CN115043443B - Low-cost high-nickel ternary positive electrode material and preparation method and application thereof - Google Patents
Low-cost high-nickel ternary positive electrode material and preparation method and application thereof Download PDFInfo
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- CN115043443B CN115043443B CN202210912244.1A CN202210912244A CN115043443B CN 115043443 B CN115043443 B CN 115043443B CN 202210912244 A CN202210912244 A CN 202210912244A CN 115043443 B CN115043443 B CN 115043443B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 117
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 109
- 239000002243 precursor Substances 0.000 claims abstract description 68
- 238000002156 mixing Methods 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 28
- 230000018044 dehydration Effects 0.000 claims abstract description 24
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 239000010405 anode material Substances 0.000 claims abstract description 10
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 4
- 238000005259 measurement Methods 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims description 164
- 239000000463 material Substances 0.000 claims description 103
- 238000005406 washing Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000010406 cathode material Substances 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 238000003756 stirring Methods 0.000 description 31
- 238000011068 loading method Methods 0.000 description 30
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000004806 packaging method and process Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000003825 pressing Methods 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- 238000012216 screening Methods 0.000 description 9
- 238000009423 ventilation Methods 0.000 description 9
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method 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
- 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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 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
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 230000035924 thermogenesis Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- 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 positive electrode material, the general formula of the components is LiNi x Co y A 1‑x‑y O 2 A 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, sr; the low-cost high-nickel ternary positive electrode material has a 7-day thermal measurement gas production of less than 15 percent, li 2 CO 3 The content is less than 2000ppm, and the LiOH content is less than 5000ppm. The method comprises the steps of firstly adopting a rotary kiln to dehydrate the precursor, mixing the dehydrated precursor with coarse powder lithium hydroxide, and then dehydrating the mixture to ensure complete dehydration, wherein the obtained positive electrode material has good comprehensive properties such as circulation, gas production and the like. The invention also provides a preparation method and application of the low-cost high-nickel ternary anode material.
Description
Technical Field
The invention belongs to the technical field of positive electrode materials, and particularly relates to a low-cost high-nickel ternary positive electrode material, and a preparation method and application thereof.
Background
In recent years, with the rise of new energy industry, new energy storage batteries occupy an important role in the whole new energy industry. Among them, lithium ion batteries are paid attention to by the industry in terms of their light weight, large capacity, cleanliness, environmental protection, no memory effect, and the like. In the lithium ion battery, the cost of the positive electrode material occupies 30 to 50 percent of the cost of the whole battery. Therefore, developing a lithium ion positive electrode 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 has high requirements on equipment and environment in the production and processing processes, and the production process is complex, so that the processing cost is high. In order to ensure that the high-nickel ternary cathode material has excellent capacity, multiplying power, circulation and other performances, most of lithium salts used in the current production of the high-nickel ternary cathode material are ternary precursors of micro-powder lithium hydroxide and crystal water. Along with the rapid development of new energy industry, the lithium ion ternary cathode material is increasingly competitive, and the cost reduction is becoming the great trend of the industry.
In the prior art, a high-nickel ternary precursor and coarse powder lithium hydroxide are uniformly mixed and then presintered by using a rotary kiln to obtain presintered materials; sintering the pre-sintered material for the first time to obtain a material after the first time; crushing, washing, drying and coating the materials after 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 needs to be further improved.
Disclosure of Invention
In view of the above, an object of the embodiments of the present invention is to provide a low-cost high-nickel ternary positive electrode material, and a preparation method and an application thereof.
The invention provides a low-cost high-nickel ternary positive electrode material, which comprises the following components in general formula:
LiNi x CoyA 1-x-y O 2 a 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, sr;
the low-cost high-nickel ternary positive electrode material has a 7-day thermal measurement gas production of less than 15 percent, li 2 CO 3 The content is less than 2000ppm, and the LiOH content is less than 5000ppm.
Preferably, the low-cost high-nickel ternary positive electrode material is prepared from a material comprising a primary sintering product;
the capacity of the primary sintering product under the conditions of 0.2C and 2.5-4.25V is more than 170mAh/g;
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 weight of Ni, co and A;
li in the primary sintering product 2 CO 3 The mass content of (C) is less than 8000ppm, and the mass content of LiOH is less than 8000ppm.
Preferably, the characteristic peaks of XRD of the primary sintered product include:
the peak intensity of 18-19 DEG is 20000-30000, the peak intensity of 36-37 DEG is 7000-8000, the peak intensity of 44-45 DEG is 11000-13000, the peak intensity of 48-49 DEG is 2000-3000, the peak intensity of 58-59 DEG is 1500-2500, the peak intensity of 64-65 DEG is 2000-3000, and the peak intensity of 68-69 DEG 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 pre-sintered product include:
the peak intensity of 18-19 DEG is 2000-3000, the peak intensity of 32-33 DEG is 1000-2000, the peak intensity of 38-39 DEG is 1500-2500, the peak intensity of 42-43 DEG is 3500-4500, and the peak intensity of 64-65 DEG is 1500-2500.
Preferably, the pre-sintering product is prepared from a material comprising a high nickel ternary precursor;
the moisture content of the high-nickel ternary precursor is less than 1wt%;
the bulk density (AD) of the high-nickel ternary precursor is 1.5-1.8 g/cc;
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 following general formula:
Ni x Co y A 1-x-y (OH) 2 the compound of the formula II 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, sr;
the high nickel ternary precursor has a bulk density (AD) of 1.4-1.8 g/cc, a moisture content of < 2wt%, and a BET of 4-12 m 2 /g；
XRD characteristic peaks of the high-nickel ternary precursor include:
the peak intensity of 19-20 DEG is 10000-12000, the peak intensity of 33-34 DEG is 6000-7000, the peak intensity of 38-39 DEG is 9000-11000, the peak intensity of 52-53 DEG is 3500-4500, the peak intensity of 59-60 DEG is 3500-4500, and the peak intensity of 63-64 DEG is 2000-3000.
The invention provides a preparation method of the low-cost high-nickel ternary positive electrode material, which comprises the following steps:
and crushing, washing, drying, doping and sintering the primary sintering product in sequence to obtain the low-cost high-nickel ternary anode material.
Preferably, the preparation method of the primary sintering product comprises the following steps:
sintering the presintered product for the first time 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 pre-sintering to obtain a pre-sintering 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 temperature of the dehydration is 100-370 ℃;
the temperature of the pre-sintering 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 positive electrode material has the technical scheme.
The prior art for preparing the anode material has low productivity and high processing cost, has high requirements on the whole atmosphere and the periodic setting of the kiln, is easy to cause that internal water vapor cannot be removed in time, and has greatly influenced the performances of caustic soda quantity, finished product capacity, circulation, gas production and the like; the precursor is dehydrated by adopting the rotary kiln, and then is mixed with coarse powder lithium hydroxide after dehydration is completed, and then dehydration is carried out, so that the dehydration is complete, and the obtained positive electrode material has good comprehensive properties such as circulation, gas production and the like.
Drawings
FIG. 1 is an SEM image of a high nickel positive electrode material prepared according to example 1 of the present invention;
FIG. 2 is an SEM image of a high nickel positive electrode material prepared according to example 2 of the present invention;
FIG. 3 is an SEM image of a high nickel positive electrode material prepared according to example 3 of the present invention;
FIG. 4 is an SEM image of a high nickel positive electrode material prepared according to example 4 of the present invention;
FIG. 5 is an SEM image of a high nickel positive electrode material prepared according to example 5 of the present invention;
FIG. 6 is an SEM image of a high nickel positive electrode material prepared according to example 6 of the present invention;
FIG. 7 is an SEM image of a high nickel positive electrode material prepared according to example 7 of the present invention;
FIG. 8 is an SEM image of a high nickel positive electrode material prepared according to comparative example 1 of the present invention;
FIG. 9 is an SEM image of a high nickel positive electrode material prepared according to comparative example 2 of the present invention;
FIG. 10 is a 7-day 70℃shelf gas production test result of the high nickel cathode materials prepared in examples and comparative examples of the present invention;
FIG. 11 shows the results of full-cycle capacity retention test of the high nickel cathode materials prepared in examples and comparative examples according to the present invention under 1C/1C charge and discharge conditions.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a low-cost high-nickel ternary positive electrode material, which comprises the following components in general formula:
LiNi x CoyA 1-x-y O 2 a 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, sr;
the low-cost high-nickel ternary positive electrode material has a 7-day thermal measurement gas production of less than 15 percent, li 2 CO 3 The content is less than 2000ppm, and the LiOH content is less than 5000ppm.
In the invention, the low-cost high-nickel ternary positive electrode material is prepared from a material comprising a primary sintering product;
in the invention, the general formula of the primary sintering product is consistent with the general formula of the low-cost high-nickel ternary positive electrode material in the technical scheme, and is 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 1.7g/cc.
In the present invention, the molar ratio of Li and M in the primary sintered product is preferably (0.95 to 1.08): 1, more preferably (0.98 to 1.02): 1, most preferably 1:1, a step of; 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, sr.
In the present invention, the primary sintered product preferably has a capacity of > 170mAh/g, more preferably 175-200 mAh/g, still more preferably 180-195 mAh/g, and most preferably 185-190 mAh/g at 0.2C and 2.5-4.25V.
In the present invention, li in the primary sintered product 2 CO 3 Preferably < 8000ppm, more preferably 2000 to 6000ppm, more preferably 3000 to 5000ppm, most preferably 4000ppm; the mass content of LiOH is preferably < 8000ppm, more preferably 2000 to 6000ppm, more preferably 3000 to 5000ppm, most preferably 4000ppm.
In the present invention, the characteristic peaks of XRD of the primary sintered product preferably include:
the peak intensity of 18 to 19 DEG is preferably 20000 to 30000, more preferably 22000 to 28000, most preferably 24000 to 26000; the peak intensity of 36 to 37 DEG is preferably 7000 to 8000, more preferably 7200 to 7800, most preferably 7400 to 7600; the peak intensity of 44 to 45 ° is preferably 11000 to 13000, more preferably 11500 to 12500, most preferably 12000; the peak intensity of 48 to 49 DEG is preferably 2000 to 3000, more preferably 2200 to 2800, most preferably 2400 to 2600; the peak intensity of 58 to 59 ° is preferably 1500 to 2500, more preferably 1800 to 2200, most preferably 2000; the peak intensity of 64 to 65 DEG is preferably 2000 to 3000, more preferably 2200 to 2800, most preferably 2400 to 2600; the peak intensity of 68 to 69 DEG is preferably 1200 to 2200, more preferably 1400 to 1800, and most preferably 1500 to 1600.
In the present invention, the primary sintered product is preferably prepared from a material comprising 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 1.4g/cc.
In the present invention, the XRD characteristic peaks of the pre-sintered product preferably include:
the peak intensity of 18 to 19 DEG is preferably 2000 to 3000, more preferably 2200 to 2800, most preferably 2400 to 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 to 39 DEG is preferably 1500 to 2500, more preferably 1800 to 2200, most preferably 2000; the peak intensity of 42 to 43 DEG is preferably 3500 to 4500, more preferably 3800 to 4200, most preferably 4000; the peak intensity of 64 to 65 DEG is preferably 1500 to 2500, more preferably 1800 to 2200, most preferably 2000.
In the present invention, the pre-sintered product is preferably prepared from a material comprising a high nickel ternary precursor having a moisture content of preferably < 1wt%, more preferably 0 to 0.5wt%, more preferably 0.1 to 0.4wt%, most preferably 0.2 to 0.3wt%.
In the present invention, the bulk density (AD) of the high-nickel ternary precursor is preferably 1.5 to 1.8g/cc, more preferably 1.6 to 1.7g/cc.
In the present invention, XRD characteristic peaks of the high nickel ternary precursor preferably include:
the peak intensity of 37-38 DEG is preferably 3000-4000, more preferably 3200-3800, most preferably 3400-3600; the peak intensity of 43 to 44 degrees is preferably 4000 to 4500, more preferably 4100 to 4400, most preferably 4200 to 4300; the peak intensity of 63 to 64 DEG is preferably 2500 to 3500, more preferably 2800 to 3200, 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 following general formula:
Ni x Co y A 1-x-y (OH) 2 the compound of the formula II 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, sr;
in the present invention, in the formula II, x is preferably 0.7 to 0.9, more preferably 0.8; y is preferably 0.1 to 0.3, more preferably 0.2.
In the present invention, the bulk density (AD) of the high-nickel ternary precursor is preferably 1.4 to 1.8g/cc, more preferably 1.5 to 1.7g/cc, and most preferably 1.6g/cc; the moisture content is preferably < 2wt%, more preferably 0.1 to 0.7wt%, more preferably 0.2 to 0.6wt%, more preferably 0.3 to 0.5wt%, most preferably 0.4wt%; the specific surface area (BET) is preferably 4 to 12m 2 Preferably 5 to 10m 2 Preferably from 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 to 20 DEG is preferably 10000 to 12000, more preferably 10500 to 11500, most preferably 11000; the peak intensity of 33 to 34 DEG is preferably 6000 to 7000, more preferably 6200 to 6800, most preferably 6400 to 6600; the peak intensity of 38 to 39 degrees is preferably 9000 to 11000, more preferably 9500 to 10500, and most preferably 10000; the peak intensity of 52 to 53 DEG is preferably 3500 to 4500, more preferably 3800 to 4200, most preferably 4000; the peak intensity of 59 to 60 DEG is preferably 3500 to 4500, more preferably 3800 to 4200, most preferably 4000; the peak intensity of 63 to 64 DEG is preferably 2000 to 3000, more preferably 2200 to 2800, and most preferably 2400 to 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 present invention, the dehydration method is preferably sintering dehydration, and the temperature of the dehydration is preferably 100 to 370 ℃, more preferably 150 to 300 ℃, and most preferably 200 to 250 ℃; the dehydration time is preferably 4 to 8 hours, more preferably 5 to 7 hours, and most preferably 6 hours; the dehydration is preferably performed under oxygen (pure oxygen) at a gas flow rate of preferably 450 to 550L/min, more preferably 480 to 520L/min, and most preferably 500L/min.
If the high-nickel ternary precursor and coarse powder lithium hydroxide are directly presintered, more water vapor is generated within 500 ℃ and is difficult to discharge in a short time, so that the caustic soda content of a product is increased, the capacity, circulation and gas production performance of the finished product are deteriorated.
In the present invention, the method for preparing the pre-sintering product preferably comprises:
and mixing the high-nickel ternary precursor, coarse powder lithium hydroxide and an additive, and then pre-sintering to obtain a pre-sintered product.
In the invention, the high nickel material needs to be prepared by lithium hydroxide due to high alkali requirement; 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 micro powder lithium hydroxide can be replaced by the coarse powder lithium hydroxide, the raw material cost can be reduced, and the conventional sagger charging of 330 x 110 can only charge 5Kg, but after the precursor and the lithium hydroxide are dehydrated, the charging amount can reach 12Kg, and the efficiency can be further improved, so that the product manufacturing cost is reduced.
In the present invention, the mass content of LiOH in the coarse powder lithium hydroxide is preferably 56.5 to 58.0wt%, more preferably 57 to 57.5%, and most preferably 57.2 to 57.3%; the particle size D10 of the coarse powder lithium hydroxide is preferably 20 to 140. Mu.m, more preferably 30 to 120. Mu.m, still more preferably 50 to 100. Mu.m, most preferably 60 to 80. Mu.m; d50 is preferably 150 to 500. Mu.m, more preferably 200 to 400. Mu.m, still more preferably 250 to 350. Mu.m, most preferably 300. Mu.m; d100 is preferably 600 to 1000. Mu.m, more preferably 700 to 900. Mu.m, most preferably 800. Mu.m.
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 One or more of BN. The invention can enable the obtained presintered product to contain doping elements by adopting the additive in the presintered process.
In the invention, the mass ratio of the high-nickel ternary precursor, the coarse powder lithium hydroxide and the additive is preferably 1000: (465-490): (2 to 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 to 350rpm, more preferably 280 to 320rpm, most preferably 300rpm; the mixing time is preferably 100 to 150 minutes, more preferably 110 to 140 minutes, and most preferably 120 to 130 minutes.
In the present invention, the pre-sintering is preferably performed in a rotary kiln, and the pre-oxidation is performed.
In the present invention, the temperature during the pre-sintering is preferably 500 to 600 ℃, more preferably 520 to 580 ℃, and most preferably 540 to 560 ℃; the pre-sintering time is preferably 4 to 8 hours, more preferably 5 to 7 hours, and most preferably 6 hours; the pre-sintering is preferably performed in an atmosphere of oxygen (pure oxygen); the flow rate of the oxygen is preferably 450 to 550L/min, more preferably 480 to 520L/min, and most preferably 500L/min.
In the present invention, the method for preparing the primary sintered product preferably comprises:
and sintering the presintered product for the first time to obtain a primary sintered product.
In the present invention, the primary sintering is preferably performed in a roller kiln, more preferably in an atmosphere roller kiln, most preferably in a 10m atmosphere roller kiln; the sagger loading amount in the primary sintering process is preferably 10-15 kg/bowl, more preferably 11-14 kg/bowl, and most preferably 12 kg/bowl; the loading height is preferably 6 to 10cm, more preferably 7 to 9cm, most preferably 8cm.
In the present invention, the temperature of the primary sintering is preferably 735 to 850 ℃, more preferably 750 to 820 ℃, and most preferably 780 to 800 ℃; the sintering time is preferably 10 to 15 hours, more preferably 11 to 14 hours, and most preferably 12 to 13 hours; the sintering atmosphere is preferably oxygen (pure oxygen), the flow rate of which is preferably 800 to 1200L/min, more preferably 900 to 1100L/min, and most preferably 1000L/min.
The invention provides a preparation method of the low-cost high-nickel ternary positive electrode material, which comprises the following steps:
and crushing, washing, drying, doping and sintering (secondary sintering) the primary sintering product in sequence to obtain the low-cost high-nickel ternary anode material.
In the present invention, the D50 after crushing is preferably 8 to 12. Mu.m, more preferably 9 to 11. Mu.m, and most preferably 10. Mu.m.
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, a step of; the time of the water washing is preferably 1 to 3min, more preferably 1.5 to 2.5min, and most preferably 2min; stirring is preferably performed during the water washing, and the stirring speed is preferably 30-50 rpm, more preferably 35-45 rpm, and most preferably 40rpm; the temperature of the water washing is preferably 3 to 7 ℃, more preferably 4 to 6 ℃, and most preferably 5 ℃.
In the present invention, the water washing is preferably followed by pressure filtration.
In the present invention, the moisture content of the dried product is preferably < 0.5wt%.
The doping is not particularly limited, and the doping substance amount of the positive electrode material known to those skilled in the art are used to dope the doping element known to those skilled in the art, and the doping substance may be H 3 BO 3 、Al 2 O 3 Etc.; the stirring and mixing are preferably performed during the doping process, and the stirring speed is preferably 100-300 rpm, more preferably 150-250 rpm, and most preferably 200rpm; the mixing time is preferably 100 to 140min, more preferably 110 to 130min, and most preferably 120min.
In the present invention, the sagger loading amount during the sintering (secondary sintering) is preferably 4.5 to 5.5 kg/bowl, more preferably 4.8 to 5.2 kg/bowl, and most preferably 5 kg/bowl; the sintering temperature is preferably 280-600 ℃, more preferably 300-500 ℃, and most preferably 400 ℃; the sintering time is preferably 6 to 10 hours, more preferably 7 to 9 hours, and most preferably 8 hours.
In the present invention, the sintering (secondary sintering) is preferably further comprised of:
and screening, removing iron and packaging the obtained sintered product to obtain the low-cost high-nickel ternary anode 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 performance of the product.
The present invention provides a battery comprising: the low-cost high-nickel ternary positive electrode material has 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 taking the low-cost high-nickel ternary positive electrode material as a positive electrode material according to the battery of the required type and the conventional battery preparation method in the art.
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 anode 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 sheet 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 positive electrode material, the acetylene black and the polyvinylidene fluoride is preferably (92-96): (2-4): (2 to 4), more preferably (93 to 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 to 90 ℃, more preferably 75 to 85 ℃, and most preferably 80 ℃.
In the present invention, the diameter of the positive electrode sheet is preferably 12 to 16mm, more preferably 13 to 15mm, and most preferably 14mm.
In the present invention, the diameter of the negative electrode sheet is preferably 14 to 18mm, more preferably 15 to 17mm, and most preferably 16mm.
In the present invention, the electrolyte is preferably lipf6+dec/EC (volume ratio 1:1) of 1 mol/L; the separator is preferably a polymeric Celgard propylene microporous membrane.
In the present invention, the assembly is preferably performed in a glove box filled with argon.
The precursor is dehydrated by adopting the rotary kiln, and then is mixed with coarse powder lithium hydroxide after dehydration is completed, and then dehydration is carried out, so that the dehydration is complete, and the obtained positive electrode material has good comprehensive properties such as circulation, gas production and the like.
The precursor Ni employed in the following examples of the present invention 0.85 Co 0.06 Mn 0.09 (OH) 2 The source of (a) is model M85610 offered by green corporation; the coarse powder lithium hydroxide is a model ZHBKE18047 product provided by Sichuan far lithium industry Co.
Example 1
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 And (3) adding the mixture into a rotary kiln for presintering and dehydration, wherein the sintering temperature is 350 ℃, the sintering time is 6 hours, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so that the presintered material is obtained. The presintered precursor and 9.45Kg of coarse powder lithium hydroxide and 10g of ZrO are mixed 2 5g SrO is stirred and mixed for 120min at 300rpm, after the materials are uniformly mixed, the mixture is put into a rotary kiln for pre-oxidation, the sintering temperature is 600 ℃, the sintering time is 6h, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so that the pre-oxidized materials are obtained. And (3) sintering the presintered material in a 10-meter atmosphere roller kiln for one time, wherein the sagger loading amount is 12 kg/bowl, the loading height is about 8cm, the sintering temperature is 755 ℃, the sintering 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. Crushing the primary sintering material, controlling the D50 at 10.0+/-1.0 mu m, then washing with water under the condition of 1:1 for 2min, controlling the rotation speed of a stirring rod at 40rpm and the water temperature at 5 ℃, and then performing filter pressing and drying to control the water content below 0.5wt%. Mixing the dried material with 10gH 3 BO 3 Stirring and mixing for 120min at 200rpm, placing the materials in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the sagger loading amount is 5.5 kg/bowl, the sintering temperature is 300 ℃, the sintering time is 8h, and obtaining the finished product high nickel ternary material after screening, deironing and packaging.
Example 2
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 And (3) adding the mixture into a rotary kiln for presintering and dehydration, wherein the sintering temperature is 350 ℃, the sintering time is 6 hours, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so that the presintered material is obtained. The presintered precursor and 9.45Kg of coarse powder lithium hydroxide and 10g of ZrO are mixed 2 5g SrO is stirred and mixed for 120min at 300rpm, after the materials are uniformly mixed, the mixture is put into a rotary kiln for pre-oxidation, the sintering temperature is 500 ℃, the sintering time is 6h, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so that the pre-oxidized materials are obtained. And (3) sintering the presintered material in a 10-meter atmosphere roller kiln for one time, wherein the sagger loading amount is 10.5 kg/bowl, the loading height is about 8cm, the sintering temperature is 755 ℃, the sintering 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. Crushing the primary sintering material, controlling the D50 at 10.0+/-1.0 mu m, then washing with water under the condition of 1:1 for 2min, controlling the rotation speed of a stirring rod at 40rpm and the water temperature at 5 ℃, and then performing filter pressing and drying to control the water content below 0.5wt%. Mixing the dried material with 10gH 3 BO 3 Stirring and mixing for 120min at 200rpm, placing the materials in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the sagger loading amount is 5.5 kg/bowl, the sintering temperature is 300 ℃, the sintering time is 8h, and obtaining the finished product high nickel ternary material after screening, deironing and packaging.
Example 3
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 And (3) adding the mixture into a rotary kiln for presintering and dehydration, wherein the sintering temperature is 350 ℃, the sintering time is 6 hours, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so that the presintered material is obtained. The presintered precursor and 9.45Kg of coarse powder lithium hydroxide and 10g of ZrO are mixed 2 5g SrO is stirred and mixed for 120min at 300rpm, after the materials are uniformly mixed, the mixture is put into a rotary kiln for pre-oxidation, the sintering temperature is 400 ℃, the sintering time is 6h, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so that the pre-oxidized materials are obtained. Sintering the presintered material in a 10m atmosphere roller kiln for 12h at a sintering temperature of 755 ℃ and a sintering atmosphere of pure, wherein the sagger loading amount is 9 kg/sagger, the loading height is about 8cmAnd (3) obtaining the primary sintering material in an oxygen atmosphere with an oxygen ventilation amount of 1000L/min. Crushing the primary sintering material, controlling the D50 at 10.0+/-1.0 mu m, then washing with water under the condition of 1:1 for 2min, controlling the rotation speed of a stirring rod at 40rpm and the water temperature at 5 ℃, and then performing filter pressing and drying to control the water content below 0.5wt%. Mixing the dried material with 10gH 3 BO 3 Stirring and mixing for 120min at 200rpm, placing the materials in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the sagger loading amount is 5.5 kg/bowl, the sintering temperature is 300 ℃, the sintering time is 8h, and obtaining the finished product high nickel ternary material after screening, deironing and packaging.
Example 4
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 And (3) adding the mixture into a rotary kiln for presintering and dehydration, wherein the sintering temperature is 350 ℃, the sintering time is 6 hours, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so that the presintered material is obtained. Adding 9.45Kg of coarse powder lithium hydroxide into a rotary kiln for presintering and dehydration, wherein the sintering temperature is 150 ℃, the sintering 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. Pre-sintered precursor, coarse powder lithium hydroxide and 10g ZrO 2 5g SrO is stirred and mixed for 120min at 300rpm, after the materials are uniformly mixed, the presintered materials are sintered once in a 10-meter atmosphere roller kiln, the sagger loading amount is 12 kg/bowl, 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 amount is 1000L/min, so that the primary sintered materials are obtained. Crushing the primary sintering material, controlling the D50 at 10.0+/-1.0 mu m, then washing with water under the condition of 1:1 for 2min, controlling the rotation speed of a stirring rod at 40rpm and the water temperature at 5 ℃, and then performing filter pressing and drying to control the water content below 0.55. Mixing the dried material with 10gH 3 BO 3 Stirring and mixing for 120min at 200rpm, placing the materials in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the sagger loading amount is 5.5 kg/bowl, the sintering temperature is 300 ℃, the sintering time is 8h, and obtaining the finished product high nickel ternary material after screening, deironing and packaging.
Example 5
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 And (3) adding the mixture into a rotary kiln for presintering and dehydration, wherein the sintering temperature is 350 ℃, the sintering time is 6 hours, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so that the presintered material is obtained. The presintered precursor and 9.45Kg of coarse powder lithium hydroxide and 10g of ZrO are mixed 2 、5gTiO 2 Stirring and mixing for 120min at 300rpm, placing the mixture into a rotary kiln for pre-oxidation after the mixture is uniformly mixed, wherein the sintering temperature is 600 ℃, the sintering time is 6h, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so as to obtain the pre-oxidized material. And (3) sintering the presintered material in a 10-meter atmosphere roller kiln for one time, wherein the sagger loading amount is 12 kg/bowl, the loading height is about 8cm, the sintering temperature is 755 ℃, the sintering 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. Crushing the primary sintering material, controlling the D50 at 10.0+/-1.0 mu m, then washing with water under the condition of 1:1 for 2min, controlling the rotation speed of a stirring rod at 40rpm and the water temperature at 5 ℃, and then performing filter pressing and drying to control the water content below 0.5%. Mixing the dried material with 10gH 3 BO 3 Stirring and mixing for 120min at 200rpm, placing the materials in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the sagger loading amount is 5.5 kg/bowl, the sintering temperature is 300 ℃, the sintering time is 8h, and obtaining the finished product high nickel ternary material after screening, deironing and packaging.
Example 6
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 And (3) adding the mixture into a rotary kiln for presintering and dehydration, wherein the sintering temperature is 350 ℃, the sintering time is 6 hours, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so that the presintered material is obtained. Pre-sintered precursor, 9.45Kg coarse powder of lithium hydroxide and 7g WO 3 3g MgO is stirred and mixed for 120min at 300rpm, after the materials are uniformly mixed, the mixture is put into a rotary kiln for pre-oxidation, the sintering temperature is 600 ℃, the sintering time is 6h, pure oxygen is selected as atmosphere, and the air flow is 500L/min, so that the pre-oxidized materials are obtained. Sintering the presintered material in a 10m atmosphere roller kiln for one time, wherein the sagger loading amount is 12 kg/bowl, the loading height is about 8cm, the sintering temperature is 755 ℃, the sintering time is 12h, the sintering atmosphere is pure oxygen atmosphere, and the oxygen ventilation amount is1000L/min to obtain the primary sintering material. Crushing the primary sintering material, controlling the D50 at 10.0+/-1.0 mu m, then washing with water under the condition of 1:1 for 2min, controlling the rotation speed of a stirring rod at 40rpm and the water temperature at 5 ℃, and then performing filter pressing and drying to control the water content below 0.5%. Mixing the dried material with 10gH 3 BO 3 、5gAl 2 O 3 Stirring and mixing for 120min at 200rpm, placing the materials in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the sagger loading amount is 5.5 kg/bowl, the sintering temperature is 300 ℃, the sintering time is 8h, and obtaining the finished product high nickel ternary material after screening, deironing and packaging.
Example 7
20Kg of precursor Ni 0.85 Co 0.06 Mn 0.09 (OH) 2 And (3) adding the mixture into a rotary kiln for presintering and dehydration, wherein the sintering temperature is 350 ℃, the sintering time is 6 hours, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so that the presintered material is obtained. Mixing the presintered precursor with 9.45Kg coarse powder lithium hydroxide, 5.5 gY 2 O 3 Stirring and mixing for 120min at 300rpm, placing the mixture into a rotary kiln for pre-oxidation after the mixture is uniformly mixed, wherein the sintering temperature is 600 ℃, the sintering time is 6h, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so as to obtain the pre-oxidized material. And (3) sintering the presintered material in a 10-meter atmosphere roller kiln for one time, wherein the sagger loading amount is 12 kg/bowl, the loading height is about 8cm, the sintering temperature is 755 ℃, the sintering 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. Crushing the primary sintering material, controlling the D50 at 10.0+/-1.0 mu m, then washing with water under the condition of 1:1 for 2min, controlling the rotation speed of a stirring rod at 40rpm and the water temperature at 5 ℃, and then performing filter pressing and drying to control the water content below 0.5%. Mixing the dried material with 10gH 3 BO 3 、5gAl 2 O 3 Stirring and mixing for 120min at 200rpm, placing the materials in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the sagger loading amount is 5.5 kg/bowl, the sintering temperature is 300 ℃, the sintering time is 8h, and obtaining the finished product high nickel ternary material after screening, deironing and packaging.
Comparative example 1
20Kg of front partNi as a precursor 0.85 Co 0.06 Mn 0.09 (OH) 2 And 9.45Kg of fine powder lithium hydroxide, 10gZrO 2 Stirring and mixing 5gSrO for 120min at 300rpm, and sintering the materials in a 10-meter atmosphere roller kiln once after the materials are uniformly mixed, wherein the sagger loading amount is 5 kg/bowl, the loading height is about 8cm, the sintering temperature is 755 ℃, the sintering time is 12h, the sintering atmosphere is pure oxygen atmosphere, and the oxygen ventilation amount is 1000L/min, so as to obtain the primary sintering material. Crushing the primary sintering material, controlling the D50 at 10.0+/-1.0 mu m, then washing with water under the condition of 1:1 for 2min, controlling the rotation speed of a stirring rod at 40rpm and the water temperature at 5 ℃, and then performing filter pressing and drying to control the water content below 0.5wt%. Mixing the dried material with 10gH 3 BO 3 Stirring and mixing for 120min at 200rpm, placing the materials in a roller kiln for secondary sintering after the materials are uniformly mixed, wherein the sagger loading amount is 5.5 kg/bowl, the sintering temperature is 300 ℃, the sintering time is 8h, and obtaining the finished product high nickel ternary material after screening, deironing and packaging.
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, 10gZrO 2 5g SrO is stirred and mixed for 120min at 300rpm, after the materials are uniformly mixed, the mixture is put into a rotary kiln for pre-oxidation, the sintering temperature is 500 ℃, the sintering time is 6h, pure oxygen is selected as the atmosphere, and the air flow is 500L/min, so that the pre-oxidized materials are obtained. And (3) sintering the presintered material in a 10-meter atmosphere roller kiln for one time, wherein the sagger loading amount is 12 kg/bowl, the loading height is about 8cm, the sintering temperature is 755 ℃, the sintering 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. Crushing the primary sintering material, controlling the D50 at 10.0+/-1.0 mu m, then washing with water under the condition of 1:1 for 2min, controlling the rotation speed of a stirring rod at 40rpm and the water temperature at 5 ℃, and then performing filter pressing and drying to control the water content below 0.5wt%. Mixing the dried material 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 sagger loading amount is 5.5 kg/bowl, the sintering temperature is 300 ℃ and the sintering time is 8h, and sieving and deironing are carried outAnd packaging to obtain the finished product of the high-nickel ternary material.
Performance detection
SEM examination (multiple 50K) of the high nickel cathode materials prepared in the examples and comparative examples of the present invention shows that the dehydration of lithium hydroxide together with the precursor results in significant alkali on the surface of the materials, which is disadvantageous for the subsequent processing (e.g., comparative examples 1 and 2).
The conditions and productivity of the high nickel cathode materials prepared in the examples and comparative examples of the present invention are as follows:
the high nickel positive electrode materials prepared by the embodiment of the invention and the comparative example are assembled into a button cell, and the specific method is as follows:
weighing high-nickel anode material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 94:3:3, uniformly mixing, adding NMP, stirring for 2 hours to form sticky slurry, uniformly coating the sticky slurry on aluminum foil, carrying out vacuum baking at 80 ℃, tabletting, and cutting an anode piece with the diameter of 14mm.
Pure lithium sheets with the diameter of 16mm are used as a negative electrode sheet, a mixed solution of 1mol/L LiPF6+DEC/EC (volume ratio of 1:1) is used as an electrolyte, a poly Celgard propylene microporous membrane is used as a diaphragm, and the battery is assembled in a glove box filled with argon.
Testing Li in the products after one sintering in the course of the high nickel cathode materials prepared in the examples and comparative examples of the present invention 2 CO 3 Content, liOH content and free Li + Is contained in the composition; the specific detection method comprises the following steps: weighing 30g of materials, adding 100ml of pure water, stirring for 30min, filtering by using double-layer medium-speed filter paper, pipetting for 10ml, titrating by using 0.05mol/L HCl, and judging the titration end point according to an acid-base titration method.
Button cells prepared from the high nickel cathode materials obtained in the above examples and comparative examples were tested for 0.2C capacity under the following conditions: the assembled button cell is charged and discharged in blue electric equipment at a test temperature of 25+/-1 ℃ and a test voltage of 2.5-4.25V and 0.2C/0.2C, and the charged cut-off current is 0.05C (1℃ nominal capacity 200 mAh/g); the detection results are as follows:
the method for detecting the thermogenesis at 70 ℃ for 7 days comprises the following steps: firstly, fully charging the battery, then testing the volume of the battery, then storing the fully charged battery at 70 ℃ for 7 days, testing the volume of the battery, and calculating the difference value of the two to obtain the thermal gas production, wherein the volume measuring equipment is an electronic solid densimeter TW-120E; the results of the detection are shown in FIG. 10 and the table above.
The capacity retention rate of 300 times of 45 ℃ cycles is detected, and the detection method comprises the following steps: the capacity retention rate is calculated by adopting Xinwei CT3008-5V3A-A1, circulating voltage is 4.25-3V, constant voltage cut-off current is 20mA, and circulating for 300 circles at 45 ℃; the results of the detection 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 higher caustic soda amount, lower 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 can be considered, and the competitiveness of the high-nickel ternary material can be effectively improved.
While the invention has been described and illustrated with reference to specific embodiments thereof, the description and illustration is not intended to limit the invention. It will be apparent to those skilled in the art that various changes may be made in this particular situation, material, composition of matter, substance, method or process without departing from the true spirit and scope of the invention as defined by the following claims, so as to adapt the objective, spirit and scope of the present application. All such modifications are intended to be within the scope of this appended claims. 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 an equivalent method without departing from the teachings of the present disclosure. Thus, unless specifically indicated herein, the order and grouping of operations is not a limitation of the present application.
Claims (7)
1. A low-cost high-nickel ternary positive electrode material comprises the following components in general formula:
LiNi x CoyA 1-x-y O 2 a 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, sr;
the low-cost high-nickel ternary positive electrode material has a 7-day thermal measurement gas production of less than 15 percent, li 2 CO 3 The content is less than 2000ppm, and the LiOH content is less than 5000ppm; the low-cost high-nickel ternary anode material is prepared from a material comprising a primary sintering product;
the capacity of the primary sintering product under the conditions of 0.2C and 2.5-4.25V is more than 170mAh/g;
the bulk density of the primary sintering 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, M is the total molar weight of Ni, co and A;
li in the primary sintering product 2 CO 3 The mass content of (2) is less than 8000ppm, and the mass content of LiOH is less than 8000ppm; characteristic peaks of XRD of the primary sintered product include:
the peak intensity of 18-19 DEG is 20000-30000, the peak intensity of 36-37 DEG is 7000-8000, the peak intensity of 44-45 DEG is 11000-13000, the peak intensity of 48-49 DEG is 2000-3000, the peak intensity of 58-59 DEG is 1500-2500, the peak intensity of 64-65 DEG is 2000-3000, and the peak intensity of 68-69 DEG is 1200-2200;
the primary sintering product is prepared by primary sintering of a presintered product; the primary sintering is carried out in a roller kiln; the temperature of the primary sintering is 735-850 ℃;
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 pre-sintering to obtain a pre-sintering product; the presintering is carried out in a rotary kiln; the temperature of the pre-sintering is 500-600 ℃;
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.
2. The low cost high nickel ternary positive electrode material of claim 1, wherein the bulk density of the pre-sintered product is 1.2 to 1.7g/cc;
the XRD characteristic peaks of the pre-sintered product include:
the peak intensity of 18-19 DEG is 2000-3000, the peak intensity of 32-33 DEG is 1000-2000, the peak intensity of 38-39 DEG is 1500-2500, the peak intensity of 42-43 DEG is 3500-4500, and the peak intensity of 64-65 DEG is 1500-2500.
3. The low cost high nickel ternary positive electrode material of claim 2, wherein the moisture content of the high nickel ternary precursor is < 1wt%;
the bulk density of the high-nickel ternary precursor is 1.5-1.8 g/cc;
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.
4. The low cost high nickel ternary positive electrode material according to claim 3, wherein the high nickel ternary precursor is prepared from a material comprising a high nickel ternary precursor;
the high-nickel ternary precursor has the following general formula:
Ni x Co y A 1-x-y (OH) 2 the compound of the formula II 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, sr;
the bulk density D of the high-nickel ternary precursor is 1.4-1.8 g/cc, the moisture content is less than 2wt%, and the BET is 4-12 m 2 /g；
XRD characteristic peaks of the high-nickel ternary precursor include:
the peak intensity of 19-20 DEG is 10000-12000, the peak intensity of 33-34 DEG is 6000-7000, the peak intensity of 38-39 DEG is 9000-11000, the peak intensity of 52-53 DEG is 3500-4500, the peak intensity of 59-60 DEG is 3500-4500, and the peak intensity of 63-64 DEG is 2000-3000.
5. A method for preparing the low-cost high-nickel ternary cathode material according to claim 1, comprising:
crushing, washing, drying, doping and sintering the primary sintering product in sequence to obtain a low-cost high-nickel ternary anode material;
the preparation method of the primary sintering product comprises the following steps:
sintering the presintered product for the first time to obtain a primary sintered product; the temperature of the primary sintering is 735-850 ℃;
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 pre-sintering to obtain a pre-sintering product; the presintering is carried out in a rotary kiln; the temperature of the pre-sintering is 500-600 ℃;
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.
6. The method of claim 5, wherein the temperature of dehydration is 100-370 ℃.
7. A battery, comprising: the low cost high nickel ternary positive electrode material of claim 1.
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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 |
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