CN115231625B - Ternary precursor material, ternary positive electrode material, preparation method of ternary positive electrode material and lithium ion battery - Google Patents
Ternary precursor material, ternary positive electrode material, preparation method of ternary positive electrode material and lithium ion battery Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 130
- 239000002243 precursor Substances 0.000 title claims abstract description 129
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000011164 primary particle Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 239000011163 secondary particle Substances 0.000 claims abstract description 20
- 230000003247 decreasing effect Effects 0.000 claims abstract description 15
- 238000005054 agglomeration Methods 0.000 claims abstract description 13
- 230000002776 aggregation Effects 0.000 claims abstract description 13
- 239000010405 anode material Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 55
- 229910052751 metal Inorganic materials 0.000 claims description 54
- 239000002184 metal Substances 0.000 claims description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 239000001301 oxygen Substances 0.000 claims description 51
- 229910052760 oxygen Inorganic materials 0.000 claims description 51
- 238000000975 co-precipitation Methods 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 44
- 239000007864 aqueous solution Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000008139 complexing agent Substances 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
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- 230000032683 aging Effects 0.000 claims description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 238000003483 aging Methods 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000009831 deintercalation Methods 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 4
- 238000009830 intercalation Methods 0.000 abstract description 4
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- 238000012360 testing method Methods 0.000 description 27
- 239000000047 product Substances 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
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- 239000011572 manganese Substances 0.000 description 10
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- 230000007423 decrease Effects 0.000 description 6
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- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 5
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- -1 and more preferably Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
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- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
-
- 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
- C01P2006/12—Surface area
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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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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the field of lithium ion batteries, and discloses a ternary precursor material, a ternary positive electrode material, a preparation method of the ternary positive electrode material and a lithium ion battery. The ternary precursor material is secondary particles formed by agglomeration of primary particles, and comprises a loose core and a compact outer layer formed on the surface of the loose core; the porosity of the loose core is greater than the porosity of the dense outer layer; the porosity of any adjacent dense outer layers is gradually decreased from the center of the particle along the radial direction, and the decreasing amounts are respectively and independently selected from 1-8%. The internal elasticity and external porosity has a gradient structure, is stable, is favorable for the intercalation and deintercalation of lithium ions, and is favorable for improving the electrochemical capacity of the anode material and the cycling stability of the material when being sintered with a lithium source, and the lithium ions are easy to diffuse to the center of secondary particles.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a ternary precursor material and a preparation method thereof, a ternary positive electrode material and a preparation method thereof, and application of the ternary precursor material and the ternary positive electrode material in lithium ion batteries.
Background
Lithium ion batteries are widely used as important power supply systems in the fields of 3C products such as computers, communication tools and electronic tools, electric vehicles such as EVs and PHEVs, and energy storage systems. The key factors of low cost and high power of the lithium ion battery are the positive electrode material, and the ternary material is one of the positive electrode materials of the lithium ion battery, and has the advantages of good safety, high specific capacity, low price and the like, so that the ternary material becomes one of the development directions of the future lithium battery industry.
The ternary positive electrode material is mostly formed by mixing and sintering a ternary precursor and a lithium source through high-temperature solid-phase reaction, and the ternary precursor material directly influences the electrochemical performance of the ternary positive electrode material. The most widely used precursor synthesis process method at present is a coprecipitation method, and the main advantage of the process is that the particle components are uniform, the size and structure can be regulated and controlled, and the operation is simple and the industrial production can be realized. The coprecipitation reaction is a complex process, and the conditions of the precipitant selection, reaction temperature, reactant concentration, pH value, feeding rate, stirring speed and the like have important influences on the structure, morphology and electrochemical performance of the material.
The ternary precursor particles prepared by the traditional preparation method are compact in interior, lithium ions are difficult to diffuse into the centers of secondary particles when being sintered with a lithium source, and a lithium deficiency state occurs, so that the electrochemical capacity and the cycle performance of the ternary positive electrode material are affected. By changing the internal structure of the ternary precursor, the electrochemical performance of the positive electrode material can be effectively improved.
CN112142123a discloses a precursor with a network structure, which comprises a loose inner core and a loose outer shell layer coated on the surface of the loose inner core, and the precursor has low tap density and compaction density, low particle strength, and the particles of the positive electrode material are easy to break when the pole piece is rolled, so that the structure of the positive electrode material is damaged, and the electrical property of the material is affected. In addition, the loose inner core and the loose outer shell of the precursor with the reticular structure are prepared by adopting a chemical corrosion precipitation method, and other impurity elements are introduced in the test process of the method to influence the performance of the product; and the conductivity and the oxidation-reduction potential need to be monitored, so that the regulation and control are not easy.
CN112047397a discloses a secondary particle precursor with more holes inside for primary particle polymerization, but the holes inside the material are concentrated in the core, lithium ions are difficult to diffuse to the center of the secondary particles, and the structure is unstable, and is easy to collapse in the process of lithium ion intercalation and deintercalation, so that the cycle performance of the positive electrode material is affected. In addition, the preparation method of the precursor also needs to introduce additives to realize the preparation of the internal porous structure, so that the product performance is affected.
Disclosure of Invention
The invention aims to solve the problems of poor electrochemical capacity and cycle stability of a ternary positive electrode material in the prior art, and provides a ternary precursor material, a ternary positive electrode material, a preparation method thereof and a lithium ion battery.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a ternary precursor material which is a secondary particle formed by agglomeration of primary particles, comprising a loose core and a dense outer layer formed on the surface of the loose core; the porosity of the loose core is greater than the porosity of the dense outer layer; the porosity of any adjacent dense outer layers is gradually decreased from the center of the particle along the radial direction, and the decreasing amounts are respectively and independently selected from 1-8%.
The second aspect of the present invention provides a method for preparing a ternary precursor material, the method comprising the steps of:
(1) In the presence of oxygen-containing gas, contacting the aqueous metal salt solution, the aqueous precipitant solution and the aqueous complexing agent solution sequentially for at least three tandem coprecipitation stages, wherein the oxygen content and the reaction pH value of the subsequent coprecipitation stage are smaller than those of the previous coprecipitation stage, and the stirring rotation speed and the liquid inlet amount of the aqueous metal salt solution of the subsequent coprecipitation stage are larger than those of the previous coprecipitation stage, so as to obtain slurry; wherein the aqueous metal salt solution contains Ni salt, co salt, mn salt and optional M salt;
(2) And (3) ageing, washing and drying the slurry in sequence to obtain the ternary precursor material.
In a third aspect, the present invention provides a ternary precursor material produced by the production method of the second aspect.
According to a fourth aspect of the invention, there is provided a ternary positive electrode material prepared by sintering a ternary precursor material according to the first or third aspect.
A fifth aspect of the present invention provides a method for preparing the ternary cathode material according to the fourth aspect, the method comprising the steps of:
s1, mixing a ternary precursor material with a lithium source to obtain a mixture;
s2, in an oxygen-containing atmosphere, sintering, crushing and screening the mixture in sequence to obtain the ternary anode material;
wherein the ternary precursor material is the ternary precursor material of the first aspect or the third aspect.
A sixth aspect of the invention provides a lithium ion battery comprising the ternary cathode material of the fourth aspect.
Through the technical scheme, the invention has the following advantages:
1. the ternary precursor material provided by the invention is a secondary particle formed by agglomeration of primary particles, and comprises a loose core and a compact outer layer formed on the surface of the loose core; the porosity of the loose core is greater than the porosity of the dense outer layer; the porosity of any adjacent dense outer layers is gradually decreased from the center of the particle along the radial direction, and the decreasing amounts are respectively and independently selected from 1-8%. The internal elasticity and external porosity have a gradient structure, are stable, are favorable for the intercalation and deintercalation of lithium ions, and are favorable for improving the electrochemical capacity of the anode material when being sintered with a lithium source, and the lithium ions are easily diffused to the center of secondary particles.
2. The ternary positive electrode material provided by the invention is beneficial to the intercalation and deintercalation of lithium ions, improves the rate performance and low-temperature performance of a lithium ion battery, effectively buffers the volume expansion caused in the charge and discharge process, avoids structural collapse, and improves the cycling stability of the material.
3. The method has simple process and easy popularization and application, and can be widely applied to the industrial production of nickel cobalt manganese hydroxide.
Drawings
FIG. 1 is a CP graph of a ternary precursor material prepared in example 1;
fig. 2 is a CP diagram of the ternary precursor material prepared in comparative example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a ternary precursor material, which is a secondary particle formed by agglomeration of primary particles, and comprises a loose core and a compact outer layer formed on the surface of the loose core; the porosity of the loose core is greater than the porosity of the dense outer layer; the porosity of any adjacent dense outer layers is gradually decreased from the center of the particle along the radial direction, and the decreasing amounts are respectively and independently selected from 1-8%.
The internal and external porosity is stable in structure with specific gradual decrease gradient change, effectively buffers volume expansion caused in the charge and discharge process, avoids structural collapse, improves the circulation stability of materials, and in addition, the internal and external porosity is loose and gradually changed to a compact structure, thereby being beneficial to the insertion and extraction of lithium ions, leading the lithium ions to be easily diffused to the center of secondary particles when the lithium source is sintered, and being beneficial to improving the electrochemical capacity of the anode material.
According to some embodiments of the invention, the porosity of the loose core is greater than the porosity of the dense outer layer; preferably, the difference between the porosity of the loose core and the porosity of the adjacent dense outer layer is 1-8%, preferably 1-5%.
According to some embodiments of the invention, the porosity of any adjacent dense outer layer decreases in radial order from the center of the particle, and the decreasing amounts are each independently selected from 1-8%. Preferably, the porosity of any adjacent said dense outer layer decreases in sequence radially from the centre of the particle and the amount of decrease is each independently selected from 1-5%. In the present invention, the decreasing amount refers to the difference between the porosities of the adjacent dense outer layers.
According to some embodiments of the invention, preferably, the diameter of the loose core and the thickness of any of the dense outer layers are each independently 18-40%, preferably 18-35%, of the diameter of the ternary precursor material.
According to some embodiments of the invention, preferably, the difference in porosity drop is 1-8% as the particle size of the ternary precursor material increases to 18-40% of the overall particle size of the material.
According to some embodiments of the invention, preferably the porosity of the loose core is 8-20%, preferably 9-17%.
According to some embodiments of the invention, the dense outer layer is not less than two layers; preferably, the dense outer layer is 2-4 layers, preferably 2-3 layers.
According to some embodiments of the invention, preferably, the loose core has a honeycomb-like structure and the dense outer layer has a radial structure.
In the invention, the porosity of the loose core and any of the dense outer layers is measured by a porosity statistical software.
According to some embodiments of the invention, preferably, the ternary precursor material has a spherical or spheroid-like morphology. In the invention, the morphology of the ternary precursor material is characterized by adopting a Scanning Electron Microscope (SEM).
According to some embodiments of the present invention, the ternary precursor material is a secondary particle formed by agglomeration of primary particles, the ternary precursor material includes a loose core and a dense outer layer formed on a surface of the loose core, the loose core has a honeycomb-like structure, and the dense outer layer has a radial structure; the compact outer layer is not less than two layers. The internal structure of the ternary precursor material is obtained by characterization through ion beam milling (CP) and scanning electron microscopy.
According to some embodiments of the invention, preferably, the primary particles comprise fibrous sheet-like primary particles and lath-like primary particles, the fibrous sheet-like primary particles being staggered to form the honeycomb-like structure, the lath-like primary particles forming the radial structure.
According to some embodiments of the invention, preferably, the fibrous sheet-like primary particles have a thickness of 10-80nm, preferably 20-60nm; and/or the thickness of the lath-shaped primary particles is 0.1 to 0.5 μm, preferably 0.2 to 0.4 μm.
In the invention, the thickness of the primary particles, the diameter of the loose core, the thickness of any dense outer layer and the diameter of the ternary precursor material are measured by ion beam milling (CP) and high power scanning electron microscopy.
According to some embodiments of the invention, preferably, the bulk density of the ternary precursor material is from 1 to 2g/cm 3 Preferably 1.3-1.8g/cm 3 . The bulk density of the ternary precursor material is measured by a bulk densitometer.
According to some embodiments of the invention, preferably, the ternary precursor material has a tap density of 1.4-2.5g/cm 3 Preferably 1.5-2.2g/cm 3 . The tap density of the ternary precursor material is measured by a tap density meter.
According to some embodiments of the invention, preferably, the ternary precursor material has a BET specific surface area of from 2 to 20m 2 Preferably 8-16m 2 And/g. The BET specific surface area of the ternary precursor material was measured by a Tri-star 3020 specific surface meter.
According to some embodiments of the invention, preferably, the ternary precursor material has a median particle diameter D 50 5-18 μm, preferably 8-15 μm. Median particle diameter D of the ternary precursor material 50 Measured by a laser particle sizer.
According to some embodiments of the invention, preferably, the ternary precursor material has a composition represented by formula I:
Ni x Co y Mn z M w (OH) 2 a formula I;
wherein x is more than or equal to 0.3 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, and w=1-x-y-z; m is selected from at least one of La, cr, mo, ca, fe, hf, ti, zn, Y, zr, si, W, nb, sm, V, mg, B, Y and Al.
Preferably, in formula I, 0.5.ltoreq.x.ltoreq.0.9, 0.1.ltoreq.y.ltoreq. 0.2,0.1.ltoreq.z.ltoreq.0.3, w=1-x-y-z.
Preferably, M is selected from at least one of Al, ti, nb, V, mg, B and Y.
The second aspect of the present invention provides a method for preparing a ternary precursor material, the method comprising the steps of:
(1) In the presence of oxygen-containing gas, contacting the aqueous metal salt solution, the aqueous precipitant solution and the aqueous complexing agent solution sequentially for at least three tandem coprecipitation stages, wherein the oxygen content and the reaction pH value of the subsequent coprecipitation stage are smaller than those of the previous coprecipitation stage, and the stirring rotation speed and the liquid inlet amount of the aqueous metal salt solution of the subsequent coprecipitation stage are larger than those of the previous coprecipitation stage, so as to obtain slurry; wherein the aqueous metal salt solution contains Ni salt, co salt, mn salt and optional M salt;
(2) And (3) ageing, washing and drying the slurry in sequence to obtain the ternary precursor material.
The inventors of the present invention found during the course of the study that the morphology and the stacking manner of the primary fibers influences the porosity of the ternary precursor material during the growth of the precursor material. The transition metal element in the precursor material is oxidized, so that the surface activity is reduced, and the primary fiber is finer and thinner; the reaction pH value influences the dynamic balance of chemical reaction, the reduction of the reaction pH value is beneficial to the growth of crystals, and the primary fiber is thicker and bigger; the stirring speed is low, primary fibers are piled up in a disordered state, and the pores are increased; the liquid inlet amount of the metal salt is increased, the reaction time is shortened, and the formation of pores in the particles is facilitated.
The preparation method provided by the invention comprises the steps of sequentially carrying out at least three tandem coprecipitation stages by contacting a metal salt aqueous solution, a precipitator aqueous solution and a complexing agent aqueous solution in the presence of oxygen-containing gas, controlling the oxygen content and the reaction pH value of the subsequent coprecipitation stages to be smaller than those of the previous coprecipitation stages, wherein the stirring rotation speed and the liquid inlet amount of the metal salt aqueous solution of the subsequent coprecipitation stages are larger than those of the previous coprecipitation stages so as to realize the regulation and control of the porosity, and the prepared ternary precursor material is secondary particles formed by agglomeration of primary particles, and comprises a loose core and a compact outer layer formed on the surface of the loose core; the porosity of the loose core is greater than the porosity of the dense outer layer; the porosity of any adjacent dense outer layers is gradually decreased from the center of the particle along the radial direction, and the decreasing amounts are respectively and independently selected from 1-8%. The ternary positive electrode material prepared from the ternary precursor material has better first charge-discharge capacity and capacity retention rate.
According to some embodiments of the invention, the formation of an internally loose externally dense structure with gradually decreasing porosity is achieved by controlling the oxygen content of the oxygen-containing gas, the reaction pH, the stirring speed, the amount of feed of the aqueous metal salt solution during the co-precipitation reaction. Preferably, as the granularity of the ternary precursor material grows, the reaction oxygen content and the reaction pH value are reduced, and the stirring speed and the liquid inlet amount of the metal salt aqueous solution are increased, so that the porosity of the material can be reduced.
According to some embodiments of the present invention, the aqueous metal salt solution, the aqueous precipitant solution and the aqueous complexing agent solution are commercially available, and may be formulated according to a conventional method in the art, without particular limitation. Preferably, before performing step (1), the method further comprises contacting the Ni salt, mn salt, water with an optional M salt to obtain an aqueous metal salt solution; preparing complexing agent into complexing agent aqueous solution; a step of preparing a precipitant into an aqueous precipitant solution.
According to some embodiments of the present invention, the metal salt may be a water-soluble salt containing a metal element, which is conventional in the art, and is not particularly limited, and may achieve the object of the present invention to some extent. The metal element comprises Ni, co, mn and optionally M, M being selected from at least one of La, cr, mo, ca, fe, hf, ti, zn, Y, zr, si, W, nb, sm, V, mg, B, Y and Al, preferably from at least one of Al, ti, nb, V, mg, B and Y. Preferably, the metal salt is selected from one or more of sulfate, nitrate and chloride salts containing a metal element.
According to some embodiments of the present invention, the precipitant may be a precipitant conventionally used in the art for preparing a precursor material, and is not particularly limited in this regard, and it can achieve the object of the present invention to some extent. Preferably, the precipitant is selected from one or more of NaOH, KOH and LiOH.
According to some embodiments of the present invention, the complexing agent may be a complexing agent conventionally used in the art for preparing precursor materials, which is not particularly limited, and which can achieve the object of the present invention to some extent. Preferably, the complexing agent is selected from one or more of ammonia, ammonium bicarbonate, ammonium carbonate, citric acid and ethylenediamine tetraacetic acid.
According to some embodiments of the invention, preferably, the concentration of the aqueous metal salt solution is 1-3mol/L; and/or the concentration of the aqueous solution of the precipitant is 3-10mol/L; and/or the concentration of the complexing agent aqueous solution is 4-13.3mol/L.
According to some embodiments of the invention, preferably the Ni salt, co salt, mn salt and optionally M salt are used in amounts such that n (Ni): n (Co): n (Mn): n (M) =x: y: and z: (1-x-y-z). Wherein, the types and the amounts of M and the values of x, y and z can be defined and selected by referring to the above description, and are not repeated here.
According to some embodiments of the invention, preferably the oxygen content of the oxygen containing gas is in the range of 1 to 30vol%, preferably 2 to 23vol%. Preferably, the oxygen-containing gas is a mixed gas of oxygen and an inert gas.
According to some embodiments of the present invention, preferably, the oxygen content in the oxygen-containing gas may be controlled by the flow rate of an inert gas, and more preferably, the inert gas is nitrogen and/or argon.
According to some embodiments of the invention, preferably, the conditions of any of the coprecipitation stages each independently comprise: the reaction temperature is 40-70 ℃, the reaction pH value is 10-12, the stirring speed is 100-800rpm, and the liquid inlet amount of the metal salt aqueous solution is 50-500mL/L; the ammonia content in the reaction system is controlled to be 1-6g/L, wherein the ammonia content refers to the concentration of ammonia radical ions in the reaction system, and the ammonia radical ions are measured by a titration method.
According to some embodiments of the invention, preferably, the coprecipitation stage is 3-5 stages.
According to some embodiments of the invention, preferably, in any two adjacent stages, the decrease in oxygen content in the subsequent coprecipitation stage is 3-8%, the decrease in reaction pH is 0.2-0.6, the increase in stirring speed is 50-200rpm, and the increase in the amount of feed aqueous solution of metal salt is 50-200mL/L, as compared to the preceding coprecipitation stage.
According to some embodiments of the invention, preferably, the coprecipitation stage is three stages, wherein the oxygen content in the first stage is 15-30vol%, the reaction pH is 11-12, the stirring speed is 100-400rpm, and the liquid inlet amount of the metal salt aqueous solution is 50-100mL/L; and/or the number of the groups of groups,
the oxygen content in the second stage is 10-18vol%, the reaction pH value is 10.8-11.8, the stirring speed is 200-500rpm, and the liquid inlet amount of the metal salt aqueous solution is 100-200mL/L; and/or the number of the groups of groups,
the oxygen content in the third stage is 4-10vol%, the reaction pH value is 10.4-11.4, the stirring speed is 300-600rpm, and the liquid inlet amount of the metal salt aqueous solution is 150-400mL/L;
according to some embodiments of the invention, more preferably, the coprecipitation stage further comprises a fourth stage, wherein the oxygen content of the fourth stage is 1-5vol%, the reaction pH value is 10-11, the stirring rotation speed is 400-700rpm, and the liquid inlet amount of the metal salt aqueous solution is 200-600mL/L.
According to some embodiments of the invention, preferably, the product obtained in the first stage has a median particle diameter D 50 1-4 μm; and/or the product obtained in the second stage has a median diameter D 50 4-7 μm; and/or the product obtained in the third stage has a median diameter D 50 7-11 μm; and/or, the fourthMedian particle diameter D of the product obtained in the stage 50 9-15 μm.
According to some embodiments of the invention, preferably, in step (2), the aging conditions include: the aging temperature is 40-70 ℃ and the aging time is 12-24h.
According to some embodiments of the present invention, the aged product is preferably washed with an alkaline solution and/or water, more preferably the aged product is alternately washed with an alkaline solution and water.
According to some embodiments of the invention, preferably, the method of preparation further comprises drying the washed product. The drying conditions include: the temperature is 100-130 ℃ and the time is 2-6h.
According to a particularly preferred embodiment of the invention, the preparation method comprises:
a. according to n (Ni): n (Co): n (Mn): n (M) =x: y: and z: the molar ratio of (1-x-y-z) is that Ni salt, co salt, mn salt and optional M salt are weighed and mixed with water to prepare metal salt aqueous solution; preparing complexing agent into complexing agent aqueous solution; preparing a precipitant into a precipitant water solution;
b. in the presence of oxygen-containing gas with oxygen content of 15-30vol%, contacting metal salt aqueous solution, precipitant aqueous solution and complexing agent aqueous solution to make first-stage coprecipitation reaction, in which the reaction temperature is 40-70 deg.C, ammonia content in the reaction system is controlled to be 1-6g/L, reaction pH value is 11-12, stirring speed is 100-400rpm, liquid inlet quantity of metal salt aqueous solution is 50-100mL/L, and using laser graininess meter to make test on slurry grain size until the median grain size D of obtained product 50 1-4 μm;
c. adjusting the oxygen content to 10-18vol%, the reaction pH value to 10.8-11.8, the stirring rotation speed to 200-500rpm, the liquid inlet amount of the metal salt aqueous solution to 100-200mL/L, performing a second-stage coprecipitation reaction, and testing the granularity of the slurry by a laser granularity meter until the median particle diameter D of the obtained product 50 4-7 μm;
d. adjusting the oxygen content to 4-10vol%, the reaction pH value to 10.4-11.4, stirring at 300-600rpm, and the aqueous solution of metal saltThe liquid inlet amount is 150-400mL/L, the third stage coprecipitation reaction is carried out, the size of the slurry is tested by a laser particle analyzer until the median particle diameter D of the obtained product 50 7-11 μm;
e. adjusting the oxygen content to 1-5vol%, the reaction pH value to 10-11, stirring at 400-700rpm, the liquid inlet amount of the metal salt aqueous solution to 200-600mL/L, performing a fourth-stage coprecipitation reaction, and testing the granularity of the slurry by using a laser granularity meter until the median particle diameter D of the obtained product 50 9-15 μm; wherein in any two adjacent stages, compared with the prior coprecipitation stage, the oxygen content in the subsequent coprecipitation stage is reduced by 3-8%, the reaction pH value is reduced by 0.2-0.6, the stirring rotation speed is increased by 50-200rpm, and the liquid inlet amount of the metal salt water solution is increased by 50-200mL/L;
f. And e, ageing, washing and drying the slurry obtained in the step e in sequence to obtain the ternary precursor material.
In the present invention, the respective amounts of the complexing agent aqueous solution and the precipitant aqueous solution are not particularly required, as long as the pH values and the ammonia contents in steps b to e are such that they satisfy the requirements of the present invention.
In a third aspect, the present invention provides a ternary precursor material produced by the production method of the second aspect.
According to some embodiments of the present invention, the ternary precursor material is the same as or similar to the ternary precursor material provided in the first aspect of the present invention, and will not be described herein.
According to a fourth aspect of the invention, there is provided a ternary positive electrode material prepared by sintering a ternary precursor material according to the first or third aspect.
According to some embodiments of the invention, preferably, the ternary positive electrode material has a composition represented by formula II:
Li c Ni x Co y Mn z M w O 2 a formula II;
wherein c is more than or equal to 0.9 and less than or equal to 1.2,0.3, x is more than or equal to 0.9, y is more than 0 and less than or equal to 0.4, z is more than 0 and less than or equal to 0.4, and w=1-x-y-z; m is selected from at least one of La, cr, mo, ca, fe, hf, ti, zn, Y, zr, si, W, nb, sm, V, mg, B, Y and Al;
according to some embodiments of the present invention, preferably, 1.ltoreq.c.ltoreq. 1.1,0.5.ltoreq.x.ltoreq.0.9, 0.1.ltoreq.y.ltoreq. 0.2,0.1.ltoreq.z.ltoreq.0.3, w=1-x-y-z; and/or, M is selected from at least one of Al, ti, nb, V, mg, B and Y.
According to some embodiments of the present invention, preferably, the ternary positive electrode material has a tap density of 2 to 3g/cm 3 A specific surface area of 0.2-2m 2 /g。
A fifth aspect of the present invention provides a method for preparing the ternary cathode material according to the fourth aspect, the method comprising the steps of:
s1, mixing a ternary precursor material with a lithium source to obtain a mixture;
s2, in an oxygen-containing atmosphere, sintering, crushing and screening the mixture in sequence to obtain the ternary anode material;
wherein the ternary precursor material is the ternary precursor material of the first aspect or the third aspect.
According to some embodiments of the invention, it is preferred that the ternary precursor material and the lithium source are used in amounts such that 0.9.ltoreq.n (Li) ]/[ n (Ni) +n (Co) +n (Mn) +n (M) ]. Ltoreq.1.2, preferably 1.ltoreq.n (Li) ]/[ n (Ni) +n (Co) +n (Mn) +n (M) ]. Ltoreq.1.1.
According to some embodiments of the present invention, the lithium source may be a lithium source conventionally used in the art for preparing a positive electrode material, and is not particularly limited in that it can achieve the object of the present invention to some extent. Preferably, the lithium source is lithium carbonate and/or lithium hydroxide.
According to some embodiments of the invention, preferably, the sintering conditions include: the sintering temperature is 600-1000 ℃ and 600-800 ℃; and/or the sintering time is 6 to 25 hours, preferably 6 to 15 hours.
A sixth aspect of the invention provides a lithium ion battery comprising the ternary cathode material of the fourth aspect.
The present invention will be described in detail by examples.
The following examples and comparative examples:
the metal salt, the precipitant and the complexing agent are all commercial products.
The oxygen content refers to the oxygen content.
The CP image was obtained by ion beam profile milling and scanning electron microscope testing.
SEM electron micrograph was obtained by scanning electron microscope test of model S-4800 of Hitachi CHI, japan.
The thickness of primary particles in the ternary precursor material, the diameter of the loose core, the thickness of each compact outer layer and the diameter of the ternary precursor material are obtained through scanning electron microscope testing.
Bulk density was measured by a bulk densitometer.
Tap density was obtained by tap densitometer testing.
BET testing was obtained by a Tri-star 3020 specific surface area meter test.
Median particle diameter D 50 And the test is carried out by a laser particle sizer.
2025 assembly of button cell:
first, a positive electrode active material for a nonaqueous electrolyte secondary battery, acetylene black and polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 95:2.5:2.5, coated on an aluminum foil, and subjected to drying treatment, and a positive electrode sheet having a diameter of 12mm and a thickness of 120 μm was press-molded with a pressure of 100MPa, and then the positive electrode sheet was put into a vacuum oven-dried at 120℃for 12 hours.
The anode uses a Li metal sheet with a diameter of 17mm and a thickness of 1 mm; the separator uses a polyethylene porous film with a thickness of 25 μm; the electrolyte uses 1mol/L LiPF 6 Equal amounts of the mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC).
And assembling the positive electrode plate, the diaphragm, the negative electrode plate and the electrolyte into a 2025 button cell in an Ar gas glove box with the water content and the oxygen content of less than 5ppm, and taking the cell at the moment as an unactivated cell.
After the button cell is manufactured, the button cell is placed for 24 hours, after the open circuit voltage is stable, the button cell is charged to the cut-off voltage of 4.6V by adopting the current density of 20mA/g, and is charged to the cut-off current of 0.024mA at the constant voltage of 4.6V. Then the same current density was discharged to a cut-off voltage of 2.0V, and the above was repeated once more, with the cell at this time being taken as an activated cell.
The performance of the button cell was evaluated as follows:
and (3) multiplying power performance test: the battery capacity of 0.2C and 1C is tested at 25 ℃ by using the activated battery in a voltage range of 2.0-4.5V, and the specific capacity obtained under different multiplying powers and the numerical value of 1C/0.2C are used for representing the multiplying power performance, wherein the larger the numerical value is, the better the multiplying power performance is represented.
And (3) testing the cycle performance: the temperature is 25 ℃, the charge and discharge are carried out at 1C in a voltage interval of 2.0-4.5V, and the retention rate is tested after 80 weeks of circulation.
Low temperature performance test: the battery capacity of 1C was tested at-20deg.C over a voltage range of 2.0-4.5V.
Example 1
(1) Weighing NiSO according to the mole ratio of Ni to Co to Mn=8 to 1 4 ·6H 2 O、CoSO 4 ·7H 2 O、MnSO 4 ·H 2 O is dissolved in deionized water to prepare 2mol/L metal salt aqueous solution; simultaneously preparing 4mol/L sodium hydroxide solution as a precipitator and 10mol/L ammonia water as a complexing agent;
(2) Adding deionized water into a 5L reaction kettle, wherein the temperature of the reaction kettle is controlled at 60 ℃, the stirring rotating speed is set to 300r/min, then adding ammonia water and sodium hydroxide solution to regulate the base solution, regulating the pH value in the reaction kettle to 11.7, and introducing mixed gas with the oxygen content of 20.8vol% and the nitrogen content of 79.2 vol%. Adding the prepared metal salt aqueous solution, sodium hydroxide aqueous solution and ammonia water into a reaction kettle through a metering pump, wherein the liquid inlet amount of the metal salt aqueous solution is set to be 50mL/h, the liquid inlet amount of the sodium hydroxide aqueous solution and the liquid inlet amount of the ammonia water are automatically regulated according to the pH value and the ammonia concentration, the ammonia content is maintained to be 3g/L, the pH value is maintained to be 11.7, and the first-stage coprecipitation reaction is carried out until the median particle diameter D of the obtained product is obtained 50 Is 3.58 μm. During the reaction, discharged through a physical settling tankAnd (3) supernatant.
(3) Adjusting the oxygen content of the mixed gas to be 14.6vol%; gradually adjusting pH value to 11.4, stirring at 400r/min, adjusting the liquid inlet amount of the metal salt aqueous solution to 100mL/h, and performing the second-stage coprecipitation reaction until the median particle diameter D of the obtained product 50 6.84 μm.
(4) Adjusting the oxygen content of the mixed gas to 8.3vol%; gradually adjusting pH value to 11.1, stirring at 500r/min, adjusting the liquid inlet amount of the metal salt aqueous solution to 200mL/h, and performing the third-stage coprecipitation reaction until the median particle diameter D of the obtained product 50 10.23 μm.
(5) Adjusting the oxygen content of the mixed gas to be 2.5vol%; gradually adjusting pH value to 10.8, stirring at 600r/min, adjusting the liquid inlet amount of the metal salt aqueous solution to 400mL/h, and performing the fourth-stage coprecipitation reaction until the median particle diameter D of the obtained product 50 14.32 μm.
(6) And (3) ageing the slurry obtained in the step (5) (ageing temperature is 60 ℃ and ageing time is 12 hours), after ageing is finished, alternately washing with an alkaline solution at 75 ℃ and pure water, and then drying a filter cake in a blast oven at 120 ℃ for 3 hours to obtain a powdery ternary precursor material A1, wherein the porosity statistics are shown in table 2, and the chemical formula composition is shown in table 3.
Fig. 1 is a CP diagram of the ternary precursor material, where it can be seen that the ternary precursor material is a secondary particle formed by agglomeration of primary particles, and includes a loose core and three dense outer layers formed on the surface of the loose core, where the loose core has a honeycomb-like structure formed by interlacing fiber sheet-like primary particles, and the dense outer layers have a radial structure formed by lath-like primary particles. The thickness of the primary particles, the diameter of the loose core, the thickness of each dense outer layer, and the diameter of the ternary precursor material in the ternary precursor material are shown in table 4.
Bulk density, tap density, BET specific surface area and median particle diameter D of the ternary precursor material 50 The test was performed and the results are shown in table 5.
Example 2
The procedure of example 1 was followed, except that the procedure was as in example 1, to obtain a powdery ternary precursor material A2 having a porosity statistical value shown in Table 2 and a chemical formula composition shown in Table 3.
As shown by ion beam profile grinding and scanning electron microscope testing, the ternary precursor material is secondary particles formed by agglomeration of primary particles, and comprises a loose core and three dense outer layers formed on the surface of the loose core, wherein the loose core is provided with a honeycomb-like structure formed by interlacing fiber sheet-shaped primary particles, and the dense outer layers are provided with radial structures formed by lath-shaped primary particles. The thickness of the primary particles, the diameter of the loose core, the thickness of each dense outer layer, and the diameter of the ternary precursor material in the ternary precursor material are shown in table 4.
Bulk density, tap density, BET specific surface area and median particle diameter D of the ternary precursor material 50 The test was performed and the results are shown in table 5.
Example 3
The procedure of example 1 was followed, except that the procedure was as in example 1, to obtain a powdery ternary precursor material A3, the porosity statistics of which are shown in Table 2, and the chemical formula composition of which is shown in Table 3.
As shown by ion beam profile grinding and scanning electron microscope testing, the ternary precursor material is secondary particles formed by agglomeration of primary particles, and comprises a loose core and three dense outer layers formed on the surface of the loose core, wherein the loose core is provided with a honeycomb-like structure formed by interlacing fiber sheet-shaped primary particles, and the dense outer layers are provided with radial structures formed by lath-shaped primary particles. The thickness of the primary particles, the diameter of the loose core, the thickness of each dense outer layer, and the diameter of the ternary precursor material in the ternary precursor material are shown in table 4.
Bulk density, tap density, BET specific surface area and median particle diameter D of the ternary precursor material 50 The test was performed and the results are shown in table 5.
Example 4
The procedure of example 1 was followed, except that the procedure was as in example 1, to obtain a powdery ternary precursor material A4, the porosity statistics of which are shown in Table 2, and the chemical formula composition of which is shown in Table 3.
As shown by ion beam profile grinding and scanning electron microscope testing, the ternary precursor material is secondary particles formed by agglomeration of primary particles, and comprises a loose core and three dense outer layers formed on the surface of the loose core, wherein the loose core is provided with a honeycomb-like structure formed by interlacing fiber sheet-shaped primary particles, and the dense outer layers are provided with radial structures formed by lath-shaped primary particles. The thickness of the primary particles, the diameter of the loose core, the thickness of each dense outer layer, and the diameter of the ternary precursor material in the ternary precursor material are shown in table 4.
Bulk density, tap density, BET specific surface area and median particle diameter D of the ternary precursor material 50 The test was performed and the results are shown in table 5.
Example 5
The procedure of example 1 is followed, except that Table 1 shows that the aqueous metal salt solution further contains titanyl sulfate, ni: co: mn: the molar ratio of Ti was 7.9:1:1:0.1, and the rest was the same as in example 1, to obtain a powdery ternary precursor material A5, the porosity statistics of which are shown in Table 2, and the chemical formula composition of which is shown in Table 3.
As shown by ion beam profile grinding and scanning electron microscope testing, the ternary precursor material is secondary particles formed by agglomeration of primary particles, and comprises a loose core and three dense outer layers formed on the surface of the loose core, wherein the loose core is provided with a honeycomb-like structure formed by interlacing fiber sheet-shaped primary particles, and the dense outer layers are provided with radial structures formed by lath-shaped primary particles. The thickness of the primary particles, the diameter of the loose core, the thickness of each dense outer layer, and the diameter of the ternary precursor material in the ternary precursor material are shown in table 4.
Bulk density, tap density, BET specific surface area and median particle diameter D of the ternary precursor material 50 The test was performed and the results are shown in table 5.
Example 6
The procedure of example 1 was followed, except that the procedure was as in example 1, to obtain a powdery ternary precursor material A6, the porosity statistics of which are shown in Table 2, and the chemical formula composition of which is shown in Table 3.
As shown by ion beam profile grinding and scanning electron microscope testing, the ternary precursor material is secondary particles formed by agglomeration of primary particles, and comprises a loose core and two dense outer layers formed on the surface of the loose core, wherein the loose core is provided with a honeycomb-like structure formed by interlacing fiber sheet-shaped primary particles, and the dense outer layers are provided with radial structures formed by lath-shaped primary particles. The thickness of the primary particles, the diameter of the loose core, the thickness of the dense outer layer, and the diameter of the ternary precursor material in the ternary precursor material are shown in table 4.
Bulk density, tap density, BET specific surface area and median particle diameter D of the ternary precursor material 50 The test was performed and the results are shown in table 5.
Comparative example 1
The procedure of example 1 was followed, except that the procedure was as in example 1, to obtain a powdery ternary precursor material D1, the porosity statistics of which are shown in Table 2, and the chemical formula composition of which is shown in Table 3.
Fig. 2 is a CP diagram of the ternary precursor material, where it can be seen that the ternary precursor material is a secondary particle formed by agglomerating primary particles, where the primary particles are in a broad and thick plate shape, and the surface is dense and has no holes. In the ternary precursor material, the thickness of the primary particles and the diameter of the ternary precursor material are shown in table 4.
Bulk density, tap density, BET specific surface area and median particle diameter D of the ternary precursor material 50 The test was performed and the results are shown in table 5.
Comparative example 2
The procedure of example 1 was followed, except that the procedure was as in example 1, to obtain a powdery ternary precursor material D2 having a porosity statistical value shown in Table 2 and a chemical formula composition shown in Table 3.
As shown by ion beam profile grinding and scanning electron microscope testing, the porosity of the ternary precursor material has no gradient change, and therefore, only if the oxygen content and the reaction pH value in the later coprecipitation stage are controlled to be smaller than those in the former coprecipitation stage, the stirring rotation speed and the liquid inlet amount of the metal salt water solution in the later coprecipitation stage are larger than those in the former coprecipitation stage, and the structure with gradient change of the internal elasticity and the external elasticity can be realized. In the ternary precursor material, the thickness of the primary particles and the diameter of the ternary precursor material are shown in table 4.
Bulk density, tap density, BET specific surface area and median particle diameter D of the ternary precursor material 50 The test was performed and the results are shown in table 5.
TABLE 1
TABLE 2
TABLE 3 Table 3
| Composition of the composition | |
| Example 1 | Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 |
| Example 2 | Ni 0.6 Co 0.2 Mn 0.2 (OH) 2 |
| Example 3 | Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 |
| Example 4 | Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 |
| Example 5 | Ni 0.79 Co 0.1 Mn 0.1 Ti 0.01 (OH) 2 |
| Example 6 | Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 |
| Comparative example 1 | Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 |
| Comparative example 2 | Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 |
TABLE 4 Table 4
Note that: * The whole is ternary precursor material
TABLE 5
| Numbering device | Bulk density of the product | Tap density | BET specific surface area | Median particle diameter D 50 |
| Unit (B) | g/cm 3 | g/cm 3 | m 2 /g | μm |
| Example 1 | 1.68 | 2.02 | 10.88 | 14.32 |
| Example 2 | 1.56 | 1.91 | 11.58 | 12.80 |
| Example 3 | 1.46 | 1.79 | 12.96 | 9.21 |
| Example 4 | 1.55 | 1.86 | 13.39 | 13.8 |
| Example 5 | 1.67 | 2.01 | 10.51 | 14.22 |
| Example 6 | 1.48 | 1.76 | 16.68 | 14.02 |
| Comparative example 1 | 1.85 | 2.20 | 5.12 | 14.15 |
| Comparative example 2 | 1.79 | 2.09 | 8.77 | 13.67 |
Application examples and comparative application examples
The ternary precursor materials prepared in examples and comparative examples are fully mixed with a lithium source according to the molar ratio of n (Li)/[ n (Ni) +n (Co) +n (Mn) +n (M) ] respectively, sintered in an oxygen atmosphere, naturally cooled, crushed and sieved to obtain the spherical high-nickel ternary positive electrode material, wherein the types of the ternary precursor materials, the types of the lithium source, the proportions of the ternary precursor materials and the lithium source and the sintering conditions are shown in Table 6, and the compositions of the prepared ternary positive electrode material are shown in Table 7. The tap density and BET specific surface area of the ternary cathode material were tested and the results are shown in table 7.
After the ternary cathode material was prepared into 2025 button cell, the discharge specific capacity, rate capability and cycle performance were tested in the voltage range of 2.0-4.5V, and the results are shown in Table 8.
TABLE 6
| Precursor body | Lithium source | n(Li)/[n(Ni)+n(Co)+n(Mn)+n(M)] | Sintering conditions | |
| Application example 1 | A1 | Lithium hydroxide | 1.04:1 | 750℃/12h |
| Application example 2 | A2 | Lithium carbonate | 1.03:1 | 680℃/8h |
| Application example 3 | A3 | Lithium carbonate | 1.03:1 | 650℃/10h |
| Application example 4 | A4 | Lithium hydroxide | 1.04:1 | 750℃/12h |
| Application example 5 | A5 | Lithium hydroxide | 1.04:1 | 750℃/12h |
| Application example 6 | A6 | Lithium hydroxide | 1.04:1 | 750℃/12h |
| Comparative application example 1 | D1 | Lithium hydroxide | 1.04:1 | 750℃/12h |
| Comparative application example 2 | D3 | Lithium hydroxide | 1.04:1 | 750℃/12h |
TABLE 7
TABLE 8
| Test item | Specific discharge capacity of 0.2C | Specific discharge capacity of 1C | Capacity retention of 50 weeks | Specific discharge capacity of 1C |
| Unit (B) | 25℃，mAh/g | 25℃，mAh/g | ％ | -20℃，mAh/g |
| Application example 1 | 207.9 | 192.3 | 96.1 | 159.61 |
| Application example 2 | 181.2 | 167.8 | 97.6 | 140.95 |
| Application example 3 | 173.4 | 162.5 | 98.8 | 138.12 |
| Application example 4 | 206.8 | 191.0 | 94.6 | 154.80 |
| Application example 5 | 207.0 | 191.9 | 97.0 | 159.20 |
| Application example 6 | 205.3 | 190.6 | 91.6 | 152.47 |
| Comparative application example 1 | 201.3 | 186.5 | 86.1 | 139.28 |
| Comparative application example 2 | 202.6 | 188.4 | 88.2 | 146.95 |
The result shows that the ternary positive electrode material prepared from the ternary precursor material with the gradient structure of internal elasticity and external porosity is applied to a lithium ion battery, has high initial charge-discharge specific capacity, high capacity retention rate and good cycle stability.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (18)
1. The ternary precursor material is characterized by being secondary particles formed by agglomeration of primary particles, and comprises a loose core and a compact outer layer formed on the surface of the loose core; the porosity of the loose core is greater than the porosity of the dense outer layer; the porosity of any adjacent dense outer layer is gradually decreased from the center of the particle along the radial direction, and the decreasing amounts are respectively and independently selected from 1-5%; the diameter of the loose core and the thickness of any of the dense outer layers are each independently 18-40% of the diameter of the ternary precursor material; the porosity of the loose core is 8-20%; the loose core has a honeycomb-like structure, and the compact outer layer has a radial structure; the difference between the porosity of the loose core and the porosity of the adjacent compact outer layer is 1-8%; the primary particles comprise fiber sheet-shaped primary particles and lath-shaped primary particles, the fiber sheet-shaped primary particles are staggered to form the honeycomb-like structure, and the lath-shaped primary particles form the radial structure; the thickness of the fiber sheet-shaped primary particles is 10-80 nm; the thickness of the lath-shaped primary particles is 0.1-0.5 mu m;
Wherein the ternary precursor material has a composition represented by formula I:
Ni x Co y Mn z M w (OH) 2 a formula I;
wherein x is more than or equal to 0.3 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.4, z is more than or equal to 0 and less than or equal to 0.4, and w=1-x-y-z; m is selected from at least one of La, cr, mo, ca, fe, hf, ti, zn, Y, zr, si, W, nb, sm, V, mg, B, Y and Al.
2. The ternary precursor material of claim 1, wherein the difference in porosity drop as the particle size of the ternary precursor material increases to 18-40% of the overall particle size of the material is 1-8%.
3. The ternary precursor material of claim 1, wherein the ternary precursor material has a bulk density of 1-2 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or tap density of 1.4-2.5 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the And/or BET specific surface area of 2-20 m 2 /g; and/or median particle diameter D 50 5-18 μm.
4. A method of preparing a ternary precursor material according to any one of claims 1 to 3, comprising the steps of:
(1) In the presence of oxygen-containing gas, contacting the aqueous metal salt solution, the aqueous precipitant solution and the aqueous complexing agent solution sequentially for at least four tandem coprecipitation stages, wherein the oxygen content and the reaction pH value of the subsequent coprecipitation stage are smaller than those of the previous coprecipitation stage, and the stirring rotation speed and the liquid inlet amount of the aqueous metal salt solution of the subsequent coprecipitation stage are larger than those of the previous coprecipitation stage, so as to obtain slurry; wherein the aqueous metal salt solution contains Ni salt, co salt and Mn salt; the concentration of the metal salt aqueous solution is 1-3 mol/L; the oxygen content in the oxygen-containing gas is 1-30vol%; the conditions of any of the co-precipitation stages each independently include: the pH value of the reaction is 10-12, the stirring rotation speed is 100-800 rpm, and the liquid inlet amount of the metal salt aqueous solution is 50-500 mL/L; in any two adjacent stages, compared with the previous coprecipitation stage, the oxygen content of the subsequent coprecipitation stage is reduced by 3-8%, the reaction pH value is reduced by 0.2-0.6, the stirring rotation speed is increased by 50-200 rpm, and the liquid inlet amount of the metal salt water solution is increased by 50-200 mL/L;
(2) And (3) ageing, washing and drying the slurry in sequence to obtain the ternary precursor material.
5. The process according to claim 4, wherein in the step (1), the aqueous metal salt solution further contains M salt.
6. The production process according to claim 5, wherein in the step (1), the concentration of the aqueous precipitant solution is 3 to 10 mol/L; and/or the concentration of the complexing agent aqueous solution is 4-13.3 mol/L;
and/or, the molar ratio of Ni, co, mn, M in the aqueous metal salt solution is x: y: and z: (1-x-y-z), wherein the x, y, z ranges from: x is more than or equal to 0.3 and less than or equal to 0.9, y is more than or equal to 0 and less than or equal to 0.4, and z is more than or equal to 0 and less than or equal to 0.4.
7. The production process according to claim 4, wherein in the step (1), the oxygen content in the oxygen-containing gas is 2 to 23vol%.
8. The production method according to claim 4, wherein in the step (1), the oxygen-containing gas is a mixed gas of oxygen and an inert gas.
9. The process of claim 4, wherein in step (1), the conditions of any of the coprecipitation stages each independently further comprise: the reaction temperature is 40-70 ℃; the ammonia content in the reaction system is controlled to be 1-6g/L.
10. The process according to claim 4, wherein the oxygen content in the first stage is 15 to 30vol%, the reaction pH is 11 to 12, the stirring speed is 100 to 400 rpm, and the feed rate of the aqueous metal salt solution is 50 to 100 mL/L; and/or the number of the groups of groups,
the oxygen content in the second stage is 10-18vol%, the reaction pH value is 10.8-11.8, the stirring speed is 200-500 rpm, and the liquid inlet amount of the metal salt aqueous solution is 100-200 mL/L; and/or the number of the groups of groups,
the oxygen content in the third stage is 4-10vol%, the reaction pH value is 10.4-11.4, the stirring speed is 300-600 rpm, and the liquid inlet amount of the metal salt aqueous solution is 150-400 mL/L.
11. The production process according to claim 10, wherein the oxygen content in the fourth stage is 1 to 5vol%, the reaction pH is 10 to 11, the stirring speed is 400 to 700 rpm, and the feed amount of the aqueous metal salt solution is 200 to 600 mL/L.
12. The process according to claim 11, wherein the product obtained in the first stage has a median particle diameter D 50 1-4 μm; and/or the product obtained in the second stage has a median diameter D 50 4-7 μm; and/or the product obtained in the third stage has a median diameter D 50 7-11 μm; and/or the product obtained in the fourth stage has a median diameter D 50 9-15 μm.
13. The production method according to any one of claims 4 to 9, wherein in the step (2), the aging conditions include: the aging temperature is 40-70 ℃ and the aging time is 12-24h.
14. A ternary positive electrode material, characterized in that it is prepared by sintering a ternary precursor material according to any one of claims 1-13.
15. The ternary cathode material of claim 14, wherein the ternary cathode material has a composition represented by formula II:
Li c Ni x Co y Mn z M w O 2 a formula II;
wherein c is more than or equal to 0.9 and less than or equal to 1.2,0.3, x is more than or equal to 0.9, y is more than 0 and less than or equal to 0.4, z is more than 0 and less than or equal to 0.4, and w=1-x-y-z; m is selected from at least one of La, cr, mo, ca, fe, hf, ti, zn, Y, zr, si, W, nb, sm, V, mg, B, Y and Al;
and/or the tap density of the ternary positive electrode material is 2-3 g/cm 3 A specific surface area of 0.2-2 m 2 /g。
16. A method of preparing the ternary cathode material of claim 14 or 15, comprising the steps of:
s1, mixing a ternary precursor material with a lithium source to obtain a mixture;
s2, in an oxygen-containing atmosphere, sintering, crushing and screening the mixture in sequence to obtain the ternary anode material;
Wherein the ternary precursor material is the ternary precursor material of any one of claims 1-13.
17. The production method according to claim 16, wherein the amount of the ternary precursor material and the lithium source satisfies 0.9.ltoreq.n (Li) ]/[ n (Ni) +n (Co) +n (Mn) +n (M) ].ltoreq.1.2;
and/or the lithium source is lithium carbonate and/or lithium hydroxide;
and/or, the sintering conditions include: the sintering temperature is 600-1000 ℃; and/or sintering time is 6-25h.
18. A lithium ion battery comprising the ternary cathode material of claim 14 or 15.
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