and discharge of comparative example 1.
TABLE 1
From the above table, it can be seen that:
(1) compared with the embodiments 4 and 5, the performance data of the embodiment 1 is superior to those of the embodiments 4 and 5, and therefore, the invention can be seen that the invention ensures the growth of primary particles in the preparation process, increases the spacing between transition metal layers and improves the capacity and the cycle retention rate by controlling the molar ratio of the tantalum source to the nickel-cobalt-manganese-aluminum quaternary precursor to be (0.0005-0.0015): 1, and if the molar ratio is lower than 0.0005:1, the tantalum element cannot play a role in increasing the spacing between the transition metal layers, so that the capacity is lower; if the molar ratio is higher than 0.0015:1, the tantalum element inhibits the growth of primary particles, and there is a problem that the cycle retention rate is low.
(2) Compared with the embodiments 6 and 7, the performance data of the embodiment 1 is superior to those of the embodiments 6 and 7, and therefore, the invention can be seen that the stability is effectively enhanced by controlling the molar ratio of the cobalt source to the nickel-cobalt-manganese-aluminum quaternary precursor to be (0.006-0.010): 1, and the invention has the advantage of high first effect, and if the molar ratio is lower than 0.006:1, the material stability is poor and the first effect is low; if the molar ratio is higher than 0.01:1, the cost is disadvantageously high.
(3) Compared with the embodiments 8 and 9, the performance data of the embodiment 1 is superior to those of the embodiments 8 and 9, and therefore, the calcining temperature is controlled to be 700-800 ℃, the uniformity of the size of primary particles in the preparation process is effectively ensured, the material capacity is improved, and if the temperature is lower than 700 ℃, the primary particles are smaller, the gas generation is serious, and the cycle retention rate is low; if the temperature is higher than 800 ℃, the material capacity cannot be exerted due to overburning.
(4) Compared with the embodiment 10, the performance data of the embodiment 1 is better than that of the embodiment 10, so that the invention can be seen that the quaternary polycrystalline positive electrode material is further coated with boron, the coating can be carried out at a lower temperature by adopting the boron coating, a uniform protective film can be formed, the capacity and the cycling stability of the material are further enhanced, and the cycle retention rate is improved.
(5) Compared with the example 11, the performance data of the example 1 is better than that of the example 11, so that the cobalt doping is carried out in the doping stage instead of regulating and controlling the cobalt content of the whole material in the raw material, the doped cobalt element can effectively play a role in inhibiting divalent nickel from entering a lithium position, reducing the lithium-nickel mixed-discharging degree, and then the electronic conductivity of the material is improved by carrying out gradient doping on the surface.
(6) Compared with the comparative examples 1 to 3, the performance data of the example 1 is superior to that of the comparative examples 1 to 3, and therefore, the invention can be seen that the adjustment of the crystal microstructure of the quaternary polycrystalline positive electrode material is carried out by Co-doping Co/Ta, so that the lattice structure is stabilized, wherein the cobalt doping mainly inhibits divalent nickel from entering a lithium position, the lithium-nickel mixed-discharging degree is reduced, and the electronic conductivity of the material is improved by carrying out gradient doping on the surface; the tantalum doping can improve the interlayer spacing of the transition metal layer, thereby improving the diffusion rate of lithium ions and further improving the cycle life of the ultra-high nickel cathode material. Furthermore, the Co/Ta Co-doping adjusts the microstructure of the anode material, stabilizes the crystal lattice, reduces the mixed arrangement degree of lithium and nickel, and improves the electronic conductivity and the lithium ion diffusion rate of the material, thereby improving the capacity and the cycling stability of the material.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
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