CN117038956B - Cobalt-free high-nickel positive electrode material, preparation method thereof and lithium ion battery - Google Patents
Cobalt-free high-nickel positive electrode material, preparation method thereof and lithium ion battery Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 23
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000005245 sintering Methods 0.000 claims abstract description 56
- 239000000463 material Substances 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005056 compaction Methods 0.000 claims abstract description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 8
- 239000006259 organic additive Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims description 3
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 18
- 238000001816 cooling Methods 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 238000010280 constant potential charging Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/10—Solid density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of lithium ion battery materials, and discloses a cobalt-free high-nickel positive electrode material with a chemical formula of LiNi x Mn 1‑x O 2 Wherein x is 0.85.ltoreq.x<1, a step of; the positive electrode material is in a shape similar to a cube, and has the tap density of 2.48-2.55g/cm 3 The compaction density is 3.71-3.78g/cm 3 . Inorganic salt and organic additives are added in the process of precursor mixing and sintering, and the cobalt-free high-nickel anode material with high tap density and high compaction density is prepared by adopting a two-stage sintering and water washing process, so that the high-voltage cycle performance of the battery is further improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a cobalt-free high-nickel positive electrode material, a preparation method and application thereof.
Background
At present, the global electric automobile is rapidly developed, and the development of the lithium ion power battery with high energy density, long cycle life, good safety and low cost is particularly important. However, due to the scarcity of cobalt, the cobalt price is increased, and the lithium ion battery anode material starts to be low-cobalt or even free of cobalt. In the existing commercial positive electrode material, the cobalt-free high nickel lithium ion positive electrode material LiNi x Mn 1-x O 2 (0.5<x<1) The method has the advantages of high energy density, rich nickel-manganese resources, low cost, high safety and the like, and becomes a research hot spot of the lithium ion battery anode material in recent years. However, cobalt-free high-nickel lithium ion positive electrode materials still have problems in terms of service life and discharge performance, especially in terms of multiplying powerImprovement is still needed in the aspects of energy, high-pressure cycle stability, lithium nickel mixed discharge and the like.
Disclosure of Invention
Based on the problems existing in the prior art, a first object of the invention is to provide a cobalt-free high-nickel positive electrode material, which improves the high-voltage cycling stability of a lithium ion battery. The second object of the invention is to provide a preparation method of the cobalt-free high-nickel cathode material. A third object of the present invention is to provide a lithium ion battery.
In order to achieve the above object, the present invention provides the following specific technical solutions.
First, the invention provides a cobalt-free high-nickel positive electrode material, the chemical general formula of which is LiNi x Mn 1-x O 2 Wherein x is 0.85.ltoreq.x<1, a step of; the positive electrode material is in a shape similar to a cube, and has the tap density of 2.48-2.55g/cm 3 The compaction density is 3.71-3.78g/cm 3 。
Secondly, the invention provides a preparation method of the cobalt-free high-nickel anode material, which comprises the following steps:
step S1, the chemical general formula is Ni x Mn 1-x (OH) 2 Mixing the precursor material of (2) with a lithium source, inorganic salt and an organic additive to obtain a mixture; wherein x is 0.85.ltoreq.x<1, a step of; the inorganic salt is NaF, KF, na 2 SiF 6 At least one of (a) and (b); the organic additive is at least one of PEG2000, PEG8000 and PEG 20000;
step S2, sintering the mixture for the first time in an oxidizing atmosphere, and sintering at 600-1200 ℃ in a heat-preserving way to obtain a sintered material;
step S3, washing a baked material with deionized water, and then drying;
and S4, sintering the material obtained in the step S3 for the second time, and performing heat preservation sintering at 400-1000 ℃ to obtain the cobalt-free high-nickel anode material.
In a further preferred embodiment, the molar ratio of the precursor to lithium in the lithium source is 0.41-1.1:1, the molar ratio of the inorganic salt to lithium in the lithium source is 0.05-0.3:1, a step of; the amount of the organic additive is 0.2% -1% of the mass of the precursor.
Advancing oneThe lithium source is LiOH or LiNO 3 、Li 2 SO 4 、Li 2 CO 3 、LiCl、C 2 H 3 LiO 2 At least one of them. Further preferred are LiOH and Li 2 CO 3 。
In a further preferred embodiment, the first sintering and the second sintering have a temperature rise rate of 1-8deg.C/min.
In a further preferred embodiment, the temperature of the first sintering and the second sintering is 3-15h.
Based on the same inventive concept, the invention provides a lithium ion battery, which comprises the cobalt-free high-nickel anode material.
The invention has the following obvious beneficial effects:
the cobalt-free high-nickel positive electrode material provided by the invention has a similar cube structure, uniform components and uniform particle size distribution, and the tap density of the positive electrode material is 2.48-2.55g/cm 3 The compaction density is 3.71-3.78g/cm 3 . After the positive electrode material is assembled into the battery, the battery has good electrochemical performance and high stability.
In the positive electrode material provided and prepared by the invention, the molar percentage of nickel is not less than 85%, and Co is not added, so that the production cost is greatly reduced.
The preparation method mainly comprises two-stage sintering and one-stage water washing, has simple process and easy operation, is beneficial to large-scale popularization, and has strong applicability to the existing equipment.
Drawings
Fig. 1 is an SEM image of the positive electrode material obtained in example 1.
Fig. 2 is an SEM image of the positive electrode material obtained in comparative example 1.
Fig. 3 is an SEM image of the positive electrode material obtained in comparative example 2.
Fig. 4 is an SEM image of the positive electrode material obtained in comparative example 3.
Fig. 5 is an SEM image of the positive electrode material obtained in comparative example 4.
Fig. 6 is a cycle performance chart of a battery assembled from the positive electrode materials obtained in examples 1 to 3 and comparative examples 1 to 4.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
Mixing: 1.09g LiOH, 2g precursor Ni 0.9 Mn 0.1 (OH) 2 Adding 0.181g of NaF and 0.01g of PEG2000 into a ball mill, and uniformly mixing to obtain a mixture;
primary sintering: placing the mixture into a sintering furnace in an oxidizing atmosphere, heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 5 hours, and cooling along with the furnace after the heat preservation is finished to obtain a sintered material;
washing: washing the primary baked material with water, and then drying the primary baked material in vacuum at 80 ℃ to obtain a secondary to-be-baked material;
secondary sintering: and (3) placing the secondary material to be sintered in a sintering furnace in an oxidizing atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat, sintering for 6 hours, and cooling along with the furnace to obtain the anode material.
Fig. 1 is an SEM image of the positive electrode material, and it can be seen from the image that the surface of the prepared positive electrode material particles is smooth, the whole tends to a more regular cube structure, the particles are finer, the size is 1.5-3 μm, and the inter-particle distribution is more dispersed and uniform.
Comparative example 1
Comparative example 1 differs from example 1 only in that: naF and PEG2000 were not added during compounding.
Mixing: 1.09g LiOH, 2g precursor Ni 0.9 Mn 0.1 (OH) 2 Adding the mixture into a ball mill for uniform mixing to obtain a mixture;
primary sintering: placing the mixture into a sintering furnace in an oxidizing atmosphere, heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 5 hours, and cooling along with the furnace after the heat preservation is finished to obtain a sintered material;
washing: washing the primary baked material with water, and then drying the primary baked material in vacuum at 80 ℃ to obtain a secondary to-be-baked material;
secondary sintering: and (3) placing the secondary material to be sintered in a sintering furnace in an oxidizing atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat, sintering for 6 hours, and cooling along with the furnace to obtain the anode material.
Fig. 2 is an SEM image of the positive electrode material, from which it can be seen that the particles have smooth surfaces, larger particle sizes and more fine particle agglomeration, and irregular morphology.
Comparative example 2
Comparative example 2 differs from example 1 only in that: naF was added during compounding, but PEG2000 was not added.
Mixing: 1.09g LiOH, 2g precursor Ni 0.9 Mn 0.1 (OH) 2 Adding 0.181g of NaF into a ball mill, and uniformly mixing to obtain a mixture;
primary sintering: placing the mixture into a sintering furnace in an oxidizing atmosphere, heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 5 hours, and cooling along with the furnace after the heat preservation is finished to obtain a sintered material;
washing: washing the primary baked material with water, and then drying the primary baked material in vacuum at 80 ℃ to obtain a secondary to-be-baked material;
secondary sintering: and (3) placing the secondary material to be sintered in a sintering furnace in an oxidizing atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat, sintering for 6 hours, and cooling along with the furnace to obtain the anode material.
Fig. 3 is an SEM image of the positive electrode material, and it can be seen from the image that the surface of the particles is smooth, agglomeration of the particles is reduced, the fine particles are more, the distribution is more dispersed, and the irregular morphology is obtained.
Comparative example 3
Comparative example 3 differs from example 1 only in that: PEG2000 was added during compounding, but no NaF was added.
Mixing: 1.09g LiOH, 2g precursor Ni 0.9 Mn 0.1 (OH) 2 Adding 0.01g PEG2000 into a ball mill, and uniformly mixing to obtain a mixture;
primary sintering: placing the mixture into a sintering furnace in an oxidizing atmosphere, heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 5 hours, and cooling along with the furnace after the heat preservation is finished to obtain a sintered material;
washing: washing the primary baked material with water, and then drying the primary baked material in vacuum at 80 ℃ to obtain a secondary to-be-baked material;
secondary sintering: and (3) placing the secondary material to be sintered in a sintering furnace in an oxidizing atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat, sintering for 6 hours, and cooling along with the furnace to obtain the anode material.
Fig. 4 is an SEM image of the positive electrode material, from which it can be seen that the overall fine particles are reduced, the size is more uniform, and the morphology is irregular.
Comparative example 4
Comparative example 4 differs from example 1 only in that: there is no water washing step.
Mixing: 1.09g LiOH, 2g precursor Ni 0.9 Mn 0.1 (OH) 2 Adding 0.181g of NaF and 0.01g of PEG2000 into a ball mill, and uniformly mixing to obtain a mixture;
primary sintering: placing the mixture into a sintering furnace in an oxidizing atmosphere, heating to 900 ℃ at a heating rate of 3 ℃/min, preserving heat for 5 hours, and cooling along with the furnace after the heat preservation is finished to obtain a sintered material;
secondary sintering: and (3) placing the sintered material in a sintering furnace in an oxidizing atmosphere, heating to 800 ℃ at a heating rate of 5 ℃/min, preserving heat and sintering for 6 hours, and then cooling along with the furnace to obtain the anode material.
Fig. 5 is an SEM image of the positive electrode material, and it can be seen from the image that the surface of the particles is smoother, the whole tends to have a more regular cube structure, the particles are finer, the size is 1.5-3 μm, but the bonding phenomenon exists between the particles.
Example 2
Mixing: will be 3.2gLi 2 CO 3 、3.27g of precursor Ni 0.85 Mn 0.15 (OH) 2 Adding 0.251gKF and 6.5mg PEG8000 into a ball mill, and uniformly mixing to obtain a mixture;
primary sintering: placing the mixture into a sintering furnace in an oxidizing atmosphere, heating to 600 ℃ at a heating rate of 1 ℃/min, preserving heat for 15h, and cooling along with the furnace after the heat preservation is finished to obtain a sintered material;
washing: washing the primary baked material with water, and then drying the primary baked material in vacuum at 80 ℃ to obtain a secondary to-be-baked material;
secondary sintering: and (3) placing the secondary material to be sintered in a sintering furnace in an oxidizing atmosphere, heating to 1000 ℃ at a heating rate of 8 ℃/min, preserving heat, sintering for 3 hours, and cooling along with the furnace to obtain the anode material.
Example 3
Mixing: 1.09g LiOH, 4.63g precursor Ni 0.95 Mn 0.05 (OH) 2 、2.57gNa 2 SiF 6 Adding 0.45g PEG20000 into a ball mill, and uniformly mixing to obtain a mixture;
primary sintering: placing the mixture into a sintering furnace in an oxidizing atmosphere, heating to 1200 ℃ at a heating rate of 8 ℃/min, preserving heat for 3 hours, and cooling along with the furnace after the heat preservation is finished to obtain a sintered material;
washing: washing the primary baked material with water, and then drying the primary baked material in vacuum at 80 ℃ to obtain a secondary to-be-baked material;
secondary sintering: and (3) placing the secondary material to be sintered in a sintering furnace in an oxidizing atmosphere, heating to 400 ℃ at a heating rate of 1 ℃/min, preserving heat, sintering for 15h, and cooling along with the furnace to obtain the anode material.
The positive electrode materials obtained in examples 1 to 3 and comparative examples 1 to 4 were respectively tested for tap density and compacted density in the following manner:
tap density: and loading the weighed powder into a measuring cylinder of a compaction device, and fixing the measuring cylinder on a support. The cam is rotated, and the orientation rod drives the support to slide up and down and impact on the anvil. Shaking 250.+ -.15 times per minute for 12 minutes. And measuring the volume of the powder in the measuring cylinder, wherein the ratio of the mass of the powder to the volume is the tap density of the powder.
Compaction density: taking the rolled pole piece, cutting out an area by a round or square cutter, measuring the thickness, weighing, washing off the positive electrode material by using an acetone alcohol mixed solution, drying, weighing the weight of the rest aluminum foil, and measuring the thickness of the aluminum foil. The difference in weight divided by the area, the areal density was calculated. The areal density divided by the thickness difference is the compacted density.
The test results are shown in Table 1. The positive electrode material prepared in example 1 had a higher tap density and a higher compacted density than those of comparative examples 1 to 4.
TABLE 1
The positive electrode materials obtained in examples 1 to 3 and comparative examples 1 to 4 were assembled into batteries in the following manner, respectively: mixing the prepared anode material, a binder PVDF and a conductive agent according to the proportion of 8:1:1, dry-grinding for 10min, adding a solvent NMP, uniformly stirring by using a homogenizer to prepare anode slurry, uniformly coating the anode slurry on an aluminum foil, drying, and rolling the anode sheet on a sheet roller press to prepare an anode; taking a metal lithium sheet as a negative electrode; lithium ion secondary electrolyte LB-037 (1M LiPF6 in DEC:EC:EMC =1:1:1 vol%) was used as electrolyte and Celgard2325 as separator to assemble the lithium ion secondary electrolyte into a button cell of LIR 2032.
The electrical properties of the cells were tested as follows: in a constant temperature box at 25 ℃, constant current charging is carried out to a voltage of 4.3V at a rate of 0.1C, constant voltage charging is carried out to a voltage of 0.01C, the constant voltage charging is carried out, then 0.1C is used for discharging to 3V, circulation is carried out twice, then the battery is charged to a voltage of 4.3V at a rate of 0.5C, constant voltage charging is carried out to a voltage of 0.05C, the constant voltage charging is carried out, then 0.5C is used for discharging to 3V, and the charge and discharge capacity is recorded.
As a result, as shown in fig. 6, after the positive electrode materials prepared in example 1 and comparative examples 1 to 4 were assembled into batteries, respectively, the high-voltage cycle performance of the batteries in which the positive electrode material was derived from example 1 was significantly superior to that of the batteries in which the positive electrode material was derived from comparative examples 1 to 4. Therefore, inorganic salt and organic additives are added in the process of precursor mixing and sintering, and a two-stage sintering and water washing process is adopted, so that the positive electrode material with high tap density and high compaction density can be prepared, and the high-pressure cycle performance of the battery can be improved.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The preparation method of the cobalt-free high-nickel cathode material is characterized by comprising the following steps of:
step S1, the chemical general formula is Ni x Mn 1-x (OH) 2 Mixing the precursor material of (2) with a lithium source, inorganic salt and an organic additive to obtain a mixture; wherein x is 0.85.ltoreq.x<1, a step of; the inorganic salt is NaF, KF, na 2 SiF 6 At least one of (a) and (b); the organic additive is at least one of PEG2000, PEG8000 and PEG 20000;
step S2, sintering the mixture for the first time in an oxidizing atmosphere, and sintering at 600-1200 ℃ in a heat-preserving way to obtain a sintered material;
step S3, washing a baked material with deionized water, and then drying;
step S4, sintering the material obtained in the step S3 for the second time, and performing heat preservation sintering at 400-1000 ℃ to obtain the cobalt-free high-nickel anode material;
the chemical general formula of the cobalt-free high-nickel positive electrode material is LiNi x Mn 1-x O 2 Wherein x is 0.85.ltoreq.x<1, a step of; the positive electrode material is in a shape similar to a cube, and has the tap density of 2.48-2.55g/cm 3 The compaction density is 3.71-3.78g/cm 3 。
2. The cobalt-free high nickel positive electrode material according to claim 1, wherein the molar ratio of the precursor to lithium in the lithium source is 0.41-1.1:1, the molar ratio of the inorganic salt to lithium in the lithium source is 0.05-0.3:1, a step of; the amount of the organic additive is 0.2% -1% of the mass of the precursor.
3. The cobalt-free high nickel positive electrode material according to claim 1, wherein the lithium source is LiOH, liNO 3 、Li 2 SO 4 、Li 2 CO 3 、LiCl、C 2 H 3 LiO 2 At least one of them.
4. A cobalt-free high nickel positive electrode material according to claim 3, wherein said lithium source is LiOH, li 2 CO 3 。
5. The cobalt-free high nickel positive electrode material according to claim 1, wherein the temperature rise rate of the first sintering and the second sintering is 1-8 ℃/min.
6. The cobalt-free high nickel positive electrode material according to claim 5, wherein the time for the first sintering and the second sintering is 3 to 15 hours.
7. A lithium ion battery comprising the cobalt-free high nickel cathode material according to any one of claims 1-6.
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