CN111422921A - Polycrystalline high-nickel ternary positive electrode material, preparation method thereof, positive plate and lithium ion battery - Google Patents
Polycrystalline high-nickel ternary positive electrode material, preparation method thereof, positive plate and lithium ion battery Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 86
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 title claims description 21
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 239000002019 doping agent Substances 0.000 claims abstract description 29
- 239000010406 cathode material Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000005406 washing Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 16
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims abstract description 12
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- 229910052726 zirconium Inorganic materials 0.000 claims description 20
- 238000004321 preservation Methods 0.000 claims description 16
- 150000004679 hydroxides Chemical class 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000009423 ventilation Methods 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims description 3
- 229910003678 NixCoyMnz(OH)2 Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 abstract description 8
- 230000002427 irreversible effect Effects 0.000 abstract description 6
- 230000007704 transition Effects 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 description 22
- 230000009467 reduction Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000003211 malignant effect Effects 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
- 238000005457 optimization Methods 0.000 description 1
- 230000021962 pH elevation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/50—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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- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a polycrystalline high-nickel ternary cathode material, a preparation method thereof, a cathode plate and a lithium ion battery, wherein the method for preparing the polycrystalline high-nickel ternary cathode material comprises the following steps: mixing a polycrystalline high-nickel ternary precursor, lithium hydroxide monohydrate and a doping agent, and performing primary sintering on the obtained first mixture to obtain a primary sintered product; washing and drying the primary sintered product in sequence to obtain washed powder; and mixing the washed powder with a surface coating agent, and sintering the obtained second mixture for the second time to obtain the polycrystalline high-nickel ternary cathode material. The polycrystalline high-nickel ternary cathode material prepared by the method has higher specific capacity under the condition of the same nickel content, namely the specific capacity can be improved on the premise of not changing the nickel content, and the problems of unstable structure, high surface residual alkali content, easy occurrence of irreversible phase transition and the like caused by overhigh nickel content are avoided.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a polycrystalline high-nickel ternary cathode material, a preparation method thereof, a cathode plate and a lithium ion battery.
Background
The nickel cobalt lithium manganate ternary positive electrode material (NCM) combines the advantages of nickel, cobalt and manganese, has the advantages of high specific capacity, long service life, safety, environmental protection and the like, and is the mainstream direction of the development of the power lithium ion battery at present. Wherein, nickel element mainly plays a role in improving the specific capacity of the material, cobalt element mainly plays a role in improving multiplying power and supporting a laminated structure, and manganese element mainly plays a role in stabilizing the whole crystal structure and realizing high circulation. Therefore, generally speaking, the higher the nickel content is, the higher the specific capacity is, so that the current power lithium ion battery is gradually developing towards the direction of high nickel, and the nickel content of some products under study even breaks through 90%.
However, the high-nickel ternary cathode material still has some obvious problems, and specifically, although the composition proportion of nickel element is improved, which is helpful to significantly increase the specific capacity of the high-nickel ternary cathode material, the poor structural stability of the high-nickel ternary cathode material is also caused, for example, the process processability is affected by too high surface residual alkali, and the irreversible phase transformation is easy to occur under high voltage due to the high oxidizability of nickel ions, so that the crystal structure of the high-nickel ternary cathode material is damaged, the cycle retention rate is reduced, and the like.
Therefore, the related art of the current high-nickel ternary cathode material still needs to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, one objective of the present invention is to provide a polycrystalline high-nickel ternary positive electrode material capable of effectively increasing specific capacity without changing nickel content, and a preparation method thereof.
In one aspect of the invention, a method of making a polycrystalline high nickel ternary positive electrode material is provided. According to an embodiment of the invention, the method comprises: mixing a polycrystalline high-nickel ternary precursor, lithium hydroxide monohydrate and a doping agent, and performing primary sintering on the obtained first mixture to obtain a primary sintered product; washing and drying the primary sintered product in sequence to obtain washed powder; and mixing the washed powder with a surface coating agent, and sintering the obtained second mixture for the second time to obtain the polycrystalline high-nickel ternary cathode material. The polycrystalline high-nickel ternary cathode material prepared by the method has higher specific capacity under the condition of the same nickel content, namely the specific capacity can be improved on the premise of not changing the nickel content, and the problems of unstable structure, high surface residual alkali content, easy occurrence of irreversible phase transition and the like caused by overhigh nickel content are avoided.
According to an embodiment of the invention, the polycrystalline high nickel ternary precursor fulfils at least one of the following conditions: the chemical composition of the polycrystalline high-nickel ternary precursor is NixCoyMnz(OH)2Wherein x is more than or equal to 0.6 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.35, z is more than or equal to 0.05 and less than or equal to 0.35, and x + y + z is 1; the molar ratio of the lithium hydroxide monohydrate to the polycrystalline high-nickel ternary precursor is 0.98-1.04: 1.
according to an embodiment of the invention, the dopant satisfies at least one of the following conditions: the dopant comprises at least one of oxides and hydroxides of Zr, Ti, Al, W, Sr and Ba, preferably at least one of oxides and hydroxides of Zr, Ti, Al and W, and further preferably at least one of oxides and hydroxides of Zr and Ti; the doping amount of the dopant is 1000 to 3000ppm, preferably 1500 to 3000ppm, and more preferably 1500 to 2000 ppm.
According to the embodiment of the invention, the primary sintering meets at least one of the following conditions that the sintering atmosphere is oxygen, the ventilation rate is 5-15L/min, preferably 10-15L/min, the heating rate is 2-4 ℃/min, the heat preservation temperature is 700-900 ℃, the heat preservation time is 5-15 h, and the cooling mode is furnace cooling.
According to an embodiment of the present invention, the washing and drying satisfy at least one of the following conditions: the solid-liquid ratio of the water washing is 2-0.5: 1, preferably 2-1: 1; the washing time is 0.5-15 min, preferably 0.5-5 min; the drying temperature is 80-150 ℃, preferably 100-150 ℃, and further preferably 120-150 ℃; the drying time is 5-18 h, preferably 3-15 h, and further preferably 5-10 h; the vacuum degree of the drying is less than or equal to-0.1 Mpa.
According to an embodiment of the invention, the coating agent satisfies at least one of the following conditions: the coating agent comprises at least one of oxides and hydroxides of Al, Zr, Ti, Ba, Mg and B, preferably at least one of oxides and hydroxides of Al, B, Ti and Zr, and further preferably at least one of oxides and hydroxides of Al and B; the coating amount of the coating agent is 400-3000 ppm; mixing the coating agent and the washed powder by using a high-speed mixer, wherein the rotation linear speed of a rotor of the high-speed mixer is 5-15 m/s, and preferably 8-12 m/s; the mixing time of the coating agent and the washed powder is 3-12 min, preferably 5-10 min.
According to the embodiment of the invention, the secondary sintering is carried out under at least one of the following conditions that the sintering atmosphere is oxygen, the ventilation rate is 5-15L/min, preferably 10-15L/min, the heating rate is 2-4 ℃/min, the heat preservation temperature is 300-600 ℃, preferably 350-550 ℃, further preferably 450-550 ℃, the heat preservation time is 5-15 h, preferably 5-10 h, further preferably 5-7 h, and the cooling mode is furnace cooling.
In another aspect of the invention, a polycrystalline high nickel ternary positive electrode material is provided. According to the embodiment of the invention, the polycrystalline high-nickel ternary cathode material is prepared by the method. Under the condition of the same nickel content, the polycrystalline high-nickel ternary cathode material has higher specific capacity, better structural stability, lower surface residual alkali content, difficult irreversible phase transformation under high voltage and higher cycle retention rate.
According to the embodiment of the invention, the chemical composition of the polycrystalline high-nickel ternary cathode material is L iaNixCoyMnzMbMcO2Wherein a is more than or equal to 0.98 and less than or equal to 1.04, x is more than or equal to 0.6 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.35, z is more than or equal to 0.05 and less than or equal to 0.35, and x +y+z＝1。
In yet another aspect of the present invention, the present invention provides a positive electrode sheet or a lithium ion battery. According to an embodiment of the invention, the positive plate or the lithium ion battery contains the polycrystalline high-nickel ternary positive electrode material. The positive plate or the lithium ion battery has all the characteristics and advantages of the polycrystalline high-nickel ternary positive electrode material, and the description is omitted.
Compared with the related art, the invention has the following beneficial effects:
(1) according to the invention, on the premise of not adjusting the proportion of main elements (nickel, cobalt and manganese) of the high-nickel ternary cathode material, the specific capacity of the prepared high-nickel ternary cathode material is obviously improved.
(2) The invention greatly reduces the residual alkali of the primary sintering material by water washing and coating and secondary sintering treatment, and has good improvement effect on the process processability.
(3) Under the condition of higher content of nickel ions, the state of the nickel ions is very unstable, and potential safety hazards are easily caused, so that the specific capacity of the material is obviously improved on the premise of not improving the proportion of one of the main elements of the high-nickel ternary cathode material, and certain guarantee is provided for the safe use of the lithium ion secondary battery.
Drawings
Fig. 1 is a schematic flow diagram of a method for preparing a polycrystalline high-nickel ternary positive electrode material according to an embodiment of the invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the invention, a method of making a polycrystalline high nickel ternary positive electrode material is provided. According to an embodiment of the invention, referring to fig. 1, the method comprises the steps of:
s10: and mixing the polycrystalline high-nickel ternary precursor, lithium hydroxide monohydrate and a doping agent, and performing primary sintering on the obtained first mixture to obtain a primary sintered product.
According to an embodiment of the present invention, the chemical composition of the polycrystalline high-nickel ternary precursor may be NixCoyMnz(OH)2Wherein x is more than or equal to 0.6 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.35, z is more than or equal to 0.05 and less than or equal to 0.35, and x + y + z is 1. Specifically, x may be 0.6, 0.7, 0.8, 0.9, etc., y may be 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, etc., and z may be 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, etc. The Ni element mainly contributes to the specific capacity of the anode material, the Co element mainly influences the rate capability of the anode material, the Mn element mainly plays a role in structural stability, the specific proportion of the three elements is within the range, the comprehensive performance of the anode material is good, and different performances can be adjusted within a certain range according to application requirements.
In some embodiments, the polycrystalline high nickel ternary precursor may be an NCM811 type polycrystalline high nickel ternary precursor (i.e., a molar ratio of nickel, cobalt, and manganese of 8:1: 1). In other embodiments, the molar ratio of nickel in the polycrystalline high-nickel ternary precursor is greater than or equal to 83% based on the total content of nickel, cobalt and manganese. Therefore, the specific capacity can be obviously improved on the premise of ensuring the stable structure of the ternary material.
According to the embodiment of the invention, the molar ratio of the lithium hydroxide monohydrate to the polycrystalline high-nickel ternary precursor is 0.98-1.04: 1 (specifically, 0.98: 1, 0.99:1, 1:1, 0.10:1, 1.02:1, 1.03:1, 1.04:1, etc.). The lithium hydroxide monohydrate has low requirements on storage and application environments, and compared with anhydrous lithium hydroxide, the lithium hydroxide monohydrate is not easy to absorb water in air, and the weighing precision is higher. Furthermore, in the proportion range, the method is suitable for most sintering temperatures on the premise of ensuring the specific capacity of the anode material. If the proportion is too large, an overburning phenomenon is generated, and the structure of the anode material is damaged. If the proportion is too small, the crystal growth of the nickel cobalt lithium manganate is incomplete, and the specific capacity of the positive electrode material is reduced because the content of lithium element is low.
According to the embodiment of the invention, the doping agent is added, so that the structure of the polycrystalline high-nickel ternary cathode material can be stabilized, the interlayer spacing is increased, and the lithium ion can be more favorably inserted and extracted. Specifically, the dopant that can be used includes at least one of oxides and hydroxides of Zr, Ti, Al, W, Sr, and Ba, that is, may be one or a combination of more of oxides of Zr, Ti, Al, W, Sr, Ba, Zr, Ti, Al, W, Sr, and Ba. In some embodiments, the dopant includes at least one of oxides and hydroxides of Zr, Ti, Al, W. In other embodiments, the dopant includes at least one of an oxide and a hydroxide of Zr, Ti.
According to the embodiment of the invention, the doping amount of the dopant can be 1000-3000 ppm (namely, one thousandth to three thousandth of the quality of a primary sintering product obtained by sintering the polycrystalline high-nickel ternary precursor and lithium hydroxide monohydrate) (specifically, 1000ppm, 1500ppm, 2000ppm, 2500ppm, 3000ppm and the like). In some embodiments, the doping amount of the dopant may be 1500 to 3000 ppm. In other embodiments, the doping amount of the dopant can be 1500-2000 ppm (specifically, 1500ppm, 1600ppm, 1700ppm, 1800ppm, 1900ppm, 2000ppm, etc.). Within the doping amount range, the crystal structure of the anode material can be effectively stabilized, and the lithium insertion and lithium removal efficiency of the anode material is improved. If the doping amount is too high, the main element in the crystal structure is occupied too much, and the specific capacity is reduced; if the doping amount is too low, the optimization effect cannot be achieved.
According to the embodiment of the invention, the primary sintering meets at least one of the following conditions that a sintering atmosphere is oxygen, the ventilation rate is 5-15L/min (specifically, 5L/min, 6L 0/min, 7L 1/min, 8L 2/min, 9L/min, 10L/min, 11L/min, 12L/min, 13L/min, 14L/min, 15L/min and the like), specifically, 10-15L/min, the heating rate is 2-4 ℃/min (specifically, 2 ℃/min, 3 ℃/min, 4 ℃/min and the like), the heat preservation temperature is 700 ℃ -900 ℃ (specifically, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ and the like), the heat preservation time is 5-15 h too long (specifically, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h and the like), the heat preservation time is 5-15 h too short, the heat preservation time can be too long (specifically, the reaction time can be reduced, the temperature reduction can be achieved, and the whole reaction can be reduced, if the temperature reduction is too fast, and the temperature reduction can be achieved.
S20: and washing and drying the primary sintered product in sequence to obtain washed powder.
Specifically, in this step, the primary sintered product is washed with water, because the surface of the high-nickel positive electrode material is easily adhered with residual alkalides such as lithium hydroxide and lithium carbonate after primary sintering, the higher the nickel content is, the higher the residual alkalides content after primary sintering is. The alkalide can generate side reaction with electrolyte in the battery circulation process, so that the electrolyte loss, the gas generation in the battery and other malignant influences are caused, and the service life of the anode material is shortened. On one hand, residual alkalides attached to the surfaces of the anode material particles can be washed clean by water washing, and on the other hand, an activation effect is generated on the surfaces of the anode material particles, so that the interface impedance is reduced, and the specific capacity of the anode material is improved.
According to an embodiment of the present invention, the washing and drying satisfy at least one of the following conditions: the solid-liquid ratio (mass ratio) of the water washing is 2-0.5: 1 (specifically, 2:1, 1.8:1, 1.5:1, 1.2:1, 1:1, 0.8:1, 0.5:1, etc.), and specifically, 2 to 1: 1; the washing time is 0.5-15 min (specifically, 0.5min, 1min, 3min, 5min, 8min, 10min, 12min, 15min, etc.), and specifically, 0.5-5 min; the drying temperature is 80-150 ℃ (specifically, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ and the like), specifically, 100-150 ℃, and more specifically, 120-150 ℃; the drying time is 3-18 h (specifically 5h, 8h, 10h, 12h, 15h, 18h and the like), specifically 3-15 h, and more specifically 5-10 h; the vacuum degree of the drying is less than or equal to-0.1 Mpa. Specifically, the washing and drying may satisfy any one, any two, any three, any four, or all five of the above conditions. In some embodiments, one sintering satisfies all five of the above conditions. Therefore, under the conditions, the device can be reasonably matched according to different used devices and different requirements of an application user. If the solid-liquid ratio is too large and the washing time is too long, an over-washing phenomenon can be generated, so that lithium in the anode material is gradually lost along with the washing; if the solid-liquid ratio is too small and the washing time is too short, the washing is insufficient, and the residual alkalinized substances attached to the surface of the positive electrode material cannot be effectively removed. If the drying temperature is too high, on one hand, the drying cost is increased, and on the other hand, the surface of the anode material is also affected by instant severe gasification of moisture; the drying temperature is too low, so that moisture cannot be timely stripped from the surface of the anode material, and side reaction is possibly generated with the anode material again to generate residual alkalinization; and if the drying time is too short, residual moisture cannot be fully stripped, and if the drying time is too long, the cost of the drying link is increased, so that resource waste is caused.
In some specific embodiments, the primary sintered product can be put into a washing and filter pressing integrated machine, deionized water is put into the machine according to a certain solid-liquid ratio, the mixture is stirred for a period of time, and powder after washing is obtained after vacuum drying.
S30: and mixing the washed powder with a surface coating agent, and sintering the obtained second mixture for the second time to obtain the polycrystalline high-nickel ternary cathode material.
According to an embodiment of the present invention, the coating agent includes at least one of oxides and hydroxides of Al, Zr, Ti, Ba, Mg and B, that is, may be one or a combination of more of oxides of Al, Zr, Ti, Ba, Mg, B, Al, Zr, Ti, Ba, Mg and B. The coating agent can perform surface modification and modification on the surface of the washed anode material, and can be used as a buffer layer between the anode material and electrolyte in a lithium ion battery to stabilize the structural stability of the anode material.
In some embodiments, the capping agent may be at least one of an oxide and a hydroxide of Al, B, Ti, Zr. In other embodiments, the coating agent may be at least one of an oxide and a hydroxide of Al, B.
In some specific embodiments, the powder after washing is put into a high-speed stirrer, then a certain amount of coating agent is added, the mixture is obtained after uniform mixing, then the obtained mixture is put into an atmosphere furnace, and the temperature is raised and the heat is preserved and sintered under the oxygen atmosphere.
According to the embodiment of the invention, the coating agent and the washed powder can be mixed uniformly by using a high-speed mixer in advance, specifically, the coating agent and the washed powder can be added into the high-speed mixer, and then the mixture can be mixed uniformly under the condition that the rotation linear speed of a rotor of the high-speed mixer is 5-15 m/s (such as 5m/s, 6m/s, 7m/s, 8m/s, 9m/s, 10m/s, 11m/s, 12m/s, 13m/s, 14m/s, 15m/s and the like), specifically 8-12 m/s, and the mixing time can be 3-12 min (specifically, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min and the like), more specifically 5-10 min. Therefore, the coating agent and the washed powder can be uniformly mixed, and the coating agent can better coat the washed powder in the secondary sintering process.
According to the embodiment of the invention, the coating amount of the coating agent can be 400-3000 ppm (namely four to three thousandths of the mass of the powder after washing and drying) (specifically, 400ppm, 500ppm, 1000ppm, 1500ppm, 2000ppm, 2500ppm, 3000ppm and the like). In the coating amount range, a coating layer formed by reaction can effectively modify and improve the surface of the anode material, if the coating amount is too high, the coating layer is too thick, the interface impedance of the anode material is improved, the reaction activity is reduced, and the specific discharge capacity is reduced; if the coating amount is too low, an effective coating layer cannot be formed.
According to the embodiment of the invention, the secondary sintering meets at least one of the following conditions that a sintering atmosphere is oxygen, an air flow is 5-15L/min (specifically, 5L/min, 6L 0/min, 7L 1/min, 8L 2/min, 9L/min, 10L/min, 11L/min, 12L/min, 13L/min, 14L/min, 15L/min and the like), specifically, 10-15L/min, a heating rate is 2-4 ℃/min (specifically, 2 ℃/min, 3 ℃/min, 4 ℃/min and the like), a heat preservation temperature is 300-600 ℃ (specifically, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃ and the like), specifically, too small a temperature can be 350-550 ℃, more specifically, 450-550 ℃, a heat preservation time is 5-15 h (specifically, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h and the like), if the temperature reduction of the sintering process is carried out, the temperature reduction is carried out, and the reaction is carried out in a slow, and the above-15 h, if the temperature reduction is carried out, and the temperature reduction is not needed, and the temperature reduction is carried out, or the reaction is not needed, and is carried out, and is not needed, or not needed.
The polycrystalline high-nickel ternary cathode material prepared by the method has higher specific capacity under the condition of the same nickel content, namely the specific capacity can be improved on the premise of not changing the nickel content, and the problems of unstable structure, high surface residual alkali content, easy occurrence of irreversible phase transition and the like caused by overhigh nickel content are avoided.
In another aspect of the invention, a polycrystalline high nickel ternary positive electrode material is provided. According to the embodiment of the invention, the polycrystalline high-nickel ternary cathode material is prepared by the method. Under the condition of the same nickel content, the polycrystalline high-nickel ternary cathode material has higher specific capacity, better structural stability and lower surface residual alkali content, is not easy to generate irreversible phase transformation under high voltage, and has higher reduced cycle retention rate.
According to the embodiment of the invention, the chemical composition of the polycrystalline high-nickel ternary cathode material is L iaNixCoyMnzMbMcO2Wherein a is more than or equal to 0.98 and less than or equal to 1.04, x is more than or equal to 0.6 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.35, z is more than or equal to 0.05 and less than or equal to 0.35, and x + y + z is equal to 1. Specifically, a may be 0.98, 0.99, 1, 1.01, 1.02, 1.03, 1.04, etc., x may be 0.6, 0.7, 0.8, 0.9, etc., y may be 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, etc., and z may be 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, etc. The Ni element mainly contributes to the specific capacity of the anode material, the Co element mainly influences the rate capability of the anode material, and the Mn element mainly plays a role in structural stability.
In yet another aspect of the present invention, the present invention provides a positive electrode sheet or a lithium ion battery. According to an embodiment of the invention, the positive plate or the lithium ion battery contains the polycrystalline high-nickel ternary positive electrode material. The positive plate or the lithium ion battery has all the characteristics and advantages of the polycrystalline high-nickel ternary positive electrode material, and the description is omitted.
It can be understood that the positive electrode sheet may be formed by preparing a positive electrode material into a slurry, and then coating the slurry on a current collector (such as a copper foil, etc.), and conventional additives, such as a conductive agent, an auxiliary agent, etc., may also be added to the slurry, which may be specifically performed with reference to a conventional process, and details of which are not repeated herein. The lithium ion battery may have, besides the polycrystalline high-nickel ternary positive electrode material, structures and components that are necessary for a conventional lithium ion battery, such as a negative electrode sheet, an electrolyte or an electrolyte, a housing, and the like, and may be specifically performed by referring to a conventional process, which is not described herein again.
The following describes embodiments of the present invention in detail.
Example 1
1) The NCM811 type polycrystalline high nickel ternary precursor (namely the chemical composition is Ni)0.8Co0.1Mn0.1(OH)2) Uniformly mixing the mixture with lithium hydroxide monohydrate and a doping agent, and then placing the mixture into an atmosphere furnace for primary sintering, wherein the molar ratio of the lithium hydroxide monohydrate to the high-nickel ternary precursor is 1.04, and the doping agent is Zr (OH)4And TiO2The doping amount of the dopant is 1500ppm, the atmosphere of primary sintering is oxygen atmosphere, the ventilation amount is 10L/min, the heating rate is 2 ℃/min, the heat preservation temperature is 800 ℃, the heat preservation time is 10h, and the cooling mode is furnace cooling.
2) And (2) under the condition of normal temperature, putting the primary sintering product obtained by sintering in the step 1) into a washing and filter pressing integrated machine, wherein the solid-to-liquid ratio (mass ratio) is 1:1, adding deionized water, stirring at 60rpm for 5min, and then drying in vacuum at the vacuum degree of less than or equal to-0.1 Mpa and the temperature of 150 ℃ for 15h to obtain the powder after water washing.
3) Putting the washed powder into a high-speed stirrer, and then adding 400ppm of B as a coating agent2O3And 2500ppm Al (OH)3The speed of the rotation linear of the rotor of the high-speed mixer is 10 m/s. And then uniformly mixing for 10min under the condition of (1) to obtain a second mixture.
4) And placing the second mixture in an atmosphere furnace, heating and insulating for sintering in an oxygen atmosphere, wherein the ventilation rate is 10L/min, the heating rate is 2 ℃/min, the insulating temperature is 500 ℃, the insulating time is 6h, and the cooling mode is furnace cooling.
5) And after cooling, sieving the secondary sintered product by a 400-mesh sieve to obtain a final finished product, namely the high-specific-capacity high-nickel ternary cathode material.
Example 2
The difference from example 1 is that the primary sintering temperature was 760 ℃.
Example 3
The difference from example 1 is that the primary sintering temperature is 760 ℃ and the amount of the coating agent is 250ppm B2O3、1250ppmAl(OH)3。
Example 4
The difference from example 1 is that the dopants are Zr oxide and Ti oxide.
Example 5
The difference from example 1 is that the dopants are Zr oxide and A L hydroxide.
Example 6
The difference from example 1 is that the dopants are an oxide of W and an oxide of A L.
Example 7
The difference from example 1 is that the dopants are an oxide of Zr and an oxide of Sr.
Example 8
The difference from example 1 is that the dopants are Zr oxide, a L oxide and Ba hydroxide.
Example 9
The difference from example 1 is that the doping amount of the dopant was 1000 ppm.
Example 10
The difference from example 1 is that the doping amount of the dopant was 2000 ppm.
Example 11
The difference from example 1 is that the doping amount of the dopant was 3000 ppm.
Example 12
The difference from example 2 is that the temperature of the primary sintering was 700 ℃.
Example 13
The difference from example 2 is that the temperature of the primary sintering was 900 ℃.
Example 14
The difference from example 2 is that the ventilation rate in the first sintering was 5L/min.
Example 15
The difference from example 2 is that the ventilation rate in the first sintering was 15L/min.
Example 16
The difference from example 2 is that the temperature increase rate was 3 ℃/min.
Example 17
The difference from example 2 is that the temperature increase rate was 4 ℃/min.
Example 18
The difference from example 2 is that the incubation time was 5 hours.
Example 19
The difference from example 2 is that the incubation time was 15 h.
Example 20
The difference from example 3 is that the coating agent is an oxide of B, an oxide of Al and Ti.
Example 21
The difference from example 3 is that the coating agent is an oxide of B, a hydroxide of Al and Zr.
Example 22
The difference from example 3 is that the coating agent is an oxide of B and Ti.
Example 23
The difference from example 3 is that the capping agent is B, Al and an oxide of Mg.
Example 24
The difference from example 3 is that the capping agent is B, Al and an oxide of Ba.
Example 25
The difference from example 3 is that 400ppm of B as a coating agent2O3And 2000ppm Al (OH)3。
Example 26
The difference from example 3 is that the coating agent is 300ppm B2O3And 1500ppm Al (OH)3。
Example 27
The difference from example 3 is that the coating agent is 100ppm B2O3And 1000ppm Al (OH)3。
Example 28
The difference from example 3 is that the coating agent is 50ppm B2O3And 400ppm Al (OH)3。
Comparative example 1
In contrast to example 1, comparative example 1 was subjected to only the step 1) treatment in example 1 and was not doped with any dopant.
Comparative example 2
Comparative example 2 compared to example 3, all the steps in example 3 were carried out, but the precursor was a high nickel single crystal precursor.
And (3) performance detection:
the specific capacity and the surface residual alkali of the ternary cathode material obtained in all the above examples and comparative examples at 0.1C discharge are shown in table 1.
TABLE 1
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method for preparing a polycrystalline high-nickel ternary cathode material is characterized by comprising the following steps:
mixing a polycrystalline high-nickel ternary precursor, lithium hydroxide monohydrate and a doping agent, and performing primary sintering on the obtained first mixture to obtain a primary sintered product;
washing and drying the primary sintered product in sequence to obtain washed powder;
and mixing the washed powder with a surface coating agent, and sintering the obtained second mixture for the second time to obtain the polycrystalline high-nickel ternary cathode material.
2. The method of claim 1, wherein the polycrystalline high-nickel ternary precursor meets at least one of the following conditions:
the chemical composition of the polycrystalline high-nickel ternary precursor is NixCoyMnz(OH)2Wherein x is more than or equal to 0.6 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.35, z is more than or equal to 0.05 and less than or equal to 0.35, and x + y + z is 1;
the molar ratio of the lithium hydroxide monohydrate to the polycrystalline high-nickel ternary precursor is 0.98-1.04: 1.
3. the method of claim 1, wherein the dopant satisfies at least one of the following conditions:
the dopant comprises at least one of oxides and hydroxides of Zr, Ti, Al, W, Sr and Ba, preferably at least one of oxides and hydroxides of Zr, Ti, Al and W, and further preferably at least one of oxides and hydroxides of Zr and Ti;
the doping amount of the dopant is 1000 to 3000ppm, preferably 1500 to 3000ppm, and more preferably 1500 to 2000 ppm.
4. The method according to claim 1, wherein the primary sintering satisfies at least one of the following conditions:
the sintering atmosphere is oxygen;
the ventilation amount is 5-15L/min, preferably 10-15L/min;
the heating rate is 2-4 ℃/min;
the heat preservation temperature is 700-900 ℃;
the heat preservation time is 5-15 h;
the cooling mode is furnace cooling.
5. The method according to claim 1, wherein the water washing and drying satisfy at least one of the following conditions:
the solid-liquid ratio of the water washing is 2-0.5: 1, preferably 2-1: 1;
the washing time is 0.5-15 min, preferably 0.5-5 min;
the drying temperature is 80-150 ℃, preferably 100-150 ℃, and further preferably 120-150 ℃;
the drying time is 3-18 h, preferably 3-15 h, and further preferably 5-10 h;
the vacuum degree of the drying is less than or equal to-0.1 Mpa.
6. The method of claim 1, wherein the capping agent satisfies at least one of the following conditions:
the coating agent comprises at least one of oxides and hydroxides of Al, Zr, Ti, Ba, Mg and B, preferably at least one of oxides and hydroxides of Al, B, Ti and Zr, and further preferably at least one of oxides and hydroxides of Al and B;
the coating amount of the coating agent is 400-3000 ppm;
mixing the coating agent and the washed powder by using a high-speed mixer, wherein the rotation linear speed of a rotor of the high-speed mixer is 5-15 m/s, and preferably 8-12 m/s;
the mixing time of the coating agent and the washed powder is 3-12 min, preferably 5-10 min.
7. The method of claim 1, wherein the secondary sintering satisfies at least one of the following conditions:
the sintering atmosphere is oxygen;
the ventilation amount is 5-15L/min, preferably 10-15L/min;
the heating rate is 2-4 ℃/min;
the heat preservation temperature is 300-600 ℃, preferably 350-550 ℃, and further preferably 450-550 ℃;
the heat preservation time is 5-15 h, preferably 5-10 h, and further preferably 5-7 h;
the cooling mode is furnace cooling.
8. A polycrystalline high-nickel ternary positive electrode material, which is prepared by the method of any one of claims 1 to 7.
9. The polycrystalline high-nickel ternary positive electrode material according to claim 8, wherein the chemical composition is L iaNixCoyMnzMbMcO2Wherein a is more than or equal to 0.98 and less than or equal to 1.04, x is more than or equal to 0.6 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.35, z is more than or equal to 0.05 and less than or equal to 0.35, and x + y + z is equal to 1.
10. A positive electrode sheet or a lithium ion battery, characterized by containing the polycrystalline high-nickel ternary positive electrode material according to claim 8 or 9.
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