CN114079049A - Preparation method of ternary cathode material - Google Patents
Preparation method of ternary cathode material Download PDFInfo
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- CN114079049A CN114079049A CN202010843672.4A CN202010843672A CN114079049A CN 114079049 A CN114079049 A CN 114079049A CN 202010843672 A CN202010843672 A CN 202010843672A CN 114079049 A CN114079049 A CN 114079049A
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- 239000010406 cathode material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 61
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 54
- 239000000654 additive Substances 0.000 claims abstract description 45
- 230000000996 additive effect Effects 0.000 claims abstract description 44
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 claims abstract description 40
- 239000011572 manganese Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 claims description 3
- 229910015150 Ni1/3Co1/3Mn1/3(OH)2 Inorganic materials 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 3
- 229910011140 Li2C2 Inorganic materials 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
- 229910015450 Ni1-x-yCoxMny(OH)2 Inorganic materials 0.000 claims 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical group [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005406 washing Methods 0.000 abstract description 9
- 239000011247 coating layer Substances 0.000 abstract description 8
- 229910001868 water Inorganic materials 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical group [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 35
- 238000000498 ball milling Methods 0.000 description 9
- 238000007873 sieving Methods 0.000 description 8
- 230000001351 cycling effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005253 cladding Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910001512 metal fluoride Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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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- Composite Materials (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a ternary cathode material, which comprises the following steps: primary sintering: mixing nickel-cobalt hydroxide, a lithium source and a doping element compound, and performing primary sintering to obtain a primary sintered product; and (3) secondary sintering: mixing the primary sintered product with an additive, and performing secondary sintering to obtain a ternary cathode material finished product; wherein the additive is nickel-cobalt-manganese hydroxide with a structural formula of Ni1‑x‑ yCoxMny(OH)2，0.1≤x＜0.5，0<y is less than 0.5. According to the invention, the special additive is added, and the subsequent sintering process is assisted, so that the additive and residual lithium react to generate the coating layer with electrochemical activity. Consuming residual lithium on the surface of the material through reaction withoutThe method needs water washing, simplifies the process, reduces the cost, and simultaneously, the obtained ternary cathode material has high discharge specific capacity and good multiplying power and cycle performance.
Description
Technical Field
The invention relates to the technical field of lithium battery anode materials, in particular to a preparation method for reducing residual lithium on the surface of a ternary anode material, and particularly relates to a preparation method for reducing residual lithium on the surface of a nickel cobalt lithium manganate material.
Background
The ternary positive electrode material is considered to be a positive electrode material of a lithium ion power battery with great application prospect, but the problem of high surface residual lithium generally exists in the current ternary positive electrode material. Li remaining on surface of ternary cathode material2CO3And LiOH is non-conductive, so that the rate performance of the material is reduced, the cycling stability of the material is influenced, and if the content of residual lithium is too high in the processing process, slurry is fruited, is difficult to coat and seriously breaks the processing performance. Therefore, the surface residual lithium content of the ternary cathode material needs to be strictly controlled.
In order to reduce the surface residual lithium content, the conventional method is to water wash the material, but Li2CO3And LiOH has limited solubility in water, the surface structure of the material can be damaged by washing, after washing, the discharge specific capacity and the cycling stability of the ternary cathode material are greatly reduced, the ternary cathode material needs to be covered and compensated after subsequent drying, the preparation process is time-consuming, and the increase of the production cost is inevitably caused.
Therefore, the preparation method capable of effectively reducing the lithium residue on the surface of the ternary cathode material is developed, the surface structure of the ternary cathode material particles is not damaged, and the method has important significance for the development of the ternary cathode material.
Disclosure of Invention
Aiming at the problems that in the prior art, due to the fact that the content of residual lithium on the surface of a ternary cathode material is too high, the rate performance of the ternary cathode material is poor, and the discharge specific capacity and the cycle performance of the ternary cathode material are rapidly reduced, the preparation method provided by the invention can effectively reduce the residual lithium on the surface of the ternary cathode material, does not need water washing, and effectively reduces the content of residual lithium on the surface of the ternary cathode material and improves the rate and the cycle performance of the ternary cathode material by adding an additive metal hydroxide to react with the residual lithium on the surface.
In order to achieve the above object, the present invention provides the following technical solutions.
The invention provides a preparation method of a ternary cathode material, which comprises the following steps:
s1: primary sintering
Mixing nickel-cobalt hydroxide, a lithium source and a doping element compound, and performing primary sintering to obtain a primary sintered product H1;
s2: secondary sintering
Mixing the primary sintered product with an additive, and performing secondary sintering to obtain a ternary cathode material finished product;
wherein the additive is nickel-cobalt-manganese hydroxide with a structural formula of Ni1-x-yCoxMny(OH)2，0.1≤x＜0.5，0<y＜0.5。
According to the invention, the special additive is added, and the subsequent sintering process is assisted, so that the additive and residual lithium react to generate the coating layer with electrochemical activity. The residual lithium on the surface of the material is consumed through reaction, the process does not need water washing, the process is simplified, the cost is reduced, and meanwhile, a coating layer generated by the reaction has electrochemical activity and can be inserted and extracted with Li+The discharge specific capacity of the material is improved, and meanwhile, the cladding layer material and the base material belong to the ternary anode material and have similar crystal structures, so that the bonding strength of the cladding layer material and the base material is higher than that of the common metal oxide or metal fluoride and the base material, and the structural stability of the obtained ternary anode is further improved.
According to an embodiment of the present invention, the method for preparing the ternary cathode material may further include the following additional features.
According to the embodiment provided by the present invention, in S1, the structural formula of the nickel cobalt hydroxide is Ni1-x-yCoxMny(OH)2，0.002＜x＜0.5，0≤y＜0.5。
According to some embodiments of the invention, the nickel cobalt hydroxide is Ni0.83Co0.12Mn0.05(OH)2。
In a preferred embodiment, the nickel cobalt hydroxide has a median particle diameter (D50) of 5 to 15 μm, such as 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, and the like.
According to some embodiments of the present invention, the nickel cobalt hydroxide has a median particle size of 6 to 11 μm.
In a more preferred embodiment, the nickel cobalt hydroxide has a median particle diameter of 9 to 10 μm.
According to an embodiment of the present invention, in S1, the nickel cobalt hydroxide and the lithium source are used in an amount such that the ratio of the total moles of Ni, Co, and Mn to the moles of Li is 1 (1 to 1.25), for example, 1:1, 1:1.05, 1:1.12, 1:1.15, 1:1.18, 1:1.2, 1:1.21, 1:1.22, 1:1.23, 1:1.24, 1:1.25, and the like.
According to some embodiments of the present invention, the nickel cobalt hydroxide and the lithium source are used in an amount such that the ratio of the total moles of Ni, Co, and Mn to the moles of Li is 1: 1.05.
The lithium source is not particularly limited. Lithium sources common in the art may be used in the present invention. According to an embodiment of the present invention, the lithium source is LiOH, LiOH H2O、Li2CO3、Li2C2O4At least one of (a).
In some embodiments, the lithium source is LiOH H2O。
According to an embodiment of the present invention, in S1, the dopant element compound is ZrO2、MgO、TiO2、WO3、Al2O3At least one of (a).
According to an embodiment of the present invention, in S1, the mass of the doping element compound is 0.01 to 8% of the mass of the nickel cobalt hydroxide, preferably 0.1 to 5%, more preferably 0.1 to 3%, and particularly preferably 0.1 to 1%.
The amount of the doping compound may be adjusted according to the kind of the doping element compound.
According to the inventionIn one embodiment, the compound of the doping element is ZrO2。
Preferably, the ZrO2The mass of (b) is 0.1% to 0.6% of the mass of the nickel cobalt hydroxide, for example, 0.1%, 0.15%, 0.18%, 0.2%, 0.25%, 0.3%, 0.35%, 0.38%, 0.4%, 0.45%, 0.48%, 0.5%, 0.55%, 0.58%, 0.6%, etc.
According to still further embodiments of the present invention, the dopant element compound is Al2O3。
Preferably, the Al2O3The mass of (b) is 0.1% to 0.5% of the mass of the nickel cobalt hydroxide, for example, 0.1%, 0.15%, 0.18%, 0.2%, 0.25%, 0.3%, 0.35%, 0.38%, 0.4%, 0.45%, etc.
According to an embodiment of the present invention, the primary sintering is performed in an oxidizing atmosphere, and the oxidizing atmosphere is an oxygen atmosphere.
According to the embodiment provided by the invention, the temperature of the primary sintering is 650-830 ℃, and the time of the primary sintering is 8-15 h.
Specifically, the temperature of the primary sintering may be: 650 deg.C, 660 deg.C, 670 deg.C, 680 deg.C, 690 deg.C, 700 deg.C, 710 deg.C, 720 deg.C, 730 deg.C, 740 deg.C, 750 deg.C, 760 deg.C, 770 deg.C, 780 deg.C, 790 deg.C, 800 deg.C, 810 deg.C, 820 deg.C, 830 deg.C, etc.
The time for the primary sintering may be: 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, and so on.
According to the embodiment provided by the invention, the additive is nickel-cobalt-manganese hydroxide, the nickel-cobalt-manganese hydroxide has better compatibility with the base material, the structure of the coating layer obtained after the reaction with residual lithium is similar to that of the base material, the coating layer and the base material have similar crystal structures, and the bonding strength between the coating layer and the base material is higher than that between common metal oxide or metal fluoride and the base material, so that the structural stability of the obtained ternary cathode material is further improved.
As a preferred embodiment, the nickel-cobalt-manganese hydroxide has the structural formula of Ni1-x-yCoxMny(OH)2，0.1≤x＜0.5，0<y＜0.5。
According to an embodiment provided by the present invention, the additive is Ni1/3Co1/3Mn1/3(OH)2、Ni0.5Co0.2Mn0.3(OH)2、Ni0.6Co0.2Mn0.2(OH)2、Ni0.8Co0.1Mn0.1(OH)2At least one of (a).
According to an embodiment of the present invention, the mass of the additive is 0.1 to 1.5% of the mass of the primary sintered product, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, and the like. The dosage of the additive needs to correspond to the lithium doping level of the primary sintering product, and if the dosage of the additive is less, the additive cannot fully react with residual lithium on the surface of the primary sintering product; if the amount of the additive is large, the additive still remains after fully reacting with residual lithium on the surface of H1, and the additive itself cannot carry out Li+Intercalation and deintercalation, i.e., the inability to provide capacity, ultimately reduces the specific discharge capacity of the material.
In a more preferred embodiment, the mass of the additive is 1.0 to 1.5% of the mass of the primary sintered product.
According to some embodiments provided herein, the additive is 1.2% by mass of the primary sintered product. According to embodiments provided herein, the additive has a median particle size of 0.5 to 3 μm, such as 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, 1.0 μm, 1.1 μm, 1.2 μm, 1.3 μm, 1.4 μm, 1.5 μm, 1.6 μm, 1.7 μm, 1.8 μm, 1.9 μm, 2.0 μm, 2.1 μm, 2.2 μm, 2.3 μm, 2.4 μm, 2.5 μm, 2.6 μm, 2.7 μm, 2.8 μm, 2.9 μm, 3.0 μm, and the like.
According to some embodiments of the invention, the additive has a median particle size of 0.8 to 1.5 μm.
In a preferred embodiment, the median particle diameter of the additive is 1.2 to 1.5 μm.
According to an embodiment of the present invention, in S2, the mixing method includes, but is not limited to, ball milling. Preferably, the primary sintered product is sieved prior to ball milling and mixing. The sieve mesh for sieving is 400 meshes.
According to an embodiment of the present invention, the primary sintering is performed in an oxidizing atmosphere, and the oxidizing atmosphere is an oxygen atmosphere, preferably an oxygen atmosphere.
According to the embodiment provided by the invention, the temperature of the secondary sintering is 650-800 ℃, and the time of the secondary sintering is 6-15 h. The secondary sintering temperature is too low, so that residual lithium on the surface of a primary sintering product and additives can not be fully reacted, an amorphous material is easily formed, the product generated by the reaction has low crystallinity and contains impurity phases, and Li is seriously influenced+Embedding and separating, thereby reducing the discharge specific capacity and the cycling stability of the material; if the secondary sintering temperature is too high, an oxygen-deficient compound is easily formed and secondary crystallization is promoted, so that primary particles of a primary sintered product grow up, and the integral rate capability of the material is reduced.
Specifically, the temperature of the secondary sintering may be exemplified by: 650 deg.C, 660 deg.C, 670 deg.C, 680 deg.C, 690 deg.C, 700 deg.C, 710 deg.C, 720 deg.C, 730 deg.C, 740 deg.C, 750 deg.C, 760 deg.C, 770 deg.C, 780 deg.C, 790 deg.C, 800 deg.C, etc.
The time of the secondary sintering may be exemplified by: 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, and so on.
According to some embodiments provided by the invention, the temperature of the secondary sintering is 700-750 ℃, and the time of the secondary sintering is 6-15 h.
On the other hand, the invention provides the ternary cathode material prepared by the preparation method, wherein the content of residual lithium on the surface is as follows: 2500-3600 ppm, and the LiOH content is 2500-3500 ppm.
In another aspect, the present invention provides a lithium ion battery comprising the above ternary cathode material, which has a high specific capacity and excellent rate capability and cycle performance.
Compared with the prior art, the invention has the following technical effects:
the preparation method provided by the invention comprises the steps of addingAdding special additive, and adding subsequent sintering process to react the additive with residual lithium to form electrochemically active coating layer. The residual lithium on the surface of the first sintering product is consumed through reaction, water washing is not needed in the process, the process is simplified, the cost is reduced, a coating layer generated by the reaction has electrochemical activity and can be inserted and extracted from Li+The discharge specific capacity of the material is improved, and meanwhile, the cladding layer material and the base material belong to the ternary cathode material and have similar crystal structures, so that the bonding strength of the cladding layer material and the base material is higher than that of the common metal oxide or metal fluoride and the base material, and the structural stability of the obtained ternary cathode material is further improved.
Drawings
Fig. 1 shows the cycling curves at 1C rate for button lithium ion batteries made from the ternary cathode materials prepared in example 3 and comparative example 1.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. All patents and publications referred to herein are incorporated by reference in their entirety. The term "comprising" or "comprises" is open-ended, i.e. comprising what is specified in the present invention, but not excluding other aspects.
According to an embodiment provided by the present invention, the present invention provides a method for preparing a ternary positive electrode material, comprising:
s1: primary sintering
Mixing nickel-cobalt hydroxide, a lithium source and a doping element compound, and performing primary sintering in an oxidizing atmosphere to obtain a primary sintered product H1;
wherein: the structural formula of the nickel-cobalt hydroxide is Ni1-x-yCoxMny(OH)2，0.002＜x＜0.5，0≤y＜0.5；
The compound of the doping element is ZrO2、MgO、TiO2、WO3、Al2O3At least one of (a).
S2: secondary sintering
Mixing the primary sintering product with additive nickel cobalt manganese hydroxide, and performing secondary sintering in an oxidizing atmosphere to obtain a finished product of the ternary cathode material;
wherein the additive is nickel-cobalt-manganese hydroxide with a structural formula of Ni1-x-yCoxMny(OH)2，0.1≤x＜0.5，0<y＜0.5。
Preferably, the additive is Ni1/3Co1/3Mn1/3(OH)2、Ni0.5Co0.2Mn0.3(OH)2、Ni0.6Co0.2Mn0.2(OH)2、Ni0.8Co0.1Mn0.1(OH)2At least one of (a).
The preparation method does not comprise a water washing process.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the following specific implementation, for convenience, the primary sintered product is denoted as H1, and the secondary sintered product, that is, the finished ternary cathode material, is denoted as H2.
Example 1
In this embodiment, the nickel cobalt hydroxide is Ni0.83Co0.12Mn0.05(OH)2The median particle size is 9-10 mu m; the use amounts of the nickel cobalt hydroxide and the lithium source meet the condition that the ratio of the total mole number of Ni, Co and Mn to the mole number of Li is 1: 1.05; the compound of the doping element being ZrO2The mass of the additive is 0.3 percent of the mass of the nickel cobalt hydroxide, and the additive is Ni0.8Co0.1Mn0.1(OH)2A median particle diameter of 1.2 to 1.5 μm, Ni0.8Co0.1Mn0.1(OH)2The mass was 0.1% of the mass of H1.
Specifically, 100gNi is weighed0.83Co0.12Mn0.05(OH)247.61g of LiOH. H as a lithium source2O、0.3gZrO2Uniformly mixing, placing in a box-type atmosphere furnace for primary sintering at 760 ℃ for 15H, and introducing oxygen at 1.5L/min to obtain a primary sintered product H1; sieving H1 with 400 mesh sieve according to Ni0.8Co0.1Mn0.1(OH)2Ni was added in an amount of 0.1% by mass based on the mass of H10.8Co0.1Mn0.1(OH)2Ball-milling and mixing for 5min, then placing the uniformly mixed material in a box-type atmosphere furnace for secondary sintering at the temperature of 750 ℃ for 12H, and introducing oxygen for 1.5L/min to obtain a ternary cathode material finished product H2.
Example 2
In this embodiment, the nickel cobalt hydroxide is Ni0.83Co0.12Mn0.05(OH)2The median particle size is 9-10 mu m; the use amounts of the nickel cobalt hydroxide and the lithium source meet the condition that the ratio of the total mole number of Ni, Co and Mn to the mole number of Li is 1: 1.05; doping element compound ZrO2The mass of the catalyst is 0.3 percent of the mass of the nickel cobalt hydroxide; the additive is Ni0.8Co0.1Mn0.1(OH)2A median particle diameter of 1.2 to 1.5 μm, Ni0.8Co0.1Mn0.1(OH)2The mass was 0.5% of the mass of H1.
Specifically, 100g of Ni was weighed0.83Co0.12Mn0.05(OH)247.61g of LiOH. H as a lithium source2O、0.3g ZrO2Uniformly mixing, placing in a box-type atmosphere furnace for primary sintering at 760 ℃ for 15H, and introducing oxygen at 1.5L/min to obtain a primary sintered product H1; sieving H1 with 400 mesh sieve according to Ni0.8Co0.1Mn0.1(OH)2Ni was added in an amount of 0.5% by mass based on the mass of H10.8Co0.1Mn0.1(OH)2Ball-milling and mixing for 5min, and then placing the uniformly mixed materials into a box-type atmosphere furnace for secondary sintering at the secondary sintering temperatureAnd (3) at 750 ℃, for 12H, and introducing oxygen at 1.5L/min to obtain a ternary cathode material finished product H2.
Example 3
In this embodiment, the nickel cobalt hydroxide is Ni0.83Co0.12Mn0.05(OH)2The median particle size is 9-10 mu m; the use amounts of the nickel cobalt hydroxide and the lithium source meet the condition that the ratio of the total mole number of Ni, Co and Mn to the mole number of Li is 1.05; doping element compound ZrO2The mass of the catalyst is 0.3 percent of the mass of the nickel cobalt hydroxide; the additive is Ni0.8Co0.1Mn0.1(OH)2A median particle diameter of 1.2 to 1.5 μm, Ni0.8Co0.1Mn0.1(OH)2The mass was 1.2% of the mass of H1.
Specifically, 100g of Ni was weighed0.83Co0.12Mn0.05(OH)247.61g of LiOH. H as a lithium source2O、0.3g ZrO2Uniformly mixing, placing in a box-type atmosphere furnace for primary sintering at 760 ℃ for 15H, and introducing oxygen at 1.5L/min to obtain a primary sintered product H1; sieving H1 with 400 mesh sieve according to Ni0.8Co0.1Mn0.1(OH)2Ni was added in an amount of 1.2% by mass based on the mass of H10.8Co0.1Mn0.1(OH)2Ball-milling and mixing for 5min, then placing the uniformly mixed material in a box-type atmosphere furnace for secondary sintering at the temperature of 750 ℃ for 12H, and introducing oxygen for 1.5L/min to obtain a ternary cathode material finished product H2.
Example 4
In this embodiment, the nickel cobalt hydroxide is Ni0.83Co0.12Mn0.05(OH)2The median particle size is 9-10 mu m; the use amounts of the nickel cobalt hydroxide and the lithium source meet the condition that the ratio of the total mole number of Ni, Co and Mn to the mole number of Li is 1: 1.05; doping element compound ZrO2The mass of the catalyst is 0.3 percent of the mass of the nickel cobalt hydroxide; the additive is Ni0.8Co0.1Mn0.1(OH)2A median particle diameter of 1.2 to 1.5 μm, Ni0.8Co0.1Mn0.1(OH)2The mass was 1.5% of the mass of H1.
Specifically, 100g of Ni was weighed0.83Co0.12Mn0.05(OH)247.61g of LiOH. H as a lithium source2O、0.3g ZrO2Uniformly mixing, placing in a box-type atmosphere furnace for primary sintering at 760 ℃ for 15H, and introducing oxygen at 1.5L/min to obtain a primary sintered product H1; sieving H1 with 400 mesh sieve according to Ni0.8Co0.1Mn0.1(OH)2Ni was added in an amount of 1.5% by mass based on the mass of H10.8Co0.1Mn0.1(OH)2Ball-milling and mixing for 5min, then placing the uniformly mixed material in a box-type atmosphere furnace for secondary sintering at the temperature of 750 ℃ for 12H, and introducing oxygen for 1.5L/min to obtain a ternary cathode material finished product H2.
Example 5
In this embodiment, the nickel cobalt hydroxide is Ni0.83Co0.12Mn0.05(OH)2The median particle size is 9-10 mu m; the use amounts of the nickel cobalt hydroxide and the lithium source meet the condition that the ratio of the total mole number of Ni, Co and Mn to the mole number of Li is 1: 1.05; doping element compound ZrO2The mass of the catalyst is 0.3 percent of the mass of the nickel cobalt hydroxide; the additive is Ni0.8Co0.1Mn0.1(OH)2A median particle diameter of 1.2 to 1.5 μm, Ni0.8Co0.1Mn0.1(OH)2The mass was 1.2% of the mass of H1.
Specifically, 100g of Ni was weighed0.83Co0.12Mn0.05(OH)247.61g of LiOH. H as a lithium source2O、0.3g ZrO2Uniformly mixing, placing in a box-type atmosphere furnace for primary sintering at 760 ℃ for 15H, and introducing oxygen at 1.5L/min to obtain a primary sintered product H1; sieving H1 with 400 mesh sieve according to Ni0.8Co0.1Mn0.1(OH)2Ni was added in an amount of 1.2% by mass based on the mass of H10.8Co0.1Mn0.1(OH)2Ball milling and mixing for 5min, and mixingAnd (3) placing the material in a box-type atmosphere furnace for secondary sintering, wherein the secondary sintering temperature is 730 ℃, the time is 12 hours, and the oxygen introducing amount is 1.5L/min, so that a ternary cathode material finished product H2 is obtained.
Example 6
In this embodiment, the nickel cobalt hydroxide is Ni0.83Co0.12Mn0.05(OH)2The median particle size is 9-10 mu m; the use amounts of the nickel cobalt hydroxide and the lithium source meet the condition that the ratio of the total mole number of Ni, Co and Mn to the mole number of Li is 1: 1.05; doping element compound ZrO2The mass of the catalyst is 0.3 percent of the mass of the nickel cobalt hydroxide; the additive is Ni0.5Co0.2Mn0.3(OH)2A median particle diameter of 1.2 to 1.5 μm, Ni0.5Co0.2Mn0.3(OH)2The mass was 1.2% of the mass of H1.
Specifically, 100g of Ni was weighed0.83Co0.12Mn0.05(OH)247.61g of LiOH. H as a lithium source2O、0.3g ZrO2Uniformly mixing, placing in a box-type atmosphere furnace for primary sintering at 760 ℃ for 15H, and introducing oxygen at 1.5L/min to obtain a primary sintered product H1; sieving H1 with 400 mesh sieve according to Ni0.5Co0.2Mn0.3(OH)2Ni was added in an amount of 1.2% by mass based on the mass of H10.5Co0.2Mn0.3(OH)2Ball-milling and mixing for 5min, then placing the uniformly mixed material in a box-type atmosphere furnace for secondary sintering at the temperature of 750 ℃ for 12H, and introducing oxygen for 1.5L/min to obtain a ternary cathode material finished product H2.
Comparative example 1
In this embodiment, the nickel cobalt hydroxide is Ni0.83Co0.12Mn0.05(OH)2The median particle size is 9-10 mu m; the use amounts of the nickel cobalt hydroxide and the lithium source meet the condition that the ratio of the total mole number of Ni, Co and Mn to the mole number of Li is 1: 1.05; doping element compound ZrO2The mass of the catalyst is 0.3 percent of the mass of the nickel cobalt hydroxide.
Specifically, 100g of Ni was weighed0.83Co0.12Mn0.05(OH)247.61g of LiOH. H as a lithium source2O、0.3g ZrO2Uniformly mixing, placing in a box-type atmosphere furnace for primary sintering at 760 ℃ for 15H, and introducing oxygen at 1.5L/min to obtain a primary sintered product H1; sieving H1 through a 400-mesh screen, adding deionized water according to the mass ratio of the deionized water to H1 of 1:1, mixing, stirring for 5min at the stirring speed of 600r/min, performing suction filtration, drying the obtained filter cake, performing ball-milling mixing with boric acid with the mass of 0.1% of that of the filter cake, then placing the uniformly mixed material in a box-type atmosphere furnace for secondary sintering at the secondary sintering temperature of 300 ℃ for 10H, and introducing oxygen for 1.5L/min to obtain the ternary cathode material finished product H2.
Performance testing
The residual lithium content on the surface of the ternary cathode material prepared in examples 1-6 and comparative example 1 was tested, and the test results are shown in table 1.
The ternary cathode materials prepared in examples 1-6 and comparative example 1 were used to prepare button lithium ion batteries, and the first discharge capacity and 100-cycle retention rate at 1C rate were tested, with the test results shown in table 1.
The ternary positive electrode materials prepared in example 3 and comparative example 1 were used to prepare button lithium ion batteries, and the cycling curve at 1C rate was tested, as shown in fig. 1.
TABLE 1
As can be seen from table 1, compared with the conventional washing process, the preparation process of the present invention can significantly reduce the surface residual lithium content of the ternary cathode material, and the specific discharge capacity and the cycle performance of the ternary cathode material are significantly improved. From examples 1 to 4, it can be seen that the residual lithium content of the material gradually decreases with the increase of the additive amount, and when the additive amount is not enough to fully consume the residual lithium, the specific discharge capacity of the material increases with the increase of the additive amount, but continues to increase, because the additive itself can not generate electrochemical reaction, and Li is inserted and pulled out+Therefore, the specific discharge capacity of the material is reduced.
As can be seen from fig. 1, example 3 has a higher specific discharge capacity and a better cycling stability, and comparative example 1, due to washing with water, destroys the surface structure of the primary sintered product to some extent, and although the primary sintered product is subsequently coated with boric acid, the cycling stability is poorer.
In the description herein, references to the description of the terms "some embodiments," "other embodiments," "an embodiment," "an example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention and examples have been shown and described above, it is understood that the above embodiments, examples are illustrative and not to be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments, examples by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of a ternary cathode material is characterized by comprising the following steps:
s1: primary sintering
Mixing nickel-cobalt hydroxide, a lithium source and a doping element compound, and performing primary sintering to obtain a primary sintered product;
s2: secondary sintering
Mixing the primary sintered product with an additive, and performing secondary sintering to obtain a ternary cathode material finished product;
wherein the additive is nickel-cobalt-manganese oxyhydrogenCompound of formula Ni1-x-yCoxMny(OH)2，0.1≤x＜0.5，0<y＜0.5。
2. The method of claim 1, wherein in S1, the structural formula of the nickel cobalt hydroxide is Ni1-x-yCoxMny(OH)2X is more than 0.002 and less than 0.5, and y is more than or equal to 0 and less than 0.5; preferably, the median particle size of the nickel cobalt hydroxide is 5-15 μm; preferably, the lithium source is LiOH, LiOH H2O、Li2CO3、Li2C2O4At least one of; more preferably, the nickel cobalt hydroxide and the lithium source are used in an amount such that the ratio of the total mole number of Ni, Co and Mn to the mole number of Li is 1 (1-1.25).
3. The method for preparing a ternary cathode material according to claim 1, wherein in S1, the mass of the doping element compound is 0.01-8% of the mass of nickel cobalt hydroxide; preferably, the doping element compound is ZrO2、MgO、TiO2、WO3、Al2O3At least one of (a).
4. The method for producing a ternary cathode material according to claim 1, wherein the primary sintering is performed in an oxidizing atmosphere, and the oxidizing atmosphere is an oxygen atmosphere; preferably, the temperature of the primary sintering is 650-830 ℃, and the time of the primary sintering is 8-15 h.
5. The method for preparing the ternary cathode material according to claim 1, wherein the mass of the additive is 0.1-1.5% of the mass of the primary sintered product; preferably, the additive is Ni1/3Co1/3Mn1/3(OH)2、Ni0.5Co0.2Mn0.3(OH)2、Ni0.6Co0.2Mn0.2(OH)2、Ni0.8Co0.1Mn0.1(OH)2At least one of; more preferably, the median particle diameter of the additive is 0.5 to 3 μm.
6. The method for producing a ternary cathode material according to claim 1, wherein the secondary sintering is performed in an oxidizing atmosphere, and the oxidizing atmosphere is an oxygen atmosphere.
7. The method for preparing a ternary cathode material according to claim 1, wherein the temperature of the secondary sintering is 650 to 800 ℃, and the time of the secondary sintering is 6 to 15 hours.
8. The ternary positive electrode material obtained by the production method according to any one of claims 1 to 7.
9. The ternary positive electrode material according to claim 8, wherein the content of residual lithium on the surface is: li2CO3The content is 2500-3600 ppm, and the LiOH content is 2500-3500 ppm.
10. A lithium ion battery comprising the ternary cathode material of claim 8 or 9.
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