CN115043443A - Low-cost high-nickel ternary cathode material and preparation method and application thereof - Google Patents
Low-cost high-nickel ternary cathode material and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 117
- 239000010406 cathode material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 108
- 239000002243 precursor Substances 0.000 claims abstract description 65
- 239000000843 powder Substances 0.000 claims abstract description 23
- 230000018044 dehydration Effects 0.000 claims abstract description 19
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 238000005259 measurement Methods 0.000 claims abstract description 8
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 110
- 239000000463 material Substances 0.000 claims description 103
- 238000000034 method Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 238000003756 stirring Methods 0.000 description 32
- 238000011068 loading method Methods 0.000 description 30
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 27
- 239000007789 gas Substances 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 238000009423 ventilation Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000012216 screening Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
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- 239000003990 capacitor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000003446 memory effect Effects 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a low-cost high-nickel ternary cathode material with a general formula of LiNi x Co y A 1‑x‑y O 2 Formula I; in the formula I, x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.4; a is selected from at least one element of Mn, Al, Ta, Ti, Nb, Ge, Y, Nb, W, Zr, B, Ce, Ca and Sr; the 7-day thermal measurement gas production rate of the low-cost high-nickel ternary cathode material is less than 15 percent, and Li 2 CO 3 The content is less than 2000ppm, and the LiOH content is less than 5000 ppm. According to the invention, the precursor is dehydrated by adopting the rotary kiln, and is mixed with the coarse powder lithium hydroxide after the dehydration is finished, and then the dehydration is carried out, so that the dehydration is complete, and the obtained anode material has good comprehensive performances such as circulation, gas generation and the like. The invention also provides a preparation method and application of the low-cost high-nickel ternary cathode material.
Description
Technical Field
The invention belongs to the technical field of cathode materials, and particularly relates to a low-cost high-nickel ternary cathode material as well as a preparation method and application thereof.
Background
In recent years, with the rise of new energy industry, new energy storage batteries occupy an important position in the whole new energy industry. Among them, lithium ion batteries are receiving industrial attention due to their advantages of light weight, large capacity, cleanness, environmental protection, no memory effect, etc. In the lithium ion battery, the cost of the anode material accounts for 30-50% of the total cost of the battery. Therefore, developing a lithium ion cathode material with low cost, high capacity and long service life has become an important issue in the lithium battery industry.
The high-nickel ternary cathode material has a plurality of advantages, but the requirements on equipment and environment in the production and processing processes are high, the production process is complex, and the processing cost is high. In order to ensure that the high-nickel ternary cathode material has excellent capacity, multiplying power, cycle performance and other performances, most of lithium salts used in the conventional production of the high-nickel ternary cathode material are micro-powder lithium hydroxide and a ternary precursor containing crystal water. With the rapid development of new energy industry, the competition of lithium ion ternary cathode materials is intensified day by day, and the reduction of cost becomes a trend of the industry.
In the prior art, a high-nickel ternary precursor and coarse lithium hydroxide are uniformly mixed and then presintered by using a rotary kiln to obtain a presintered material; performing primary sintering on the pre-sintered material to obtain a primary sintered material; crushing, washing, drying and coating the materials subjected to primary sintering, and then performing secondary sintering to obtain a positive electrode material; the product performance of the high-nickel cathode material prepared by the method is to be further improved.
Disclosure of Invention
In view of this, an object of the embodiments of the present invention is to provide a low-cost high-nickel ternary cathode material, and a preparation method and an application thereof.
The invention provides a low-cost high-nickel ternary cathode material, which has a general formula as follows:
LiNi x CoyA 1-x-y O 2 formula I;
in the formula I, x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.4;
a is selected from at least one element of Mn, Al, Ta, Ti, Nb, Ge, Y, Nb, W, Zr, B, Ce, Ca and Sr;
the 7-day thermal measurement gas production rate of the low-cost high-nickel ternary cathode material is less than 15 percent, and Li 2 CO 3 The content is less than 2000ppm, and the LiOH content is less than 5000 ppm.
Preferably, the low-cost high-nickel ternary cathode material is prepared from a material comprising a primary sintered product;
the capacity of the primary sintered product is more than 170mAh/g under the conditions of 0.2C and 2.5-4.25V;
the bulk density (AD) of the primary sintered product is 1.5-1.9 g/cc;
the molar ratio of Li to M in the primary sintering product is (0.95-1.08): 1, wherein M is the total molar amount of Ni, Co and A;
li in the primary sintered product 2 CO 3 The mass content of the active carbon is less than 8000ppm, and the mass content of LiOH is less than 8000 ppm.
Preferably, the characteristic peaks of XRD of the primary sintered product include:
the peak intensity of 18-19 degrees is 20000-30000, the peak intensity of 36-37 degrees is 7000-8000, the peak intensity of 44-45 degrees is 11000-13000, the peak intensity of 48-49 degrees is 2000-3000, the peak intensity of 58-59 degrees is 1500-2500, the peak intensity of 64-65 degrees is 2000-3000, and the peak intensity of 68-69 degrees is 1200-2200.
Preferably, the primary sintered product is prepared from a material comprising a pre-sintered product;
the bulk density (AD) of the pre-sintered product is 1.2-1.7 g/cc;
the XRD characteristic peaks of the presintered product comprise:
the peak intensity of 18-19 degrees is 2000-3000, the peak intensity of 32-33 degrees is 1000-2000, the peak intensity of 38-39 degrees is 1500-2500, the peak intensity of 42-43 degrees is 3500-4500, and the peak intensity of 64-65 degrees is 1500-2500.
Preferably, the presintered product is prepared from a material comprising a high nickel ternary precursor;
the moisture content of the high-nickel ternary precursor is less than 1 wt%;
the bulk density (AD) of the high-nickel ternary precursor is 1.5-1.8 g/cc;
the XRD characteristic peaks of the high-nickel ternary precursor comprise:
the peak intensity of 37-38 degrees is 3000-4000, the peak intensity of 43-44 degrees is 4000-4500, and the peak intensity of 63-64 degrees is 2500-3500.
Preferably, the high-nickel ternary precursor is prepared from a material comprising the high-nickel ternary precursor;
the high-nickel ternary precursor has the general formula:
Ni x Co y A 1-x-y (OH) 2 in the formula II, the compound is shown in the specification,
in the formula II, x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.4;
a is selected from at least one element of Mn, Al, Ta, Ti, Nb, Ge, Y, Nb, W, Zr, B, Ce, Ca and Sr;
the bulk density (AD) of the high-nickel ternary precursor is 1.4-1.8 g/cc, the moisture content is less than 2 wt%, and the BET is 4-12 m 2 /g；
The XRD characteristic peaks of the high-nickel ternary precursor comprise:
the peak intensity of 19-20 degrees is 10000-12000, the peak intensity of 33-34 degrees is 6000-7000, the peak intensity of 38-39 degrees is 9000-11000, the peak intensity of 52-53 degrees is 3500-4500, the peak intensity of 59-60 degrees is 3500-4500, and the peak intensity of 63-64 degrees is 2000-3000.
The invention provides a preparation method of a low-cost high-nickel ternary cathode material, which comprises the following steps:
and sequentially crushing, washing, drying, doping and sintering the primary sintered product to obtain the low-cost high-nickel ternary cathode material.
Preferably, the preparation method of the primary sintered product comprises the following steps:
performing primary sintering on the pre-sintered product to obtain a primary sintered product;
the preparation method of the presintered product comprises the following steps:
mixing a high-nickel ternary precursor, coarse powder lithium hydroxide and an additive, and then presintering to obtain a presintering product;
the preparation method of the high-nickel ternary precursor comprises the following steps:
and dehydrating the high-nickel ternary precursor to obtain the high-nickel ternary precursor.
Preferably, the dehydration temperature is 100-370 ℃;
the pre-sintering temperature is 500-600 ℃;
the temperature of the primary sintering is 735-850 ℃;
the sintering temperature is 280-600 ℃.
The present invention provides a battery comprising: the low-cost high-nickel ternary cathode material is prepared by the technical scheme.
The anode material prepared by the prior art has low productivity, high processing cost, high requirements for the overall atmosphere and period of a kiln, easily causes that the internal water vapor cannot be removed in time, and greatly affects the performance of caustic soda amount, finished product capacity, circulation, gas generation and the like; according to the invention, the precursor is dehydrated by adopting the rotary kiln, and is mixed with the coarse powder lithium hydroxide after the dehydration is finished, and then the dehydration is carried out, so that the dehydration is complete, and the obtained anode material has good comprehensive performances such as circulation, gas generation and the like.
Drawings
Fig. 1 is an SEM image of a high nickel cathode material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a high nickel cathode material prepared in example 2 of the present invention;
FIG. 3 is an SEM image of a high nickel cathode material prepared in example 3 of the present invention;
FIG. 4 is an SEM image of a high nickel cathode material prepared in example 4 of the present invention;
FIG. 5 is an SEM image of a high nickel cathode material prepared in example 5 of the present invention;
FIG. 6 is an SEM image of a high nickel cathode material prepared in example 6 of the present invention;
FIG. 7 is an SEM image of a high nickel cathode material prepared in example 7 of the present invention;
FIG. 8 is an SEM image of a high nickel cathode material prepared in comparative example 1 of the present invention;
fig. 9 is an SEM image of a high nickel cathode material prepared in comparative example 2 of the present invention;
FIG. 10 is a result of a shelf gassing test at 70 ℃ for 7 days for high nickel positive electrode materials prepared in examples of the present invention and comparative examples;
fig. 11 is a full electric cycle capacity retention rate test result of the high nickel cathode materials prepared in the examples of the present invention and the comparative examples under 1C/1C charging and discharging conditions.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a low-cost high-nickel ternary cathode material, which has a general formula as follows:
LiNi x CoyA 1-x-y O 2 formula I;
in the formula I, x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.4;
a is selected from at least one element of Mn, Al, Ta, Ti, Nb, Ge, Y, Nb, W, Zr, B, Ce, Ca and Sr;
the 7-day thermal measurement gas production rate of the low-cost high-nickel ternary cathode material is less than 15 percent, and Li 2 CO 3 The content is less than 2000ppm, and the LiOH content is less than 5000 ppm.
In the invention, the low-cost high-nickel ternary cathode material is prepared from a material comprising a primary sintered product;
in the invention, the general formula of the primary sintered product is the same as that of the low-cost high-nickel ternary cathode material in the technical scheme, and details are not repeated here.
In the present invention, the bulk density (AD) of the primary sintered product is preferably 1.5 to 1.9g/cc, more preferably 1.6 to 1.8g/cc, and most preferably 1.7 g/cc.
In the invention, the molar ratio of Li to M in the primary sintered product is preferably (0.95-1.08): 1, more preferably (0.98 to 1.02): 1, most preferably 1: 1; m is the total molar weight of Ni, Co and A; the A is at least one element selected from Mn, Al, Ta, Ti, Nb, Ge, Y, Nb, W, Zr, B, Ce, Ca and Sr.
In the invention, the capacity of the primary sintering product under the conditions of 0.2C and 2.5-4.25V is preferably more than 170mAh/g, more preferably 175-200 mAh/g, more preferably 180-195 mAh/g, and most preferably 185-190 mAh/g.
In the present invention, Li in the primary sintered product 2 CO 3 The mass content of (A) is preferably less than 8000ppm, more preferably 2000-6000 ppm, more preferably 3000-5000 ppm, and most preferably 4000 ppm; the LiOH content is preferably < 8000ppm, more preferably 2000-6000 ppm, even more preferably 3000-5000 ppm, and most preferably 4000ppm by mass.
In the present invention, the characteristic peaks of XRD of the primary sintered product preferably include:
the peak intensity of 18-19 degrees is preferably 20000-30000, more preferably 22000-28000, and most preferably 24000-26000; the peak intensity of 36-37 degrees is preferably 7000-8000, more preferably 7200-7800, and most preferably 7400-7600; the peak intensity of 44-45 degrees is preferably 11000-13000, more preferably 11500-12500 and most preferably 12000; the peak intensity of 48-49 degrees is preferably 2000-3000, more preferably 2200-2800, and most preferably 2400-2600; the peak intensity of 58-59 degrees is preferably 1500-2500, more preferably 1800-2200, and most preferably 2000; the peak intensity of 64-65 degrees is preferably 2000-3000, more preferably 2200-2800, and most preferably 2400-2600; the peak intensity of 68-69 degrees is preferably 1200-2200, more preferably 1400-1800, and most preferably 1500-1600.
In the present invention, the primary sintered product is preferably prepared from a material including a pre-sintered product having a bulk density (AD) of preferably 1.2 to 1.7g/cc, more preferably 1.3 to 1.6g/cc, and most preferably 1.4 to 1.4 g/cc.
In the present invention, XRD characteristic peaks of the pre-sintered product preferably include:
the peak intensity of 18-19 degrees is preferably 2000-3000, more preferably 2200-2800, and most preferably 2400-2600; the peak intensity of 32-33 degrees is preferably 1000-2000, more preferably 1200-1800, and most preferably 1400-1600; the peak intensity of 38-39 degrees is preferably 1500-2500, more preferably 1800-2200, and most preferably 2000; the peak intensity of 42-43 degrees is preferably 3500-4500, more preferably 3800-4200, and most preferably 4000; the peak intensity of 64-65 degrees is preferably 1500-2500, more preferably 1800-2200, and most preferably 2000.
In the invention, the presintered product is preferably prepared from a material comprising a high nickel ternary precursor, and the moisture content of the high nickel ternary precursor is preferably less than 1 wt%, more preferably 0-0.5 wt%, more preferably 0.1-0.4 wt%, and most preferably 0.2-0.3 wt%.
In the present invention, the bulk density (AD) of the high-nickel ternary precursor is preferably 1.5 to 1.8g/cc, and more preferably 1.6 to 1.7 g/cc.
In the present invention, XRD characteristic peaks of the high-nickel ternary precursor preferably include:
the peak intensity of 37-38 degrees is preferably 3000-4000, more preferably 3200-3800, and most preferably 3400-3600; the peak intensity of 43-44 DEG is preferably 4000-4500, more preferably 4100-4400, and most preferably 4200-4300; the peak intensity of 63-64 DEG is preferably 2500-3500, more preferably 2800-3200, and most preferably 3000.
In the invention, the high-nickel ternary precursor is preferably prepared from a material comprising the high-nickel ternary precursor; the high-nickel ternary precursor has the general formula:
Ni x Co y A 1-x-y (OH) 2 in the formula II, the compound is shown in the specification,
in the formula II, x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.4;
a is selected from at least one element of Mn, Al, Ta, Ti, Nb, Ge, Y, Nb, W, Zr, B, Ce, Ca and Sr;
in the invention, in the formula II, x is preferably 0.7-0.9, and more preferably 0.8; y is preferably 0.1 to 0.3, more preferably 0.2.
In the invention, the Apparent Density (AD) of the high-nickel ternary precursor is preferably 1.4-1.8 g/cc, more preferably 1.5-1.7 g/cc, and most preferably 1.6 g/cc; the moisture content is preferably < 2 wt.%, more preferably 0.1 to 0.7 wt.%, more preferably 0.2 to 0.6 wt.%, more preferably 0.3 to 0.5 wt.%, most preferably 0.4 wt.%; the specific surface area (BET) is preferably 4 to 12m 2 A concentration of 5 to 10m 2 (iv) g, most preferably 6 to 8m 2 /g。
In the present invention, XRD characteristic peaks of the high-nickel ternary precursor preferably include:
the peak intensity of 19-20 degrees is preferably 10000-12000, more preferably 10500-11500, and most preferably 11000; the peak intensity of 33-34 degrees is preferably 6000-7000, more preferably 6200-6800, and most preferably 6400-6600; the peak intensity of 38-39 degrees is preferably 9000-11000, more preferably 9500-10500, and most preferably 10000; the peak intensity of 52-53 degrees is preferably 3500-4500, more preferably 3800-4200, and most preferably 4000; the peak intensity of 59-60 degrees is preferably 3500-4500, more preferably 3800-4200, and most preferably 4000; the peak intensity of 63-64 degrees is preferably 2000-3000, more preferably 2200-2800, and most preferably 2400-2600.
In the present invention, the preparation method of the high-nickel ternary precursor preferably includes:
and dehydrating the high-nickel ternary precursor to obtain the high-nickel ternary precursor.
In the present invention, the dehydration is preferably performed using a rotary kiln.
In the invention, the dehydration method is preferably sintering dehydration, and the dehydration temperature is preferably 100-370 ℃, more preferably 150-300 ℃, and most preferably 200-250 ℃; the dehydration time is preferably 4-8 h, more preferably 5-7 h, and most preferably 6 h; the dehydration process is preferably carried out under the condition of oxygen (pure oxygen), and the gas flow rate of the oxygen is preferably 450-550L/min, more preferably 480-520L/min, and most preferably 500L/min.
If the high-nickel ternary precursor and the coarse lithium hydroxide are directly presintered, more water vapor is generated within 500 ℃, and the water vapor is difficult to discharge in a short time, so that the caustic soda content of a product is increased, and the capacity, the cycle and the gas production performance of a finished product are deteriorated.
In the present invention, the method for producing the pre-sintered product preferably includes:
and mixing the high-nickel ternary precursor, the coarse powder lithium hydroxide and the additive, and then performing presintering to obtain a presintering product.
In the invention, the high nickel material needs to be prepared by using lithium hydroxide due to high requirement on alkali amount; the price of the micro powder lithium hydroxide is about 40 ten thousand yuan/ton, but the price of the coarse powder lithium hydroxide is about 39 ten thousand yuan/ton, in the production of the high-nickel ternary cathode material, if the coarse powder lithium hydroxide can be used for replacing the micro powder lithium hydroxide, the raw material cost can be reduced, the conventional 330 x 110 sagger charging can only be 5Kg, but after the precursor and the lithium hydroxide are dehydrated, the loading amount can reach 12Kg, and the efficiency can be further improved, so that the product manufacturing cost is reduced.
In the invention, the mass content of LiOH in the coarse lithium hydroxide is preferably 56.5-58.0 wt%, more preferably 57-57.5%, and most preferably 57.2-57.3%; the granularity D10 of the coarse lithium hydroxide powder is preferably 20-140 μm, more preferably 30-120 μm, more preferably 50-100 μm, and most preferably 60-80 μm; d50 is preferably 150-500 μm, more preferably 200-400 μm, more preferably 250-350 μm, and most preferably 300 μm; d100 is preferably 600 to 1000 μm, more preferably 700 to 900 μm, and most preferably 800 μm.
In the present invention, the additive is preferably selected from ZrO 2 、Al 2 O 3 、WO 3 、Y 2 O 3 、MgO、Ta 2 O 5 、CeF 3 、SrO、CeO 2 And one or more of BN. The invention can lead the obtained presintered product to contain doping elements by adopting the additive in the presintering process.
In the invention, the mass ratio of the high-nickel ternary precursor, the coarse lithium hydroxide and the additive is preferably 1000: (465-490): (2-10), more preferably 1000: (470-485): (3-8), most preferably 1000: (475-480): (4-6).
In the present invention, the mixing is preferably performed under stirring; the stirring speed is preferably 250-350 rpm, more preferably 280-320 rpm, and most preferably 300 rpm; the mixing time is preferably 100-150 min, more preferably 110-140 min, and most preferably 120-130 min.
In the present invention, the pre-sintering is preferably performed in a rotary kiln, and pre-oxidation is performed.
In the invention, the temperature in the pre-sintering process is preferably 500-600 ℃, more preferably 520-580 ℃, and most preferably 540-560 ℃; the pre-sintering time is preferably 4-8 h, more preferably 5-7 h, and most preferably 6 h; the pre-sintering is preferably carried out in an atmosphere of oxygen (pure oxygen); the flow rate of the oxygen is preferably 450-550L/min, more preferably 480-520L/min, and most preferably 500L/min.
In the present invention, the method for preparing the primary sintered product preferably includes:
and carrying out primary sintering on the pre-sintered product to obtain a primary sintered product.
In the present invention, the primary sintering is preferably carried out in a roller kiln, more preferably in an atmosphere roller kiln, most preferably in a 10m atmosphere roller kiln; the loading amount of the sagger in the primary sintering process is preferably 10-15 kg/sagger, more preferably 11-14 kg/sagger and most preferably 12 kg/sagger; the filling height is preferably 6-10 cm, more preferably 7-9 cm, and most preferably 8 cm.
In the invention, the temperature of the primary sintering is preferably 735-850 ℃, more preferably 750-820 ℃, and most preferably 780-800 ℃; the sintering time is preferably 10-15 h, more preferably 11-14 h, and most preferably 12-13 h; the sintering atmosphere is preferably oxygen (pure oxygen), and the flow rate of the oxygen is preferably 800-1200L/min, more preferably 900-1100L/min, and most preferably 1000L/min.
The invention provides a preparation method of a low-cost high-nickel ternary cathode material, which comprises the following steps:
and sequentially crushing, washing, drying, doping and sintering (secondary sintering) the primary sintered product to obtain the low-cost high-nickel ternary cathode material.
In the present invention, the D50 after crushing is preferably 8 to 12 μm, more preferably 9 to 11 μm, and most preferably 10 μm.
In the invention, the mass ratio of the crushed product to water in the water washing process is preferably (0.8-1.2): 1, more preferably 1: 1; the time for washing is preferably 1-3 min, more preferably 1.5-2.5 min, and most preferably 2 min; stirring is preferably carried out in the water washing process, and the stirring speed is preferably 30-50 rpm, more preferably 35-45 rpm, and most preferably 40 rpm; the temperature of the water washing is preferably 3-7 ℃, more preferably 4-6 ℃, and most preferably 5 ℃.
In the present invention, the washing is preferably followed by pressure filtration.
In the present invention, the moisture content in the dried product is preferably < 0.5 wt%.
The doping is not particularly limited in the present invention, and the doping element known to those skilled in the art may be doped with the doping substance of the cathode material and the doping amount known to those skilled in the art, and the doping substance may be H 3 BO 3 、Al 2 O 3 Etc.; stirring and mixing are preferably carried out in the doping process, and the stirring speed is preferably 100-300 rpm, more preferably 150-250 rpm, and most preferably 200 rpm; the mixing time is preferably 100-140 min, more preferably 110-130 min, and most preferably 120 min.
In the invention, the loading amount of the sagger in the sintering (secondary sintering) process is preferably 4.5-5.5 kg/sagger, more preferably 4.8-5.2 kg/sagger, and most preferably 5 kg/sagger; the sintering temperature is preferably 280-600 ℃, more preferably 300-500 ℃, and most preferably 400 ℃; the sintering time is preferably 6-10 h, more preferably 7-9 h, and most preferably 8 h.
In the present invention, after the completion of the sintering (secondary sintering), it is preferable to further include:
and screening, deironing and packaging the obtained sintered product to obtain the low-cost high-nickel ternary cathode material.
The method provided by the invention can obviously reduce the production and processing cost of the high-nickel ternary lithium ion battery anode material while ensuring the product performance.
The present invention provides a battery comprising: the low-cost high-nickel ternary cathode material is prepared by the technical scheme.
The preparation method of the battery is not particularly limited, and a person skilled in the art can prepare the battery by using the low-cost high-nickel ternary cathode material as a cathode material according to the conventional battery preparation method in the field according to the required battery.
In the present invention, the battery is preferably a button cell battery.
In the present invention, the method for manufacturing the battery preferably includes:
mixing a low-cost high-nickel ternary positive electrode material, acetylene black, polyvinylidene fluoride and NMP to obtain slurry;
coating the slurry on an aluminum foil, drying, tabletting and cutting to obtain a positive plate;
taking a lithium plate as a negative plate;
and assembling the positive plate, the negative plate, the electrolyte and the diaphragm to obtain the button cell.
In the invention, the mass ratio of the low-cost high-nickel ternary cathode material to the acetylene black to the polyvinylidene fluoride is preferably (92-96): (2-4): (2-4), more preferably (93-95): (2.5-3.5): (2.5 to 3.5), most preferably 94: 3: 3.
in the present invention, the mixing is preferably performed under stirring; the stirring time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and most preferably 2 hours.
In the present invention, the drying method is preferably vacuum baking; the drying temperature is preferably 70-90 ℃, more preferably 75-85 ℃, and most preferably 80 ℃.
In the invention, the diameter of the positive electrode sheet is preferably 12-16 mm, more preferably 13-15 mm, and most preferably 14 mm.
In the invention, the diameter of the negative electrode piece is preferably 14-18 mm, more preferably 15-17 mm, and most preferably 16 mm.
In the present invention, the electrolyte is preferably 1mol/L LiPF6+ DEC/EC (volume ratio 1: 1); the separator is preferably a polycegard propylene microporous membrane.
In the present invention, the assembly is preferably performed in a glove box filled with argon gas.
According to the invention, the precursor is dehydrated by adopting the rotary kiln, and is mixed with the coarse powder lithium hydroxide after the dehydration is finished, and then the dehydration is carried out, so that the dehydration is complete, and the obtained anode material has good comprehensive performances such as circulation, gas generation and the like.
Precursor Ni used in the following examples of the invention 0.85 Co 0.06 Mn 0.09 (OH) 2 Is a product of model number M85610 supplied by greens americas limited; coarse powder lithium hydroxide is a product of model ZHBKE18047 provided by Sichuan Yongyuan lithium industry Co.
Example 1
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding into a rotary kiln for presintering and dehydrating at 350 deg.C for 6 hr in the presence of pure oxygen at a flow rate of 500L/min to obtain presintered material. The presintered precursor, 9.45Kg of coarse powder lithium hydroxide and 10g of ZrO 2 Stirring and mixing 5g of SrO at 300rpm for 120min, placing the mixture into a rotary kiln for pre-oxidation after the materials are uniformly mixed, wherein the sintering temperature is 600 ℃, the time is 6h, the atmosphere is pure oxygen, and the gas flow is 500L/min to obtain pre-oxidized mixtureAnd (3) feeding. And (3) performing primary sintering on the pre-sintered material in a roller kiln with the atmosphere of 10 meters, wherein the loading amount of a sagger is 12 kg/sagger, the loading height is about 8cm, the sintering temperature is 755 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, and the oxygen ventilation amount is 1000L/min, so as to obtain the primary sintered material. Pulverizing the primary sintering material, controlling D50 at 10.0 + -1.0 μm, washing with water at a ratio of 1:1 for 2min at a stirring rod rotation speed of 40rpm and a water temperature of 5 deg.C, press-filtering, and drying to control water content below 0.5 wt%. The dried material was combined with 10gH 3 BO 3 Stirring and mixing for 120min at 200rpm, placing the mixture in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 300 ℃, the sintering time is 8 hours, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
Example 2
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding into a rotary kiln for presintering and dehydrating at 350 deg.C for 6 hr in the presence of pure oxygen at a flow rate of 500L/min to obtain presintered material. The presintered precursor, 9.45Kg of coarse powder lithium hydroxide and 10g of ZrO 2 And 5g of SrO is stirred and mixed for 120min at 300rpm, after the materials are uniformly mixed, the materials are placed into a rotary kiln for pre-oxidation, the sintering temperature is 500 ℃, the time is 6h, the atmosphere is pure oxygen, and the gas flow is 500L/min, so that the pre-oxidized materials are obtained. And (3) performing primary sintering on the pre-sintered material in a roller kiln with the atmosphere of 10 meters, wherein the loading amount of a sagger is 10.5 kg/sagger, the loading height is about 8cm, the sintering temperature is 755 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, and the oxygen ventilation amount is 1000L/min, so as to obtain the primary sintered material. Pulverizing the primary sintering material, controlling D50 at 10.0 + -1.0 μm, washing with water at a ratio of 1:1 for 2min at a stirring rod rotation speed of 40rpm and a water temperature of 5 deg.C, press-filtering, and drying to control water content below 0.5 wt%. The dried material was combined with 10gH 3 BO 3 Stirring and mixing at 200rpm for 120min, placing in roller kiln for secondary sintering after the materials are uniformly mixed, wherein the loading amount of sagger is 5.5 kg/sagger, the sintering temperature is 300 ℃, the sintering time is 8h, and sievingAnd removing iron and packaging to obtain the finished high-nickel ternary material.
Example 3
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding the mixture into a rotary kiln for presintering and dehydrating, wherein the sintering temperature is 350 ℃, the time is 6 hours, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so as to obtain the presintered material. The presintered precursor, 9.45Kg of coarse powder lithium hydroxide and 10g of ZrO 2 And 5g of SrO is stirred and mixed for 120min at 300rpm, after the materials are uniformly mixed, the materials are placed into a rotary kiln for pre-oxidation, the sintering temperature is 400 ℃, the time is 6h, the atmosphere is pure oxygen, and the gas flow is 500L/min, so that the pre-oxidized materials are obtained. And (3) performing primary sintering on the pre-sintered material in a roller kiln with the atmosphere of 10 meters, wherein the loading amount of a sagger is 9 kg/sagger, the loading height is about 8cm, the sintering temperature is 755 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, and the oxygen ventilation amount is 1000L/min, so as to obtain the primary sintered material. Pulverizing the primary sintering material, controlling D50 at 10.0 + -1.0 μm, washing with water at a ratio of 1:1 for 2min at a stirring rod rotation speed of 40rpm and a water temperature of 5 deg.C, press-filtering, and drying to control water content below 0.5 wt%. The dried material was combined with 10gH 3 BO 3 Stirring and mixing for 120min at 200rpm, placing the mixture in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 300 ℃, the sintering time is 8 hours, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
Example 4
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding the mixture into a rotary kiln for presintering and dehydrating, wherein the sintering temperature is 350 ℃, the time is 6 hours, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so as to obtain the presintered material. 9.45Kg of coarse powder lithium hydroxide is added into a rotary kiln for presintering and dehydration, the sintering temperature is 150 ℃, the time is 6 hours, the atmosphere is pure oxygen, and the gas flow is 500L/min, so that the presintering material is obtained. Pre-sintered precursor, coarse powder of lithium hydroxide and 10g of ZrO 2 5g of SrO is stirred and mixed for 120min at 300rpm, and after the materials are uniformly mixed, the presintered material is added into 10mAnd performing primary sintering in an atmosphere roller kiln, wherein the loading amount of a sagger is 12 kg/sagger, the loading height of the sagger is about 8cm, the sintering temperature is 755 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, and the oxygen ventilation volume is 1000L/min, so that a primary sintering material is obtained. Pulverizing the primary sintering material, controlling D50 at 10.0 + -1.0 μm, washing with water at a ratio of 1:1 for 2min at a stirring rod rotation speed of 40rpm and a water temperature of 5 deg.C, press-filtering, and drying to control water content below 0.55. The dried material was combined with 10gH 3 BO 3 Stirring and mixing for 120min at 200rpm, placing the mixture in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 300 ℃, the sintering time is 8 hours, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
Example 5
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding into a rotary kiln for presintering and dehydrating at 350 deg.C for 6 hr in the presence of pure oxygen at a flow rate of 500L/min to obtain presintered material. Pre-burning the precursor, 9.45Kg of coarse powder lithium hydroxide and 10g of ZrO 2 、5gTiO 2 Stirring and mixing at 300rpm for 120min, placing into a rotary kiln for pre-oxidation after the materials are uniformly mixed, wherein the sintering temperature is 600 ℃, the time is 6h, the atmosphere is pure oxygen, and the gas flow is 500L/min, so as to obtain the pre-oxidized materials. And (3) performing primary sintering on the pre-sintered material in a roller kiln with the atmosphere of 10 meters, wherein the loading amount of a sagger is 12 kg/sagger, the loading height is about 8cm, the sintering temperature is 755 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, and the oxygen ventilation amount is 1000L/min, so as to obtain the primary sintered material. Pulverizing the primary sintering material, controlling D50 at 10.0 + -1.0 μm, washing with water at a ratio of 1:1 for 2min at a stirring rod rotation speed of 40rpm and a water temperature of 5 deg.C, press-filtering, and drying to control water content below 0.5%. The dried material was combined with 10gH 3 BO 3 Stirring and mixing at 200rpm for 120min, placing in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 300 ℃, the sintering time is 8h, and obtaining the material after sieving, deironing and packagingThe finished product is high-nickel ternary material.
Example 6
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding into a rotary kiln for presintering and dehydrating at 350 deg.C for 6 hr in the presence of pure oxygen at a flow rate of 500L/min to obtain presintered material. The presintered precursor, 9.45Kg of coarse powder lithium hydroxide and 7g of WO were mixed 3 And 3g of MgO is stirred and mixed for 120min at 300rpm, after the materials are uniformly mixed, the materials are put into a rotary kiln for pre-oxidation, the sintering temperature is 600 ℃, the time is 6h, the atmosphere is pure oxygen, and the air flow is 500L/min, so that the pre-oxidized materials are obtained. And (3) performing primary sintering on the pre-sintered material in a roller kiln with the atmosphere of 10 meters, wherein the loading amount of a sagger is 12 kg/sagger, the loading height is about 8cm, the sintering temperature is 755 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, and the oxygen ventilation amount is 1000L/min, so as to obtain the primary sintered material. Pulverizing the primary sintering material, controlling D50 at 10.0 + -1.0 μm, washing with water at a ratio of 1:1 for 2min at a stirring rod rotation speed of 40rpm and a water temperature of 5 deg.C, press-filtering, and drying to control water content below 0.5%. The dried material was combined with 10gH 3 BO 3 、5gAl 2 O 3 Stirring and mixing for 120min at 200rpm, placing the mixture in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 300 ℃, the sintering time is 8 hours, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
Example 7
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 Adding into a rotary kiln for presintering and dehydrating at 350 deg.C for 6 hr in the presence of pure oxygen at a flow rate of 500L/min to obtain presintered material. The presintering precursor, 9.45Kg of coarse powder lithium hydroxide and 5gY 2 O 3 Stirring and mixing at 300rpm for 120min, placing into a rotary kiln for pre-oxidation after the materials are uniformly mixed, wherein the sintering temperature is 600 ℃, the time is 6h, the atmosphere is pure oxygen, and the gas flow is 500L/min, so as to obtain the pre-oxidized materials. Roller kiln for presintering materials in 10m atmosphereAnd performing primary sintering, wherein the loading amount of the sagger is 12 kg/sagger, the loading height is about 8cm, the sintering temperature is 755 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, and the oxygen ventilation capacity is 1000L/min, so as to obtain a primary sintering material. Pulverizing the primary sintering material, controlling D50 at 10.0 + -1.0 μm, washing with water at a ratio of 1:1 for 2min at a stirring rod rotation speed of 40rpm and a water temperature of 5 deg.C, press-filtering, and drying to control water content below 0.5%. The dried material was combined with 10gH 3 BO 3 、5gAl 2 O 3 Stirring and mixing for 120min at 200rpm, placing the mixture in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 300 ℃, the sintering time is 8 hours, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
Comparative example 1
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 And 9.45Kg of fine powder of lithium hydroxide, 10g of ZrO 2 And stirring and mixing 5g of SrO at 300rpm for 120min, after the materials are uniformly mixed, performing primary sintering on the materials in a roller kiln with the atmosphere of 10m, wherein the loading amount of a sagger is 5 kg/sagger, the loading height is about 8cm, the sintering temperature is 755 ℃, the time is 12h, the sintering atmosphere is pure oxygen atmosphere, and the oxygen ventilation volume is 1000L/min, so that the primary sintered material is obtained. Pulverizing the primary sintering material, controlling D50 at 10.0 + -1.0 μm, washing with water at a ratio of 1:1 for 2min at a stirring rod rotation speed of 40rpm and a water temperature of 5 deg.C, press-filtering, and drying to control water content below 0.5 wt%. The dried material was combined with 10gH 3 BO 3 Stirring and mixing for 120min at 200rpm, placing the mixture in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 300 ℃, the sintering time is 8 hours, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
Comparative example 2
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 And 9.45Kg of coarse powder lithium hydroxide, 10g of ZrO 2 5g of SrO is stirred and mixed for 120min at 300rpm, and after the materials are uniformly mixed, the materials are put into a rotary kiln to be fedPre-oxidizing at 500 deg.c for 6 hr in the atmosphere of pure oxygen and gas flow rate of 500L/min to obtain pre-oxidized material. And (3) performing primary sintering on the pre-sintered material in a roller kiln with the atmosphere of 10 meters, wherein the loading amount of a sagger is 12 kg/sagger, the loading height is about 8cm, the sintering temperature is 755 ℃, the time is 12 hours, the sintering atmosphere is pure oxygen atmosphere, and the oxygen ventilation amount is 1000L/min, so as to obtain the primary sintered material. Pulverizing the primary sintering material, controlling D50 at 10.0 + -1.0 μm, washing with water at a ratio of 1:1 for 2min at a stirring rod rotation speed of 40rpm and a water temperature of 5 deg.C, press-filtering, and drying to control water content below 0.5 wt%. The dried material was combined with 10gH 3 BO 3 Stirring and mixing at 200rpm for 120min, after the materials are uniformly mixed, placing the materials in a roller kiln for secondary sintering, wherein the loading amount of a sagger is 5.5 kg/sagger, the sintering temperature is 300 ℃, the sintering time is 8 hours, and screening, deironing and packaging are carried out to obtain the finished high-nickel ternary material.
Performance detection
When SEM examination (50K times) is performed on the high nickel cathode materials prepared in the examples and comparative examples of the present invention, the examination results are shown in fig. 1 to 9, and it can be seen that dehydration of lithium hydroxide together with the precursor results in a significant alkali on the surface of the material, which is not favorable for subsequent processing (e.g., comparative examples 1 and 2).
The conditions and productivity for preparing the high nickel cathode material according to the embodiments of the present invention and the comparative examples are as follows:
the button cell is assembled by the high-nickel positive electrode materials prepared in the embodiment and the comparative example, and the specific method comprises the following steps:
weighing the high-nickel positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 94: 3, uniformly mixing, adding NMP, stirring for 2 hours to form viscous slurry, uniformly coating the slurry on an aluminum foil, then carrying out vacuum baking at 80 ℃, tabletting, and cutting a positive electrode plate with the diameter of 14 mm.
A pure lithium sheet with the diameter of 16mm is used as a negative electrode sheet, 1mol/L LiPF6+ DEC/EC (volume ratio of 1: 1) mixed solution is used as electrolyte, a poly Celgard propylene microporous membrane is used as a diaphragm, and the button cell is assembled in a glove box filled with argon.
Testing of Li in the products after primary sintering during the production of the high-nickel cathode materials prepared in the examples of the present invention and comparative examples 2 CO 3 Content, LiOH content and free Li + The content of (a); the specific detection method comprises the following steps: weighing 30g of materials, adding 100ml of pure water, stirring for 30min, filtering by adopting double-layer medium-speed filter paper, transferring 10ml of liquid, titrating by adopting 0.05mol/L HCl, and judging the titration endpoint according to an acid-base titration method.
The button cell prepared by the high nickel cathode material obtained in the above examples and comparative examples is tested for 0.2C capacity under the following detection conditions: the assembled button cell is charged and discharged in a blue-electricity device at the test temperature of 25 +/-1 ℃ and the test voltage of 2.5-4.25V at 0.2C/0.2C, and the cut-off current of the charging is 0.05C (1℃ nominal capacity of 200 mAh/g); the detection results are as follows:
detecting the generated gas by heat measurement at 70 ℃ for 7 days, wherein the detection method comprises the following steps: the method comprises the steps of firstly testing the volume of a fully charged battery after the battery is fully charged, then storing the fully charged battery at the high temperature of 70 ℃ for 7 days, then testing the volume of the battery, and calculating the difference value of the volume of the fully charged battery and the volume of the fully charged battery to obtain the thermal measurement produced gas, wherein the volume measuring equipment is an electronic solid densimeter TW-120E; the results of the measurements are shown in FIG. 10 and the table above.
The capacity retention rate of 300 cycles at 45 ℃ is detected, and the detection method comprises the following steps: calculating the capacity retention rate of the capacitor by adopting Xinwei CT3008-5V3A-A1, circulating the voltage of 4.25-3V, cutting off the current of 20mA at the constant voltage and circulating the current for 300 circles at the temperature of 45 ℃; the results of the measurements are shown in FIG. 11 and the table above.
The invention provides a low-cost high-nickel ternary cathode material and a preparation method thereof. The invention can obviously improve the problems of high caustic soda amount, low finished product capacity, poor cycle performance and poor gas production caused by mixed pre-oxidation; meanwhile, the processing cost of the high-nickel ternary cathode material can be effectively reduced, the cycle and gas production performance of the high-nickel ternary cathode material are considered, and the competitiveness of the high-nickel ternary cathode material can be effectively improved.
While the invention has been described and illustrated with reference to specific embodiments thereof, such description and illustration are not intended to limit the invention. It will be clearly understood by those skilled in the art that various changes in form and details may be made therein without departing from the true spirit and scope of the invention as defined by the appended claims, to adapt a particular situation, material, composition of matter, substance, method or process to the objective, spirit and scope of this application. All such modifications are intended to be within the scope of the claims appended hereto. Although the methods disclosed herein have been described with reference to particular operations being performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form equivalent methods without departing from the teachings of the present disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations is not a limitation of the present application.
Claims (10)
1. A low-cost high-nickel ternary cathode material has a general formula:
LiNi x CoyA 1-x-y O 2 formula I;
in the formula I, x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.4;
a is selected from at least one element of Mn, Al, Ta, Ti, Nb, Ge, Y, Nb, W, Zr, B, Ce, Ca and Sr;
the 7-day thermal measurement gas production rate of the low-cost high-nickel ternary cathode material is less than 15 percent, and Li 2 CO 3 The content is less than 2000ppm, and the LiOH content is less than 5000 ppm.
2. The low-cost high-nickel ternary cathode material according to claim 1, wherein the low-cost high-nickel ternary cathode material is prepared from a material comprising a primary sintered product;
the capacity of the primary sintered product is more than 170mAh/g under the conditions of 0.2C and 2.5-4.25V;
the bulk density of the primary sintered product is 1.5-1.9 g/cc;
the molar ratio of Li to M in the primary sintering product is (0.95-1.08): 1, wherein M is the total molar weight of Ni, Co and A;
li in the primary sintered product 2 CO 3 The mass content of the active carbon is less than 8000ppm, and the mass content of LiOH is less than 8000 ppm.
3. The low-cost high-nickel ternary positive electrode material according to claim 2, wherein the characteristic peaks of XRD of the primary sintered product comprise:
the peak intensity of 18-19 degrees is 20000-30000, the peak intensity of 36-37 degrees is 7000-8000, the peak intensity of 44-45 degrees is 11000-13000, the peak intensity of 48-49 degrees is 2000-3000, the peak intensity of 58-59 degrees is 1500-2500, the peak intensity of 64-65 degrees is 2000-3000, and the peak intensity of 68-69 degrees is 1200-2200.
4. The low-cost high-nickel ternary positive electrode material according to claim 2, wherein the primary sintered product is prepared from a material comprising a pre-sintered product;
the loose packed density of the pre-sintered product is 1.2-1.7 g/cc;
the XRD characteristic peaks of the presintered product comprise:
the peak intensity of 18-19 degrees is 2000-3000, the peak intensity of 32-33 degrees is 1000-2000, the peak intensity of 38-39 degrees is 1500-2500, the peak intensity of 42-43 degrees is 3500-4500, and the peak intensity of 64-65 degrees is 1500-2500.
5. The low-cost high-nickel ternary cathode material according to claim 4, wherein the pre-sintered product is prepared from a material comprising a high-nickel ternary precursor;
the moisture content of the high-nickel ternary precursor is less than 1 wt%;
the bulk density of the high-nickel ternary precursor is 1.5-1.8 g/cc;
the XRD characteristic peaks of the high-nickel ternary precursor comprise:
the peak intensity of 37-38 degrees is 3000-4000, the peak intensity of 43-44 degrees is 4000-4500, and the peak intensity of 63-64 degrees is 2500-3500.
6. The low-cost high-nickel ternary cathode material according to claim 5, wherein the high-nickel ternary precursor is prepared from a material comprising a high-nickel ternary precursor;
the high-nickel ternary precursor has the general formula:
Ni x Co y A 1-x-y (OH) 2 in the formula II, the compound is shown in the specification,
in the formula II, x is more than or equal to 0.6 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 0.4;
a is at least one element selected from Mn, Al, Ta, Ti, Nb, Ge, Y, Nb, W, Zr, B, Ce, Ca and Sr;
the bulk density D of the high-nickel ternary precursor is 1.4-1.8 g/cc, the moisture content is less than 2 wt%, and the BET is 4-12 m 2 /g；
The XRD characteristic peaks of the high-nickel ternary precursor comprise:
the peak intensity of 19-20 degrees is 10000-12000, the peak intensity of 33-34 degrees is 6000-7000, the peak intensity of 38-39 degrees is 9000-11000, the peak intensity of 52-53 degrees is 3500-4500, the peak intensity of 59-60 degrees is 3500-4500, and the peak intensity of 63-64 degrees is 2000-3000.
7. A method for preparing the low-cost high-nickel ternary cathode material of claim 1, comprising:
and sequentially crushing, washing, drying, doping and sintering the primary sintered product to obtain the low-cost high-nickel ternary cathode material.
8. The method of claim 7, wherein the method of preparing the primary sintered product comprises:
performing primary sintering on the pre-sintered product to obtain a primary sintered product;
the preparation method of the presintered product comprises the following steps:
mixing a high-nickel ternary precursor, coarse powder lithium hydroxide and an additive, and then presintering to obtain a presintering product;
the preparation method of the high-nickel ternary precursor comprises the following steps:
and dehydrating the high-nickel ternary precursor to obtain the high-nickel ternary precursor.
9. The method according to claim 8, wherein the temperature of the dehydration is 100-370 ℃;
the pre-sintering temperature is 500-600 ℃;
the temperature of the primary sintering is 735-850 ℃;
the sintering temperature is 280-600 ℃.
10. A battery, comprising: the low-cost high-nickel ternary positive electrode material of claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594231A (en) * | 2022-10-19 | 2023-01-13 | 湖南长远锂科新能源有限公司（Cn） | Method for preparing cathode material by using crude lithium source |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108923043A (en) * | 2018-07-02 | 2018-11-30 | 湖南德景源科技有限公司 | A kind of preparation method of nickelic polynary positive pole material |
| CN110137488A (en) * | 2019-05-28 | 2019-08-16 | 郑州中科新兴产业技术研究院 | A kind of nickelic positive electrode of secondary lithium batteries and preparation method thereof |
| CN110896674A (en) * | 2018-03-21 | 2020-03-20 | 浙江林奈新能源有限公司 | Nickel-cobalt-aluminum ternary lithium ion battery positive electrode material, preparation method and application thereof, and lithium ion battery |
| CN111217407A (en) * | 2020-01-16 | 2020-06-02 | 东莞东阳光科研发有限公司 | High-nickel anode material and preparation method and application thereof |
| CN112125353A (en) * | 2020-05-26 | 2020-12-25 | 宜宾锂宝新材料有限公司 | Preparation method of high-nickel ternary cathode material for lithium ion battery |
| CN112687868A (en) * | 2020-12-28 | 2021-04-20 | 大连博融新材料有限公司 | High-nickel ternary cathode material and preparation method thereof |
| CN112794371A (en) * | 2020-12-31 | 2021-05-14 | 宜宾锂宝新材料有限公司 | Low-cost high-nickel ternary lithium ion battery cathode material and preparation method thereof |
| CN113422046A (en) * | 2021-06-30 | 2021-09-21 | 湖南杉杉能源科技有限公司 | High-nickel single crystal nickel-cobalt-aluminum ternary cathode material and preparation method thereof |
| CN114590848A (en) * | 2022-03-01 | 2022-06-07 | 合肥国轩高科动力能源有限公司 | Modified single-crystal high-nickel ternary material and preparation method and application thereof |
-
2022
- 2022-07-29 CN CN202210912244.1A patent/CN115043443B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110896674A (en) * | 2018-03-21 | 2020-03-20 | 浙江林奈新能源有限公司 | Nickel-cobalt-aluminum ternary lithium ion battery positive electrode material, preparation method and application thereof, and lithium ion battery |
| CN108923043A (en) * | 2018-07-02 | 2018-11-30 | 湖南德景源科技有限公司 | A kind of preparation method of nickelic polynary positive pole material |
| CN110137488A (en) * | 2019-05-28 | 2019-08-16 | 郑州中科新兴产业技术研究院 | A kind of nickelic positive electrode of secondary lithium batteries and preparation method thereof |
| CN111217407A (en) * | 2020-01-16 | 2020-06-02 | 东莞东阳光科研发有限公司 | High-nickel anode material and preparation method and application thereof |
| CN112125353A (en) * | 2020-05-26 | 2020-12-25 | 宜宾锂宝新材料有限公司 | Preparation method of high-nickel ternary cathode material for lithium ion battery |
| CN112687868A (en) * | 2020-12-28 | 2021-04-20 | 大连博融新材料有限公司 | High-nickel ternary cathode material and preparation method thereof |
| CN112794371A (en) * | 2020-12-31 | 2021-05-14 | 宜宾锂宝新材料有限公司 | Low-cost high-nickel ternary lithium ion battery cathode material and preparation method thereof |
| CN113422046A (en) * | 2021-06-30 | 2021-09-21 | 湖南杉杉能源科技有限公司 | High-nickel single crystal nickel-cobalt-aluminum ternary cathode material and preparation method thereof |
| CN114590848A (en) * | 2022-03-01 | 2022-06-07 | 合肥国轩高科动力能源有限公司 | Modified single-crystal high-nickel ternary material and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115594231A (en) * | 2022-10-19 | 2023-01-13 | 湖南长远锂科新能源有限公司（Cn） | Method for preparing cathode material by using crude lithium source |
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