CN114538532B - Preparation method of high-nickel ternary cathode material and prepared high-nickel ternary cathode material - Google Patents
Preparation method of high-nickel ternary cathode material and prepared high-nickel ternary cathode material Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010406 cathode material Substances 0.000 title claims description 29
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 239000007774 positive electrode material Substances 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 238000007873 sieving Methods 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 13
- 159000000002 lithium salts Chemical class 0.000 abstract description 13
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000002019 doping agent Substances 0.000 description 26
- 238000011049 filling Methods 0.000 description 13
- 239000011572 manganese Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002994 raw material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910013716 LiNi Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013330 LiNiO2 LiMnO2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01P2006/40—Electric properties
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention discloses a preparation method of a high-nickel ternary positive electrode material, which comprises the steps of uniformly mixing a precursor containing the ternary positive electrode material with a lithium source, compacting a mixed material, and performing low-temperature sintering on the compacted mixed material in an oxygen atmosphere to obtain a low-temperature sintered product; the low-temperature sintering temperature is 550-650 ℃ and the sintering time is 3-8 h; uniformly mixing the low-temperature sintering product and the additive, then sintering at high temperature in oxygen atmosphere, and then cooling, grinding and sieving to obtain the doped modified high-nickel ternary anode material; the high-temperature sintering temperature is 700-950 ℃ and the sintering time is 8-15 h. According to the invention, the shallow doped and coated high-nickel ternary anode material is obtained by mixing and compacting the lithium salt and the precursor, then presintering, and then adding the additive for sintering, so that the rate performance and the cycle life of the material are greatly improved; meanwhile, the obtained high-nickel ternary anode material reduces residual alkali and improves the utilization rate of lithium salt.
Description
Technical Field
The invention relates to a ternary positive electrode material of a lithium ion battery, in particular to a preparation method of a high-nickel ternary positive electrode material.
Background
Lithium ionBatteries are widely used in life, such as notebook computers, cellular phones, digital cameras, electric vehicles, and the like. And the positive electrode material is taken as a component part of the battery and plays an important role in the performance of the battery. Currently, ternary cathode material LiNi x Mn y Co z O 2 (x+y+z=1) has a remarkable ternary synergistic effect, forming LiCoO 2 /LiNiO 2 /LiMnO 2 Three-phase solid solution system, which gives consideration to LiCoO 2 、LiNiO 2 LiMnO 2 The advantages of the three materials are achieved, and the defects of the three materials are overcome to a certain extent. With LiNiO2 and LiMnO 2 In comparison with LiNi 1-x-y Co x Mn y O 2 Has good stability and easy preparation. And spinel LiMn 2 O 4 In comparison with LiNi x Mn y Co z O 2 Jahn-Teller distortion effect is not easy to occur; with LiFePO 4 In comparison with LiNi x Mn y Co z O 2 Has high voltage platform, high conductivity high tap density and the like.
With the improvement of the national and market energy density requirements of the power battery and the shortage of cobalt metal, the high-nickel ternary cathode material LiNi x Mn y Co z O 2 The use and development of (x+y+z=1, x.gtoreq.0.6) is receiving increasing attention, and the production process is also becoming mature. With the increase of nickel content, the multiplying power performance and the cycle performance of the ternary material are obviously reduced, and in order to improve the problem, a great deal of researches on the proportion of nickel, cobalt and manganese, doping coating elements and means are carried out by a plurality of researchers, such as a concentration gradient material prepared by CN102631875A, but the concentration gradient generated by a precursor in the actual high-temperature sintering process is disappeared, so that the expected effect is difficult to achieve. The Chinese patent application CN112080800A discloses a modification method of a monocrystal ternary positive electrode material, which comprises the steps of pre-burning a precursor and a dopant at a low temperature, uniformly coating most of the dopant after pre-burning on the surface of the precursor in an oxide form, sintering the pre-burned precursor and lithium salt at a high temperature to prevent the dopant from forming an oxide coating layer on the surface of the ternary positive electrode material, thereby reducing the internal resistance of the ternary positive electrode material althoughThe cycle performance of the lithium ion battery is improved, but the multiplying power performance is not effectively improved, so that a method for simultaneously improving the multiplying power performance and the cycle performance of the high-nickel ternary positive electrode material is needed to be searched for, and the characteristics of high multiplying power and long service life of the high-nickel ternary positive electrode material are achieved.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a high-nickel ternary cathode material, which further improves the multiplying power performance of the high-nickel ternary cathode material on the basis of improving the cycle performance of the high-nickel ternary cathode material.
The technical scheme adopted for solving the technical problems is as follows: the preparation method of the high-nickel ternary anode material comprises the following steps,
(1) Uniformly mixing a precursor containing ternary positive electrode materials with a lithium source, and compacting the mixed materials, wherein the ratio of the volume of the compacted mixed materials to the volume of the mixed materials in a natural state is 1/4-1:1;
(2) Carrying out low-temperature sintering on the compacted mixture obtained in the step (1) in an oxygen atmosphere to obtain a low-temperature sintering product; the low-temperature sintering temperature is 550-650 ℃ and the sintering time is 3-8 h;
(3) Uniformly mixing the low-temperature sintering product and the additive, then sintering at high temperature in oxygen atmosphere, and then cooling, grinding and sieving to obtain the doped modified high-nickel ternary anode material; the high-temperature sintering temperature is 700-950 ℃ and the sintering time is 8-15 h.
Further, the ratio of the volume of the compacted mixture obtained in the step (1) to the volume of the mixture with the same mass in the natural state is 1/4-1/2:1.
Further, in the step (1), the molar ratio Li/Me of lithium metal in the lithium source to metal in the precursor is 1.01-1.04:1.
Further, the oxygen atmosphere is air, oxygen or a mixed atmosphere of air and oxygen.
Further, the additive in the step (3) is at least one of an oxide or a hydroxyl oxide, a fluoride or a nitride of Al, zr, ti, mg, nb, W, sr.
Further, the mass ratio of the precursor to the dopant is 1:0.001-0.0.005.
Further, the mass ratio of the precursor to the dopant is 1:0.0015 to 0.0.0035.
Further, the lithium source in the step (1) is at least one of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate and lithium citrate.
The high-nickel ternary positive electrode material is prepared by the preparation method of any one of the high-nickel ternary positive electrode materials.
Further, the molecular formula of the high-nickel ternary positive electrode material is as follows: li (Li) 1+m (Ni 1-x-y A x B y ) 1-m O 2-n A is one or more elements of Mn, zr and Ti, B is one or more elements of Al and Co, m, x, y, z is expressed in mol, wherein x+y is more than or equal to 0.1 and less than or equal to 0.4, n is more than or equal to 0 and less than or equal to 0.05, and m is more than or equal to 0 and less than or equal to 0.05.
The beneficial effects of the invention are as follows: according to the invention, the shallow doped and coated high-nickel ternary anode material is obtained by mixing and compacting the lithium salt and the precursor, then presintering, and then adding the additive for sintering, so that the rate performance and the cycle life of the material are greatly improved; meanwhile, the obtained high-nickel ternary anode material reduces residual alkali and improves the utilization rate of lithium salt.
Drawings
FIG. 1 is an SEM of a high nickel ternary cathode material according to example 1 of the present invention;
FIG. 2 is an SEM of the high nickel ternary cathode material of comparative example 3 of the present invention;
FIG. 3 is a graph showing the rate discharge curves of the high nickel ternary cathode materials obtained in example 1 and comparative example 3 of the present invention;
fig. 4 is a normal temperature cycle curve of the high nickel ternary cathode material obtained in example 2 and comparative examples 1, 3, and 4 of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and examples.
Example 1:
with Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 、LiOH·H 2 O, dopant (ZrO) 2 ) As a raw material, li/me=1.04, the mass ratio of precursor to dopant is 1:0.003. firstly, mixing a precursor and lithium salt, filling the mixture into a sagger in a loose manner, marking the weight as m, and then compacting the material to fill the sagger so as to enable the material amount to be 2m; then placing the mixture in a muffle furnace, and presintering the mixture for 5 hours at 600 ℃ in an oxygen atmosphere; dispersing the materials after cooling, adding the doping agent, uniformly mixing, filling the sagger loosely, placing the sagger in a muffle furnace, and sintering the sagger for 10 hours at 800 ℃ in an oxygen atmosphere; and finally grinding and sieving to obtain the target product of the high-nickel ternary cathode material.
Example 2:
with Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 、LiOH·H 2 O, dopant (ZrO) 2 ) As a raw material, li/me=1.04, the mass ratio of precursor to dopant is 1:0.003. firstly, mixing a precursor and lithium salt, filling the mixture into a sagger in a loose manner, marking the weight as m, and then compacting the material to fill the sagger so as to ensure that the material amount is 3m; then placing the mixture in a muffle furnace, and presintering the mixture for 5 hours at 600 ℃ in an oxygen atmosphere; dispersing the materials after cooling, adding the doping agent, uniformly mixing, filling the sagger loosely, placing the sagger in a muffle furnace, and sintering the sagger for 10 hours at 800 ℃ in an oxygen atmosphere; and finally grinding and sieving to obtain the target product of the high-nickel ternary cathode material.
Example 3:
with Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 、LiOH·H 2 O, dopant (ZrO) 2 ) As a raw material, li/me=1.01, the mass ratio of precursor to dopant is 1:0.003. firstly, mixing a precursor and lithium salt, filling the mixture into a sagger in a loose manner, marking the weight as m, and then compacting the material to fill the sagger so as to enable the material amount to be 2m; then placing the mixture in a muffle furnace, and presintering the mixture for 5 hours at 600 ℃ in an oxygen atmosphere; dispersing the materials after cooling, adding the doping agent, uniformly mixing, filling the sagger loosely, placing the sagger in a muffle furnace, and sintering the sagger for 10 hours at 800 ℃ in an oxygen atmosphere; and finally grinding and sieving to obtain the target product of the high-nickel ternary cathode material.
Comparative example 1: (the burn-in temperature was 500 ℃ C. And the other steps were the same as in example 1)
With Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 、LiOH·H 2 O, dopant (ZrO) 2 ) As a raw material, li/me=1.04, the mass ratio of precursor to dopant is 1:0.003. firstly, mixing a precursor and lithium salt, filling the mixture into a sagger in a loose manner, marking the weight as m, and then compacting the material to fill the sagger so as to enable the material amount to be 2m; then placing the mixture in a muffle furnace, and presintering the mixture for 5 hours at 500 ℃ in an oxygen atmosphere; dispersing the materials after cooling, adding the doping agent, uniformly mixing, filling the sagger loosely, placing the sagger in a muffle furnace, and sintering the sagger for 10 hours at 800 ℃ in an oxygen atmosphere; and finally grinding and sieving to obtain the target product of the high-nickel ternary cathode material.
Comparative example 2: (first sintering without compaction, otherwise the same as in example 1)
With Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 、LiOH·H 2 O, dopant (ZrO) 2 ) As a raw material, li/me=1.04, the mass ratio of precursor to dopant is 1:0.003. firstly, mixing a precursor and lithium salt, filling the mixture into a sagger in a loose manner, placing the sagger in a muffle furnace with the weight of m, and presintering for 5 hours at 600 ℃ in an oxygen atmosphere; dispersing the materials after cooling, adding the doping agent, uniformly mixing, filling the sagger loosely, placing the sagger in a muffle furnace, and sintering the sagger for 10 hours at 800 ℃ in an oxygen atmosphere; and finally grinding and sieving to obtain the target product of the high-nickel ternary cathode material.
Comparative example 3: (without presintering, otherwise the same as in example 1)
With Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 、LiOH·H 2 O, dopant (ZrO) 2 ) As a raw material, li/me=1.04, the mass ratio of precursor to dopant is 1:0.003. firstly, mixing a precursor and lithium salt, filling the mixture into a sagger in a loose manner, marking the weight as m, and then compacting the material to fill the sagger so as to enable the material amount to be 2m; then placing the mixture in a muffle furnace, and sintering the mixture for 10 hours at 800 ℃ in an oxygen atmosphere; and finally grinding and sieving to obtain the target product of the high-nickel ternary cathode material.
Comparative example 4: (simultaneous mixing of precursor, lithium salt and dopant, other examples 1)
With Ni 0.83 Co 0.11 Mn 0.06 (OH) 2 、LiOH·H 2 O, dopant (ZrO) 2 ) As a raw material, li/me=1.04, the mass ratio of precursor to dopant is 1:0.003. firstly, mixing a precursor, lithium salt and a doping agent, filling the mixture into a sagger in a loose manner, marking the weight as m, and then compacting the material to fill the sagger so as to enable the material amount to be 2m; then placing the mixture in a muffle furnace, and presintering the mixture for 5 hours at 600 ℃ in an oxygen atmosphere; dispersing the materials after cooling, filling the sagger loosely, placing the sagger in a muffle furnace, and sintering the sagger for 10 hours at 800 ℃ in an oxygen atmosphere; and finally grinding and sieving to obtain the target product of the high-nickel ternary cathode material.
The test method adopted by the invention comprises the following steps:
alkali content test: chemical reagent potentiometric titration for testing LiOH and Li 2 CO 3 The content is as follows. For testing the alkali content of the powder material, firstly, weighing 30g of the material, mixing and stirring with 100mL of pure water for 30min, carrying out suction filtration to obtain clear liquid, taking 10mL of liquid, titrating with 0.05mol/L of standard solution HCl, and calculating to obtain LiOH and Li 2 CO 3 Is a measure of (2);
pH test: weighing 5.00g of material, adding 50g of purified water without carbon dioxide, stirring on an electromagnetic stirrer for 5min, placing the stirred solution and a standard solution with the pH=6.86 and 9.18 in a water bath kettle at 25 ℃ for 30min, and testing the pH value by using a pH meter;
the method for testing the electricity-buckling performance comprises the following steps: the sample obtained in the example was prepared as a positive electrode of a 2025 type button cell, wherein positive electrode ratio, SP ratio, pvdf=90:5:5; the negative electrode is lithium metal; electrolyte solution: new Meibon (M10). Finally, the 2025 button cell is assembled for electrochemical performance test, and the test conditions are as follows: the charge-discharge voltage ranges from 3.0V to 4.3V;
the target products obtained in examples 1 to 3 and comparative example were subjected to performance test, and the results are shown in Table 1:
TABLE 1
As can be seen from table 1, comparative example 2 has a lower rate capability of 3C than example 1, although it has a higher cycle retention rate due to the fact that no compaction is performed at the time of the first sintering, and comparative example 3 has a lower rate capability than example 1, although it has compacted the material, but it has no pre-sintering.
Claims (9)
1. The preparation method of the high-nickel ternary cathode material is characterized by comprising the following steps of: comprises the steps of,
(1) Uniformly mixing a precursor containing ternary cathode materials with a lithium source, and compacting the mixed materials, wherein the ratio of the volume of the compacted mixed materials to the volume of the mixed materials in a natural state is 1/4-1:1;
(2) Carrying out low-temperature sintering on the compacted mixture obtained in the step (1) in an oxygen atmosphere to obtain a low-temperature sintering product; the low-temperature sintering temperature is 550-650 ℃, and the sintering time is 3-8 hours;
(3) Uniformly mixing the low-temperature sintering product and the additive, then sintering at high temperature in oxygen atmosphere, and then cooling, grinding and sieving to obtain the doped modified high-nickel ternary anode material; the additive is at least one of an oxide or a hydroxyl oxide, a fluoride or a nitride of Al, zr, ti, mg, nb, W, sr; the high-temperature sintering temperature is 700-950 ℃ and the sintering time is 8-15 h; the molecular formula of the high-nickel ternary positive electrode material is as follows: li (Li) 1+m (Ni 1-x-y A x B y ) 1-m O 2-n M, x, y, z is expressed in mol, wherein x+y is 0.1.ltoreq.x+y.ltoreq.0.4, n is 0.ltoreq.0.05, and m is 0.ltoreq.m.ltoreq.0.05.
2. The method for preparing the high-nickel ternary cathode material according to claim 1, wherein the method comprises the following steps: the ratio of the volume of the compacted mixture in the step (1) to the volume of the mixture in a natural state is 1/4-1/2:1.
3. The method for preparing the high-nickel ternary cathode material according to claim 1, wherein the method comprises the following steps: and (2) the molar ratio Li/Me of lithium metal in the lithium source to metal in the precursor in the step (1) is 1.01-1.04:1.
4. The method for preparing the high-nickel ternary cathode material according to claim 1, wherein the method comprises the following steps: the oxygen atmosphere is air, oxygen or a mixed atmosphere of air and oxygen.
5. The method for preparing the high-nickel ternary cathode material according to claim 1, wherein the method comprises the following steps: the mass ratio of the precursor to the additive is 1:0.001-0.005.
6. The method for preparing the high-nickel ternary cathode material according to claim 5, wherein the method comprises the following steps: the mass ratio of the precursor to the additive is 1:0.0015-0.0.0035.
7. The method for preparing the high-nickel ternary cathode material according to claim 1, wherein the method comprises the following steps: the lithium source in the step (1) is at least one of lithium hydroxide, lithium carbonate, lithium acetate, lithium oxalate and lithium citrate.
8. The high nickel ternary positive electrode material is characterized in that: a high nickel ternary positive electrode material prepared by the method for preparing a high nickel ternary positive electrode material according to any one of claims 1 to 7.
9. The high nickel ternary cathode material according to claim 8, wherein: the molecular formula of the high-nickel ternary positive electrode material is as follows: li (Li) 1+m (Ni 1-x-y A x B y ) 1-m O 2-n A is one or more elements of Mn, zr and Ti, B is one or more elements of Al and Co, m, x, y, z is expressed in mol, wherein x+y is more than or equal to 0.1 and less than or equal to 0.4, n is more than or equal to 0 and less than or equal to 0.05, and m is more than or equal to 0 and less than or equal to 0.05.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105374996A (en) * | 2015-09-23 | 2016-03-02 | 彩虹集团电子股份有限公司 | Method for treatment on high-voltage Ni-Co-Mn ternary positive electrode material by surface drying method |
| CN105826553A (en) * | 2016-05-17 | 2016-08-03 | 湖南杉杉能源科技股份有限公司 | High-temperature rate type lithium cobalt oxide anode material and preparation method thereof |
| CN108232147A (en) * | 2017-12-28 | 2018-06-29 | 合肥国轩高科动力能源有限公司 | Lithium ion battery high-nickel ternary positive electrode material with surface coated with lithium yttrium oxide and preparation method thereof |
| CN108461737A (en) * | 2018-03-21 | 2018-08-28 | 苏州林奈新能源有限公司 | A kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the Preparation method and use of cladding |
| CN108502937A (en) * | 2018-04-17 | 2018-09-07 | 哈尔滨工业大学 | A kind of polynary persursor material of ball-shaped lithium-ion battery anode and its preparation method and application |
| CN109888242A (en) * | 2019-03-12 | 2019-06-14 | 四川纳创时代新能源科技有限公司 | A kind of high-tap density cobalt nickel lithium manganate ternary material and preparation method thereof |
| CN110699744A (en) * | 2019-09-10 | 2020-01-17 | 龙能科技（苏州）有限责任公司 | Single crystal ternary positive electrode material containing trace elements |
| CN111244419A (en) * | 2020-01-17 | 2020-06-05 | 乳源东阳光磁性材料有限公司 | High-nickel ternary cathode material and preparation method and application thereof |
| CN111477867A (en) * | 2020-05-21 | 2020-07-31 | 苏州大学 | Modification method of high-nickel ternary cathode material of lithium ion battery |
| CN111952585A (en) * | 2020-08-18 | 2020-11-17 | 光鼎铷业(广州)集团有限公司 | High-compaction-density rubidium-doped lithium battery positive electrode material and preparation method thereof |
| CN112038611A (en) * | 2020-09-15 | 2020-12-04 | 天津市捷威动力工业有限公司 | Method for improving compacted density of high-nickel ternary positive plate |
| CN112117454A (en) * | 2020-10-09 | 2020-12-22 | 中伟新材料股份有限公司 | Ternary cathode material, preparation method thereof, lithium ion battery and power utilization equipment |
-
2022
- 2022-01-11 CN CN202210027334.2A patent/CN114538532B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105374996A (en) * | 2015-09-23 | 2016-03-02 | 彩虹集团电子股份有限公司 | Method for treatment on high-voltage Ni-Co-Mn ternary positive electrode material by surface drying method |
| CN105826553A (en) * | 2016-05-17 | 2016-08-03 | 湖南杉杉能源科技股份有限公司 | High-temperature rate type lithium cobalt oxide anode material and preparation method thereof |
| CN108232147A (en) * | 2017-12-28 | 2018-06-29 | 合肥国轩高科动力能源有限公司 | Lithium ion battery high-nickel ternary positive electrode material with surface coated with lithium yttrium oxide and preparation method thereof |
| CN108461737A (en) * | 2018-03-21 | 2018-08-28 | 苏州林奈新能源有限公司 | A kind of nickel cobalt aluminium ternary anode material for lithium-ion batteries, the Preparation method and use of cladding |
| CN108502937A (en) * | 2018-04-17 | 2018-09-07 | 哈尔滨工业大学 | A kind of polynary persursor material of ball-shaped lithium-ion battery anode and its preparation method and application |
| CN109888242A (en) * | 2019-03-12 | 2019-06-14 | 四川纳创时代新能源科技有限公司 | A kind of high-tap density cobalt nickel lithium manganate ternary material and preparation method thereof |
| CN110699744A (en) * | 2019-09-10 | 2020-01-17 | 龙能科技（苏州）有限责任公司 | Single crystal ternary positive electrode material containing trace elements |
| CN111244419A (en) * | 2020-01-17 | 2020-06-05 | 乳源东阳光磁性材料有限公司 | High-nickel ternary cathode material and preparation method and application thereof |
| CN111477867A (en) * | 2020-05-21 | 2020-07-31 | 苏州大学 | Modification method of high-nickel ternary cathode material of lithium ion battery |
| CN111952585A (en) * | 2020-08-18 | 2020-11-17 | 光鼎铷业(广州)集团有限公司 | High-compaction-density rubidium-doped lithium battery positive electrode material and preparation method thereof |
| CN112038611A (en) * | 2020-09-15 | 2020-12-04 | 天津市捷威动力工业有限公司 | Method for improving compacted density of high-nickel ternary positive plate |
| CN112117454A (en) * | 2020-10-09 | 2020-12-22 | 中伟新材料股份有限公司 | Ternary cathode material, preparation method thereof, lithium ion battery and power utilization equipment |
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