CN114188527A - NCMA (non-volatile memory alloy) positive electrode material with core-shell structure and preparation method thereof - Google Patents
NCMA (non-volatile memory alloy) positive electrode material with core-shell structure and preparation method thereof Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 title claims description 20
- 229910001285 shape-memory alloy Inorganic materials 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000010405 anode material Substances 0.000 claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 8
- -1 lithium nickel cobalt manganese aluminum metal oxide Chemical class 0.000 claims abstract description 5
- 229910013172 LiNixCoy Inorganic materials 0.000 claims abstract description 4
- ACKHWUITNXEGEP-UHFFFAOYSA-N aluminum cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Co+2].[Ni+2] ACKHWUITNXEGEP-UHFFFAOYSA-N 0.000 claims abstract description 4
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 239000008139 complexing agent Substances 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 239000012716 precipitator Substances 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 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
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 10
- 238000001354 calcination Methods 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 4
- 229910014746 LiNiaCobMn1−a−bO2 Inorganic materials 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 239000011164 primary particle Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- IWTZGPIJFJBSBX-UHFFFAOYSA-G aluminum;cobalt(2+);nickel(2+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Co+2].[Ni+2] IWTZGPIJFJBSBX-UHFFFAOYSA-G 0.000 abstract description 2
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 2
- 159000000002 lithium salts Chemical class 0.000 abstract description 2
- 239000011257 shell material Substances 0.000 description 18
- 230000001276 controlling effect Effects 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229940053662 nickel sulfate Drugs 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 239000012066 reaction slurry Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000007812 deficiency Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
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- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
An NCMA anode material with a core-shell structure and a preparation method thereof, wherein the anode material is a lithium nickel cobalt manganese aluminum metal oxide with a core-shell structure and has a chemical formula of LiNixCoyMnzAl1‑x‑y‑zO2X is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than or equal to 0 and less than 0.2, and x + y + z is less than 1; the core of the anode material is lithium-containing nickel-cobalt-manganese oxide with a chemical formula of LiNiaCobMn1‑a‑bO2A is more than or equal to 0.8 and less than 1, b is more than 0 and less than 0.2, wherein a + b is less than 1; the shell of the anode material is lithium-containing nickel-cobalt-aluminum oxide with the chemical formula of LiNicCodAl1‑c‑dO2Wherein c is more than or equal to 0.8 and less than 1, d is more than 0 and less than 0.2, and the thickness of the outer shell layer accounts for 5-45% of the particle size of the whole core-shell structure material. The preparation method comprises the following steps: 1) synthesizing a nickel-cobalt-manganese ternary hydroxide precursor by using a coprecipitation method and controlling the pH value and the ammonia concentration; 2) adjusting pH and ammonia concentration based on the aboveGrowing an Al-doped nickel-cobalt-aluminum hydroxide precursor shell with needle-shaped primary particles by taking the nickel-cobalt-manganese ternary precursor as a core; 3) and mixing the NCMA hydroxide precursor with the core-shell structure with lithium salt, and calcining to obtain the NCMA cathode material with the core-shell structure. The material prepared by the invention has high structural stability and good cycle performance.
Description
Technical Field
The invention relates to the field of electrode materials and chemical power supplies, in particular to an NCMA positive electrode material with a core-shell structure and a preparation method thereof.
Background
With the increasing energy density of lithium ion batteries, the pursuit of the capacity of positive and negative electrode materials is also increasing, and due to the difference of the capacities of the positive and negative electrodes, the positive electrode material is often the bottleneck influencing the energy density of the batteries. From the current technical level, the high-nickel ternary lithium ion battery positive electrode material is regarded as a lithium ion power battery positive electrode material with great application prospect by virtue of the advantages of high specific capacity, low cost, excellent safety and the like.
Currently, high nickel materials fall into two main categories: the reversible capacity of the NCM and NCA materials has high energy density, and the application of the NCM and the NCA materials is expected to enable the endurance of a power automobile based on the lithium ion battery to exceed 300 miles. In order to enable the energy density of the lithium ion battery to exceed 300Wh/kg, a strategy of increasing the nickel content is generally adopted to increase the specific capacity and increase the working voltage window, but the cycle life of the battery is seriously influenced, and the main reason of the phenomenon is that the structural stability is deteriorated due to multiple phase changes in the charging process along with the increase of the nickel content.
Therefore, the research on the attenuation mechanism of the high-nickel material becomes a research hotspot in recent years, and an Arumugam Manthiram topic group (DOI: 10.1002/aenm.201703154) carries out systematic comparison and analysis from two aspects of the cycle performance and the attenuation mechanism of NCM and NCA materials, and the research shows that the Li/Ni mixed discharge is more serious after the NCM material is cycled for a long time, particularly the NCM material is cycled under high voltage, the Li removal degree of the material is higher, the Li/Ni mixed discharge is further promoted, and the attenuation speed of the NCM in the long-term cycle is faster than that of the NCA; in addition, other researchers find that the doping of Al in NCA can reduce the cation mixed-discharge degree, and the effect of inhibiting the dissolution and irreversible phase change of transition metal elements is obviously better than that of the doping of Mn element in NCM, but the differentiation and crushing degree of secondary particles of NCA material in long-term circulation is more serious than that of NCM material.
The patent with publication number CN112563474A provides an in-situ coated NCMA quaternary positive electrode material and a preparation method thereof, which adopts the in-situ coating technology to uniformly coat a matrix material on an NCMA precursor, and carries out bulk phase doping on the basis of the in-situ coating.
The patent with publication number CN111697235A provides an NCMA quaternary gradient material and a preparation method thereof, the quaternary material sequentially comprises a core structure, a shell structure and a coating layer from inside to outside, and the Ni content of the material is distributed in a concentration gradient from the core to the content of Ni and Mn of an EDS energy spectrum of the shell. The anode material is obtained by sintering through the method, the volume change of lithium ions in the process of de-intercalation of the anode material is reduced by doping Al, the appearance and expansion of microcracks in secondary particles are effectively inhibited, and good physical and chemical properties are shown. However, the above technical means have some technical defects, the coating and doping of the high-nickel quaternary material need to be sintered or coated on the basis of the precursor, the synthesis process is complicated, and the period is long; the energy density of the high-nickel cathode material is reduced to a certain extent by the coating layer of the precursor. Therefore, how to solve the capacity and cycle problems becomes the key point of breakthrough of the nickel-cobalt-manganese-aluminum material in performance.
Therefore, how to solve the above-mentioned deficiencies of the prior art is a problem to be solved by the present invention.
Disclosure of Invention
The invention aims to provide an NCMA positive electrode material with a core-shell structure and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
NCMA positive pole with core-shell structureThe anode material is a lithium nickel cobalt manganese aluminum metal oxide with a core-shell structure and has a chemical general formula of LiNixCoyMnzAl1-x-y-zO2Wherein x, y, z satisfy the following conditions: x is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than or equal to 0 and less than 0.2, and x + y + z is less than 1;
the core of the anode material is lithium-containing nickel-cobalt-manganese oxide with a chemical general formula of LiNiaCobMn1-a-bO2A is more than or equal to 0.8 and less than 1, b is more than 0 and less than 0.2, wherein a + b is less than 1; the shell of the anode material is lithium-containing nickel-cobalt-aluminum oxide with a chemical general formula of LiNicCodAl1-c-dO2Wherein c is more than or equal to 0.8 and less than 1, d is more than 0 and less than 0.2, and the thickness of the outer shell layer accounts for 5-45% of the particle size of the whole core-shell structure material.
In order to achieve the purpose, the technical scheme adopted by the invention in the technical layer is as follows:
a preparation method of an NCMA positive electrode material with a core-shell structure comprises the following steps:
step one, preparing a ternary nickel-cobalt-manganese metal salt solution with the molar concentration of 1.0-2.5 mol/L, and preparing a binary nickel-cobalt metal salt solution with the molar concentration of 1.0-2.5 mol/L;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 2-10 mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 1.0-8.0 mol/L as a complexing agent;
step two, adding aluminum soluble metal salt into hot pure water at the temperature of 50-80 ℃, uniformly stirring until the aluminum soluble metal salt is completely dissolved, and preparing to obtain aluminum liquid with the aluminum concentration of 4-10 g/L;
adding pure water and a complexing agent into the reaction system, starting stirring to prepare a base solution, wherein the concentration of ammonium in the base solution is 0.15-0.6 mol/L; continuously introducing nitrogen or inert gas, adding a precipitator to adjust the pH value of the base solution to 11.0-13.0, and controlling the temperature of the reaction system to be 40-65 ℃;
step four, injecting the prepared ternary nickel-cobalt-manganese metal salt solution, a precipitator and a complexing agent into the base solution in the step three; controlling the pH value of the reaction solution to be 11.0-13.0, controlling the ammonium ion concentration in the reaction solution to be 0.25-0.45 mol/L, maintaining the temperature of the reaction system at 40-65 ℃, carrying out stage I reaction, and stopping the reaction when the granularity meets the requirement of the kernel particle size;
step five, suspending injection of a ternary nickel-cobalt-manganese metal salt solution, injecting the binary nickel-cobalt metal salt solution into a reaction system, injecting a precipitator and a complexing agent to adjust the pH value of the reaction solution to 11.5-12.5, controlling the ammonium ion concentration in the reaction solution to be 0.35-0.55 mol/L, and controlling the temperature of the reaction system to be 50-75 ℃;
then injecting the aluminum liquid prepared in the second step into the reaction system, carrying out stage II reaction, and finishing the reaction when the granularity growth meets the shell thickness requirement, thereby completing the synthesis of the precursor;
sixthly, washing and drying to obtain an NCMA precursor material with a core-shell structure;
and step seven, mixing the NCMA precursor material obtained in the step six with a lithium source, and sintering in an oxygen atmosphere to obtain the NCMA cathode material with the core-shell structure.
The relevant content in the above technical solution is explained as follows:
1. in the above scheme, in the first step, a ternary nickel-cobalt-manganese metal salt solution with a molar concentration of 1.0-2.5 mol/L and a binary nickel-cobalt metal salt solution with a molar concentration of 1.0-2.5 mol/L (i.e. when z is 0) may be configured according to the relationship of x, y, and z in the general formula.
2. In the above scheme, the "requirement for the particle size of the inner core" in the fourth step and the "requirement for the thickness of the outer shell" in the fifth step satisfy the following conditions: the average particle diameter of the NCMA precursor material with the core-shell structure is more than or equal to 8um and less than or equal to D50 and less than or equal to 18um, the particle size distribution radial distance is more than or equal to 0.4 and less than or equal to span and less than or equal to 0.7, and the tap density is more than or equal to 1.75 and less than or equal to TD and less than or equal to 2.15g/cm3Specific surface area of 8m2/g≤BET≤20m2(ii)/g; and the thickness of the shell layer accounts for 5-45% of the particle size of the whole core-shell structure material.
3. In the scheme, the metal salt solution is one or more of sulfate, chloride, nitrate and acetate;
the aluminum soluble metal salt is one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and sodium metaaluminate;
the complexing agent can also comprise one or more of EDTA, citric acid and oxalic acid, namely ammonia water is used as a main complexing agent, and the other complexing agents are auxiliary complexing agents.
The inert gas is one of argon and helium.
4. In the scheme, the stirring speed of the stage I is 300-750 rpm, and the stirring speed of the stage II is 250-500 rpm.
5. In the scheme, in the seventh step, the oxygen concentration of the oxygen atmosphere is greater than 90%, the sintering process comprises two processes of heating and constant-temperature sintering, the heating rate is 5-10 ℃/min, the temperature is increased to 550-850 ℃, and then constant-temperature sintering is carried out for 8-20 hours.
6. In the above scheme, in the seventh step, the lithium source is LiOH · H2O、Li2CO3、Li2One or more of O; the molar weight of Li element in the lithium source is calculated according to n (Li) = (Li/Me) × n (Ni + Co + Mn + Al), wherein n represents the molar weight of the element, and Li/Me represents the designed ratio of the molar weight of Li element in the added lithium source to the total molar weight of metal elements Ni + Co + Mn + Al added into the precursor, and the ratio ranges from 1.02 to 1.18.
The working principle and the advantages of the invention are as follows:
the invention discloses an NCMA (negative polarity alternating current) positive electrode material with a core-shell structure and a preparation method thereof, belonging to the field of lithium ion battery materials. The anode material is lithium nickel cobalt manganese aluminum metal oxide with a core-shell structure, and the chemical general formula is LiNixCoyMnzAl1-x-y-zO2Wherein x, y, z satisfy the following conditions: x is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than or equal to 0 and less than 0.2, and x + y + z is less than 1; the core of the anode material is lithium-containing nickel-cobalt-manganese oxide with a chemical general formula of LiNiaCobMn1-a-bO2A is more than or equal to 0.8 and less than 1, b is more than 0 and less than 0.2, wherein a + b is less than 1; the shell of the anode material is lithium-containing nickel-cobalt-aluminum oxide with a chemical general formula of LiNicCodAl1-c-dO2Wherein c is more than or equal to 0.8 and less than 1, d is more than 0 and less than 0.2, and the thickness of the outer shell layer accounts for 5-45% of the particle size of the whole core-shell structure material. The preparation method mainly comprises the following three steps: 1) synthesizing nickel by coprecipitation method and controlling pH value and ammonia concentrationCobalt manganese ternary hydroxide precursor; 2) adjusting the pH value and the ammonia concentration on the basis, and growing an Al-doped nickel-cobalt-aluminum hydroxide precursor shell with needle-shaped primary particles by taking a nickel-cobalt-manganese ternary precursor as a core; 3) and mixing the NCMA hydroxide precursor with the core-shell structure with lithium salt, and calcining at high temperature in an oxygen atmosphere to obtain the NCMA cathode material with the core-shell structure.
According to the invention, a coprecipitation method is utilized to carry out reaction in stages, so that the uniform distribution of Ni, Co, Mn and Al elements is realized, the respective disadvantages of NCM and NCA materials are mutually compensated through the structural design of an NCM core-NCA shell, the structural stability of a precursor material is improved, the high capacity advantage of a high-nickel anode material can be fully exerted, and the cycle performance of the anode material is effectively improved.
The beneficial effects of the invention include:
1. the invention adopts the structural design of NCM core-NCA shell, uses NCM as the inner core, and provides electrons for Ni through Jahn-teller effect, thereby stabilizing the internal structure of the material, effectively relieving the accumulation of stress in the particle of the NCA material in long-term circulation, and reducing the phenomena of secondary particle crushing and cracking;
2. according to the invention, the NCM core-NCA shell structure design is adopted, and the NCA is taken as an outer shell layer, so that Mn element dissolution and transition element migration of an NCM core to a negative electrode are avoided to a great extent, SEI (solid electrolyte interphase) film damage and active Li consumption are avoided, the respective advantages of NCM and NCA materials are further integrated, and the cycle life is greatly prolonged;
3. according to the NCMA cathode material provided by the invention, uniform and fine pores are formed between primary particles from the inner core to the outer shell, so that the lithium ions can be conveniently taken out and inserted, the sintered cathode material can well inherit the internal structural characteristics of a precursor, and the NCMA cathode material has the advantages of high specific capacity and good cycle stability;
4. the NCMA cathode material with the core-shell structure and the preparation process are relatively simple, the sizes of the core and the shell are adjustable, the NCMA cathode material can be well suitable for the existing reaction equipment, the difficulty of mass production and conversion is small, and the NCMA cathode material is convenient for large-scale industrial production.
Drawings
FIG. 1 is an electron microscope image I (3000 times magnification) of a NCMA high-nickel ternary precursor with a core-shell structure prepared in example 1 of the present invention;
FIG. 2 is an electron microscope image II (30000 times magnification) of the NCMA high-nickel ternary precursor with the core-shell structure prepared in example 1 of the present invention;
FIG. 3 is a graph showing the comparison of cycle characteristics of the positive electrode materials of example 1 of the present invention and comparative examples 1, 2 and 3;
fig. 4 is an electron micrograph (6000 times magnification) of the NCMA high-nickel ternary precursor with the core-shell structure prepared in example 1 of the present invention.
Detailed Description
The invention is further described with reference to the following figures and examples:
the present disclosure will be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the disclosure may be shown and described, and which, when modified and varied by the techniques taught herein, can be made by those skilled in the art without departing from the spirit and scope of the disclosure.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The singular forms "a", "an", "the" and "the", as used herein, also include the plural forms.
As used herein, the terms "comprising," "including," "having," and the like are open-ended terms that mean including, but not limited to.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
Referring to fig. 1 and 2, in this example 1, the synthesis of the NCMA positive electrode material with the core-shell structure is used as an illustration, and the method includes the following steps:
step 1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into a nickel-cobalt-manganese ternary solution with a total metal concentration of 2mol/L according to a metal molar ratio of 93: 5: 2, and preparing nickel sulfate and cobalt sulfate into a nickel-cobalt binary solution with a total metal concentration of 2mol/L according to a metal molar ratio of 94.9: 5.01; adopting 10mol/L alkali liquor as a precipitator; 2mol/L ammonia water solution is taken as a complexing agent;
step 2, adding a certain amount of aluminum sulfate into hot water at 50 ℃, uniformly stirring until the aluminum sulfate is completely dissolved, and preparing aluminum liquid with the aluminum concentration of 5 g/L;
step 3, adding a certain amount of hot pure water and ammonia water into a reaction system (namely a closed reaction kettle), regulating the stirring speed of the reaction kettle to be 500rpm, continuously introducing nitrogen, controlling the reaction temperature to be 50-70 ℃, and adding 10mol/L precipitator to regulate the pH value to be 12.1-12.5;
step 4, injecting the nickel-cobalt-manganese ternary solution, the precipitator and the complexing agent in the step 1 into the base solution in the step 2, controlling the pH of the reaction solution to be 11.6-12.2, and performing stage I reaction until the reaction granularity reaches 8.5um, namely suspending the reaction;
step 5, switching the metal raw material liquid to a nickel-cobalt binary solution, adjusting the pH value of a reaction system to 11.5-12.0, adjusting the ammonia concentration to 0.35-0.55 mol/L, slowly increasing the temperature of the reaction system to be stable, injecting the nickel-cobalt binary solution, a precipitator, a complexing agent and the aluminum liquid prepared in the step 2 into the reaction system, carrying out stage II reaction, and finishing the reaction when the particle size growth reaches 15 um;
step 6, after the synthesis of the precursor is finished, aging the reaction slurry obtained in the step 5 for 10 hours under a stirring state, then washing, drying in an oven at the temperature of 180 ℃, and finally sieving and deironing to obtain the NCMA precursor material with the core-shell structure; the thickness of the outer shell layer accounts for 5-45% of the particle size of the whole core-shell structure material, as shown in fig. 4, the inner surface of a middle dotted line circle represents an inner core, and the outer surface of a dotted line represents an outer shell.
And 7, uniformly mixing the NCMA precursor material with the core-shell structure with lithium hydroxide according to the ratio of 1:1.05, and calcining for 12 hours at 750 ℃ in an oxygen atmosphere to obtain the NCMA core-shell cathode material.
Comparative example 1
Taking the positive electrode material for synthesizing NCM as a comparison illustration, the method comprises the following steps:
step 1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into a nickel-cobalt-manganese ternary solution with a total metal concentration of 2mol/L according to a metal molar ratio of 93: 5: 2; adopting 10mol/L alkali liquor as a precipitator; 2mol/L ammonia water solution is taken as a complexing agent;
step 2, adding a certain amount of hot pure water and ammonia water into the reaction kettle, regulating the stirring speed of the reaction kettle to be 500rpm, continuously introducing nitrogen, controlling the reaction temperature to be 50-60 ℃, and adding 10mol/L liquid caustic soda to regulate the pH value to be 12.1-12.4;
step 4, injecting the nickel-cobalt-manganese ternary solution, the precipitator and the complexing agent in the step 1 into the base solution in the step 2, controlling the pH of the reaction solution to be 11.3-12.3, and carrying out a synthesis reaction, wherein the reaction is suspended when the reaction granularity reaches 15 um;
after the synthesis of the precursor is finished, aging the reaction slurry obtained in the step (5) for 10 hours under a stirring state, then washing, drying in an oven at 180 ℃, and finally, sieving and performing iron removal post-treatment to obtain the NCMA precursor material with the core-shell structure;
and 6, uniformly mixing the NCM precursor material with lithium hydroxide according to the ratio of 1:1.05, and calcining for 12 hours at 750 ℃ in an oxygen atmosphere to obtain the NCM anode material.
Comparative example 2
Taking the positive electrode material of the synthesized NCA as a comparison illustration, the method comprises the following steps:
step 1, preparing nickel sulfate and cobalt sulfate in a proportion of 94.9: 5.01 into a nickel-cobalt binary solution with a total metal concentration of 2 mol/L; adopting 10mol/L alkali liquor as a precipitator; 2mol/L ammonia water solution is taken as a complexing agent;
step 2, adding a certain amount of aluminum sulfate into hot water at 50 ℃, uniformly stirring until the aluminum sulfate is completely dissolved, and preparing aluminum liquid with the aluminum concentration of 5 g/L;
step 3, adding a certain amount of hot pure water and ammonia water into the reaction kettle, regulating the stirring speed of the reaction kettle to be 500rpm, continuously introducing nitrogen, controlling the reaction temperature to be 50-70 ℃, adding 32% of industrial alkali liquor, and adjusting the pH to be 12.3-12.5;
step 4, injecting the nickel-cobalt binary solution, the precipitator and the complexing agent in the step 1 into the base solution in the step 3, then injecting the aluminum liquid prepared in the step 2, controlling the pH of the reaction solution to be 11.5-12.5, carrying out a synthesis reaction, and finishing the reaction when the particle size growth reaches 15 um;
after the synthesis of the precursor is finished, aging the reaction slurry obtained in the step (5) for 10 hours under a stirring state, then washing, drying in an oven at 180 ℃, and finally, sieving and performing iron removal post-treatment to obtain the NCA precursor material with the core-shell structure;
and 6, uniformly mixing the NCA precursor material with the core-shell structure and lithium hydroxide according to the ratio of 1:1.05, and calcining for 12 hours at 750 ℃ in an oxygen atmosphere to obtain the NCA cathode material.
Comparative example 3
Taking a positive electrode material of synthetic NMCA as a comparison illustration, the method comprises the following steps:
step 1, preparing nickel sulfate, cobalt sulfate and manganese sulfate into a nickel-cobalt-manganese ternary solution with a total metal concentration of 2mol/L according to a metal molar ratio of 93.9: 5.05: 1; adopting 10mol/L alkali liquor as a precipitator; 2mol/L ammonia water solution is taken as a complexing agent;
step 2, adding a certain amount of aluminum sulfate into hot water at 50 ℃, uniformly stirring until the aluminum sulfate is completely dissolved, and preparing aluminum liquid with the aluminum concentration of 5 g/L;
step 3, adding a certain amount of hot pure water and ammonia water into the reaction kettle, regulating the stirring speed of the reaction kettle to be 500rpm, continuously introducing nitrogen, controlling the reaction temperature to be 50-70 ℃, and adding 32% of industrial liquid caustic soda to regulate the pH value to be 12.3-12.5;
step 4, injecting the nickel-cobalt-manganese ternary solution, the precipitator and the complexing agent in the step 1 into the base solution in the step 3, then injecting the aluminum liquid prepared in the step 2, controlling the pH of the reaction solution to be 11.60-12.4, carrying out a synthesis reaction, and finishing the reaction when the particle size reaches 15 um;
after the synthesis of the precursor is finished, aging the reaction slurry obtained in the step (5) for 10 hours under a stirring state, then washing, drying in an oven at 180 ℃, and finally, sieving and performing iron removal post-treatment to obtain the NCA precursor material with the core-shell structure;
and step 6, uniformly mixing the NCMA precursor material with lithium hydroxide according to the ratio of 1:1.05, and calcining for 12 hours at 750 ℃ in an oxygen atmosphere to obtain the NCMA anode material.
Table 1 shows detailed electrochemical test data of 1-50th of four positive electrode materials prepared in specific examples at a current density of 1C
As can be seen from table 1, the NCMA positive electrode material having the core-shell structure in example 1 has the highest capacity retention rate, and the capacity retention rate after 50 cycles at a rate of 1C is still 95.16%.
Fig. 3 is a comparison graph of cycle performance of the cathode materials of example 1 and comparative examples 1, 2, and 3 of the present invention, and it can be known from fig. 3 that the initial discharge capacity of the NCMA core-shell material of example 1 is not lower than that of the NCM material but higher than that of the NCA material, and the specific discharge capacity after 50 cycles is much higher than that of the NCM and NCA materials, so that the cycle advantage of the NCA material is well inherited, the cation mixed-discharge degree is effectively reduced, the defect of too fast attenuation of the NCM material is further overcome, and meanwhile, the NCMA core-shell material maintains the high capacity characteristic of the NCM material.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (7)
1. An NCMA positive electrode material with a core-shell structure is characterized in that: the anode material is lithium nickel cobalt manganese aluminum metal oxide with a core-shell structure, and the chemical general formula is LiNixCoyMnzAl1-x-y-zO2Wherein x, y, z satisfy the following conditions: x is more than or equal to 0.8 and less than 1, y is more than 0 and less than 0.2, z is more than or equal to 0 and less than 0.2, and x + y + z is less than 1;
the core of the anode material is lithium-containing nickel-cobalt-manganese oxide with a chemical general formula of LiNiaCobMn1-a-bO2，0.8≤a＜1，0＜b＜0.2，Wherein a + b is less than 1; the shell of the anode material is lithium-containing nickel-cobalt-aluminum oxide with a chemical general formula of LiNicCodAl1-c-dO2Wherein c is more than or equal to 0.8 and less than 1, d is more than 0 and less than 0.2, and the thickness of the outer shell layer accounts for 5-45% of the particle size of the whole core-shell structure material.
2. A preparation method of an NCMA positive electrode material with a core-shell structure is characterized by comprising the following steps: the method comprises the following steps:
step one, preparing a ternary nickel-cobalt-manganese metal salt solution with the molar concentration of 1.0-2.5 mol/L, and preparing a binary nickel-cobalt metal salt solution with the molar concentration of 1.0-2.5 mol/L;
preparing a sodium hydroxide or potassium hydroxide solution with the molar concentration of 2-10 mol/L as a precipitator;
preparing an ammonia water solution with the molar concentration of 1.0-8.0 mol/L as a complexing agent;
step two, adding aluminum soluble metal salt into hot pure water at the temperature of 50-80 ℃, uniformly stirring until the aluminum soluble metal salt is completely dissolved, and preparing to obtain aluminum liquid with the aluminum concentration of 4-10 g/L;
adding pure water and a complexing agent into the reaction system, starting stirring to prepare a base solution, wherein the concentration of ammonium in the base solution is 0.15-0.6 mol/L; continuously introducing nitrogen or inert gas, adding a precipitator to adjust the pH value of the base solution to 11.0-13.0, and controlling the temperature of the reaction system to be 40-65 ℃;
step four, injecting the prepared ternary nickel-cobalt-manganese metal salt solution, a precipitator and a complexing agent into the base solution in the step three; controlling the pH value of the reaction solution to be 11.0-13.0, controlling the ammonium ion concentration in the reaction solution to be 0.25-0.45 mol/L, maintaining the temperature of the reaction system at 40-65 ℃, carrying out stage I reaction, and stopping the reaction when the granularity meets the requirement of the kernel particle size;
step five, suspending injection of a ternary nickel-cobalt-manganese metal salt solution, injecting the binary nickel-cobalt metal salt solution into a reaction system, injecting a precipitator and a complexing agent to adjust the pH value of the reaction solution to 11.5-12.5, controlling the ammonium ion concentration in the reaction solution to be 0.35-0.55 mol/L, and controlling the temperature of the reaction system to be 50-75 ℃;
then injecting the aluminum liquid prepared in the second step into the reaction system, carrying out stage II reaction, and finishing the reaction when the granularity growth meets the shell thickness requirement, thereby completing the synthesis of the precursor;
sixthly, washing and drying to obtain an NCMA precursor material with a core-shell structure;
and step seven, mixing the NCMA precursor material obtained in the step six with a lithium source, and sintering in an oxygen atmosphere to obtain the NCMA cathode material with the core-shell structure.
3. The method of claim 2, wherein:
the metal salt solution is one or more of sulfate, chloride, nitrate and acetate;
the aluminum soluble metal salt is one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and sodium metaaluminate;
the complexing agent also comprises one or more of EDTA, citric acid and oxalic acid;
the inert gas is one of argon and helium.
4. The method of claim 2, wherein: the stirring speed of the stage I is 300-750 rpm, and the stirring speed of the stage II is 250-500 rpm.
5. The method of claim 2, wherein: in the sixth step, the average grain diameter of the NCMA precursor material with the core-shell structure is more than or equal to 8um and less than or equal to D50 and less than or equal to 18um, the grain size distribution radial distance is more than or equal to 0.4 and less than or equal to 0.7, and the tap density is more than or equal to 1.75 and less than or equal to TD and less than or equal to 2.15g/cm3Specific surface area of 8m2/g≤BET≤20m2/g。
6. The method of claim 2, wherein: and seventhly, the oxygen concentration of the oxygen atmosphere is more than 90%, the sintering process comprises two processes of heating and constant-temperature sintering, the heating rate is 5-10 ℃/min, the temperature is increased to 550-850 ℃, and then constant-temperature sintering is carried out for 8-20 hours.
7. The method of claim 2, wherein: in the seventh step, the lithium source is LiOH. H2O、Li2CO3、Li2One or more of O; the molar weight of Li element in the lithium source is calculated according to n (Li) = (Li/Me) × n (Ni + Co + Mn + Al), wherein n represents the molar weight of the element, and Li/Me represents the designed ratio of the molar weight of Li element in the added lithium source to the total molar weight of metal elements Ni + Co + Mn + Al added into the precursor, and the ratio ranges from 1.02 to 1.18.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114744188A (en) * | 2022-06-13 | 2022-07-12 | 河南科隆新能源股份有限公司 | Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof |
| CN114792794A (en) * | 2022-05-28 | 2022-07-26 | 天津巴莫科技有限责任公司 | Core-shell structured layered high-nickel cathode material and preparation method thereof |
| CN114804234A (en) * | 2022-05-18 | 2022-07-29 | 宁夏中化锂电池材料有限公司 | NCM/NCA core-shell structure ternary precursor material and preparation method thereof |
| CN115140782A (en) * | 2022-04-27 | 2022-10-04 | 南通金通储能动力新材料有限公司 | Lithium-rich manganese-based positive electrode material precursor with core-shell structure and preparation method thereof |
| CN115367815A (en) * | 2022-10-26 | 2022-11-22 | 河南科隆新能源股份有限公司 | Multilayer annular hole nickel-cobalt-aluminum precursor, preparation method and anode material thereof |
| CN116239162A (en) * | 2023-03-31 | 2023-06-09 | 蜂巢能源科技(无锡)有限公司 | Positive electrode material precursor and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107968202A (en) * | 2017-11-21 | 2018-04-27 | 宁波纳微新能源科技有限公司 | A kind of positive electrode of nickel cobalt manganese core shell structure containing aluminium and preparation method thereof |
| US20190081322A1 (en) * | 2017-02-22 | 2019-03-14 | Lionano Inc. | Core-shell electroactive materials |
| CN111092205A (en) * | 2019-12-19 | 2020-05-01 | 中冶瑞木新能源科技有限公司 | Core-double shell structure composite nickel-cobalt-manganese ternary precursor material and preparation method and application thereof |
| CN111952590A (en) * | 2020-07-08 | 2020-11-17 | 河南科隆新能源股份有限公司 | Lithium ion battery positive electrode material for improving safety and cycle performance and preparation method thereof |
| CN112018335A (en) * | 2019-05-28 | 2020-12-01 | 比亚迪股份有限公司 | Composite lithium ion battery anode material, lithium ion battery anode, lithium battery, battery module, battery pack and vehicle |
| CN113437262A (en) * | 2020-03-23 | 2021-09-24 | 飞翼新能源公司 | Preparation method of lithium nickel cobalt manganese aluminum composition, positive electrode material and lithium ion battery |
| CN113437263A (en) * | 2020-03-23 | 2021-09-24 | 飞翼新能源公司 | Lithium nickel cobalt manganese aluminum oxide |
| CN113501554A (en) * | 2021-07-02 | 2021-10-15 | 荆门市格林美新材料有限公司 | Nickel-cobalt-manganese-aluminum quaternary positive electrode material precursor and preparation method thereof |
| CN113683129A (en) * | 2021-08-24 | 2021-11-23 | 南通金通储能动力新材料有限公司 | Novel small-particle ternary precursor and preparation method thereof |
-
2021
- 2021-11-26 CN CN202111421634.0A patent/CN114188527A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190081322A1 (en) * | 2017-02-22 | 2019-03-14 | Lionano Inc. | Core-shell electroactive materials |
| CN107968202A (en) * | 2017-11-21 | 2018-04-27 | 宁波纳微新能源科技有限公司 | A kind of positive electrode of nickel cobalt manganese core shell structure containing aluminium and preparation method thereof |
| CN112018335A (en) * | 2019-05-28 | 2020-12-01 | 比亚迪股份有限公司 | Composite lithium ion battery anode material, lithium ion battery anode, lithium battery, battery module, battery pack and vehicle |
| CN111092205A (en) * | 2019-12-19 | 2020-05-01 | 中冶瑞木新能源科技有限公司 | Core-double shell structure composite nickel-cobalt-manganese ternary precursor material and preparation method and application thereof |
| CN113437262A (en) * | 2020-03-23 | 2021-09-24 | 飞翼新能源公司 | Preparation method of lithium nickel cobalt manganese aluminum composition, positive electrode material and lithium ion battery |
| CN113437263A (en) * | 2020-03-23 | 2021-09-24 | 飞翼新能源公司 | Lithium nickel cobalt manganese aluminum oxide |
| CN111952590A (en) * | 2020-07-08 | 2020-11-17 | 河南科隆新能源股份有限公司 | Lithium ion battery positive electrode material for improving safety and cycle performance and preparation method thereof |
| CN113501554A (en) * | 2021-07-02 | 2021-10-15 | 荆门市格林美新材料有限公司 | Nickel-cobalt-manganese-aluminum quaternary positive electrode material precursor and preparation method thereof |
| CN113683129A (en) * | 2021-08-24 | 2021-11-23 | 南通金通储能动力新材料有限公司 | Novel small-particle ternary precursor and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115140782A (en) * | 2022-04-27 | 2022-10-04 | 南通金通储能动力新材料有限公司 | Lithium-rich manganese-based positive electrode material precursor with core-shell structure and preparation method thereof |
| CN115140782B (en) * | 2022-04-27 | 2023-11-14 | 南通金通储能动力新材料有限公司 | Core-shell structured lithium-rich manganese-based positive electrode material precursor and preparation method thereof |
| CN114804234A (en) * | 2022-05-18 | 2022-07-29 | 宁夏中化锂电池材料有限公司 | NCM/NCA core-shell structure ternary precursor material and preparation method thereof |
| CN114804234B (en) * | 2022-05-18 | 2024-06-07 | 宁夏中化锂电池材料有限公司 | NCM/NCA core-shell structure ternary precursor material and preparation method thereof |
| CN114792794A (en) * | 2022-05-28 | 2022-07-26 | 天津巴莫科技有限责任公司 | Core-shell structured layered high-nickel cathode material and preparation method thereof |
| CN114744188A (en) * | 2022-06-13 | 2022-07-12 | 河南科隆新能源股份有限公司 | Lithium ion battery anode material with non-hollow porous structure and preparation method and application thereof |
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| CN115367815B (en) * | 2022-10-26 | 2023-01-24 | 河南科隆新能源股份有限公司 | Multilayer annular hole nickel-cobalt-aluminum precursor, preparation method and anode material thereof |
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