CN115403077B - Ternary positive electrode material with high compaction and low cost and preparation method thereof - Google Patents
Ternary positive electrode material with high compaction and low cost and preparation method thereof Download PDFInfo
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- CN115403077B CN115403077B CN202211144586.XA CN202211144586A CN115403077B CN 115403077 B CN115403077 B CN 115403077B CN 202211144586 A CN202211144586 A CN 202211144586A CN 115403077 B CN115403077 B CN 115403077B
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- 238000005056 compaction Methods 0.000 title claims abstract description 54
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 177
- 239000013078 crystal Substances 0.000 claims abstract description 62
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 238000009826 distribution Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000010405 anode material Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims description 51
- 229910013716 LiNi Inorganic materials 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 239000010406 cathode material Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 230000001788 irregular Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 39
- 230000008569 process Effects 0.000 abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 25
- 239000001301 oxygen Substances 0.000 description 25
- 229910052760 oxygen Inorganic materials 0.000 description 25
- 239000011572 manganese Substances 0.000 description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 23
- 229910052744 lithium Inorganic materials 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 16
- 239000002243 precursor Substances 0.000 description 16
- 238000007873 sieving Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 13
- 238000005406 washing Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 10
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 10
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 10
- 239000008187 granular material Substances 0.000 description 9
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 5
- 239000011236 particulate material Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910001936 tantalum oxide Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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- 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
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- 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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- 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
- C01P2006/40—Electric properties
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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
- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a ternary positive electrode material with high compaction and low cost, which comprises the following components: polycrystalline particles and monocrystalline particles; the mixing proportion, the granularity and the granularity distribution of the ternary positive electrode material with high compaction and low cost meet the following conditions of SPAN (experience value) ＝X*SPAN (polycrystal) /(X+(1‑X)/Y)+(1‑X)*SPAN (Single crystal) /(XY+1‑X)，0.9*SPAN (experience value) ≤SPAN≤1.4*SPAN (experience value) . According to the invention, the size particles are mixed according to the difference of the granularity of the polycrystal and the granularity of the monocrystal, the compaction density of the anode material is improved while the high capacity is maintained, the compressive strength of the pole piece is improved, and the crushing phenomenon of the material in the circulation process is reduced. The invention also provides a preparation method of the ternary positive electrode material with high compaction and low cost.
Description
Technical Field
The invention belongs to the technical field of positive electrode materials, and particularly relates to a high-compaction low-cost ternary positive electrode material and a preparation method thereof.
Background
With the continuous improvement of the continuous voyage mileage requirement of new energy automobiles in the market, the improvement of the compaction density of the positive electrode material and the further improvement of the volumetric energy density become an effective method for solving the problems. Layered LiNi 1-x-y Co x M y O 2 The high nickel (Ni is more than or equal to 80%) ternary material has the advantages of high discharge capacity, long cycle life, small self-discharge rate and the like, and has been widely applied to power batteries. However, research shows that the high-nickel polycrystalline material can be broken in the pole piece rolling process, so that the electrode surface reactivity is increased, the electrochemical performance is deteriorated, meanwhile, the compaction density of the polycrystalline material is relatively low, and in order to solve the problem, the method can be used for solving the problem by filling single crystal materials with smaller particle size and better strength, and improving the circulation stability of the materials while improving the compaction densitySex.
In the prior art, by adopting nickel cobalt manganese hydroxide precursors with two particle sizes, mixing the precursors according to a certain proportion, adding a lithium source, and sintering at a high temperature to synthesize the high-compaction ternary positive electrode material, although the positive electrode material containing particles with different particle sizes is expected to be improved and compacted by mixing and sintering the precursors with different particle sizes, the phenomenon of uneven sintering among the particles is caused. Currently, the performance of ternary cathode materials is still to be further improved.
Disclosure of Invention
In view of the above, an object of the embodiments of the present invention is to provide a high-compaction low-cost ternary positive electrode material and a preparation method thereof.
The invention provides a ternary positive electrode material with high compaction and low cost, which comprises the following components:
polycrystalline particles and monocrystalline particles;
the mixing proportion (X) and the granularity (D) of the ternary positive electrode material with high compaction and low cost 50 ) The following conditions are satisfied with the particle size distribution (SPAN):
SPAN (experience value) ＝X*SPAN (polycrystal) /(X+(1-X)/Y)+(1-X)*SPAN (Single crystal) /(XY+1-X)，
0.9*SPAN (experience value) ≤SPAN≤1.4*SPAN (experience value) ，
X is the mole ratio of polycrystal blending, the blending ratio of polycrystal particles is 70-90%, Y is D 50 (polycrystal) /D 50 (Single crystal) Is a ratio of (2);
D 50 (polycrystal) Is the granularity of polycrystal particles;
D 50 (Single crystal) Is the granularity of single crystal particles;
SPAN is the particle size distribution of the ternary positive electrode material after blending;
SPAN (polycrystal) Is the particle size distribution of the polycrystalline particles;
SPAN (Single crystal) Is the particle size distribution of the single crystal particles.
Preferably, the polycrystalline particles have a composition formula:
LiNi x Co y M z R 1-x-y-z O 2 a formula II;
in the formula II, x is 0.6-1, y is 0-0.2, and z is 0-0.2;
m is selected from at least one element of Mn or Al;
r is selected from one or more of Al, ti, mg, zr, W, mo, ta, nb, Y, co, sr, B, ce, la.
Preferably, dmax of the polycrystalline particles is 28-35 mu m, dmin of the polycrystalline particles is 0.5-2.0 mu m, and D50 of the polycrystalline particles is 8-13 mu m;
the volume particle size distribution of the polycrystalline particles satisfies the following conditions:
SPAN ((D90-D10)/D50) is 1.43-1.72.
Preferably, the specific surface area of the polycrystalline particles is 0.30-0.70 m 2 /g；
Free Li in the polycrystalline grain + The mass content is less than or equal to 0.18wt%;
the polycrystalline particles are charged and discharged at room temperature and 0.2C, and the initial charge capacity is 200-215 mAh/g.
Preferably, the single crystal particles have the following general formula:
LiNi x Co y M z R 1-x-y-z O 2 formula III;
in the formula III, x is 0.6-1, y is 0-0.1, and z is 0-0.15;
m is selected from at least one element of Mn or Al;
r is selected from one or more of Al, ti, mg, zr, W, mo, ta, nb, Y, co, sr, B, ce, la.
Preferably, dmax of the single crystal particles is 20-25 μm, dmin of the single crystal particles is 1-1.5 μm, and D50 of the single crystal particles is 3.0-4.5 μm;
the volume particle size distribution of the single crystal particles satisfies the following conditions:
SPAN ((D90-D10)/D50) is 1.20-1.54;
the monocrystal particles are charged and discharged at room temperature at 0.2C, and the initial charge capacity is 195-205 mAh/g.
Preferably, the single crystal particles have a specific surface area of 0.60 to 1.20m 2 /g；
Free Li in the single crystal grain + The mass content is less than or equal to 0.16wt%;
the monocrystalline particles are irregular blocks, and the edges and corners are smooth;
the diameter of the single crystal particles satisfies the following conditions:
the center of the single crystal particle block is taken as an origin, and the ratio of the longest diameter to the shortest diameter of particles passing through the origin is 1-3.
Preferably, the molar ratio of the polycrystalline particles to the monocrystalline particles is (7-9): (3-1);
the volume fraction of the polycrystalline particles in the ternary positive electrode material with high compaction and low cost is more than or equal to 85 percent, and the volume fraction of the monocrystalline particles in the ternary positive electrode material with high compaction and low cost is less than or equal to 15 percent.
Preferably, the high-compaction low-cost ternary positive electrode material has a compaction density of 3.60-3.80 g/cm 3 ；
The ternary positive electrode material with high compaction and low cost is charged and discharged at room temperature under 0.2C, and the initial charge capacity is 200-210 mAh/g.
The invention provides a preparation method of the ternary positive electrode material with high compaction and low cost, which comprises the following steps:
mixing and sintering the polycrystalline particles and the monocrystalline particles to obtain a ternary anode material with high compaction and low cost;
the sintering temperature is 200-300 ℃.
The invention provides a ternary positive electrode material with high compaction and low cost and a preparation method thereof, which aims to solve the problem of low compaction density of a high-nickel polycrystalline positive electrode material, and comprises the following steps: preparing a polycrystalline material; preparing a single crystal material; and (3) preparing the blended coated cathode material. According to the invention, the size particles are mixed according to the difference of the granularity of the polycrystal and the granularity of the monocrystal, so that the compaction density of the anode material is improved, the compressive strength of the pole piece is improved, and the crushing phenomenon of the material in the circulation process is reduced while the high capacity is maintained.
Drawings
FIG. 1 is an SEM image of a polycrystalline particulate material prepared according to example 1 of the invention;
FIG. 2 is an SEM image of single crystal particulate material prepared according to example 1 of the invention;
fig. 3 is an SEM image of the positive electrode material prepared in example 1 of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a ternary positive electrode material with high compaction and low cost, which comprises the following components:
polycrystalline particles and monocrystalline particles;
the mixing proportion (X) and the granularity (D) of the ternary positive electrode material with high compaction and low cost 50 ) The following conditions are satisfied with the particle size distribution (SPAN):
SPAN (experience value) ＝X*SPAN (polycrystal) /(X+(1-X)/Y)+(1-X)*SPAN (Single crystal) /(XY+1-X)，
0.9*SPAN (experience value) ≤SPAN≤1.4*SPAN (experience value) ，
X is the mixing proportion of polycrystal, the mixing proportion (mole percent) of polycrystal particles is 70-90%, Y is D 50 (polycrystal) /D 50 (Single crystal) Is a ratio of (2);
D 50 (polycrystal) Is the granularity of polycrystal particles;
D 50 (Single crystal) Is the granularity of single crystal particles;
SPAN is the particle size distribution of the ternary positive electrode material after blending;
SPAN (polycrystal) Is the particle size distribution of the polycrystalline particles;
SPAN (Single crystal) Is the particle size distribution of the single crystal particles.
In the present invention, the X is preferably 75 to 85%, more preferably 80%.
In the present invention, the polycrystalline particles preferably have a composition formula:
LiNi x Co y M z R 1-x-y-z O 2 a formula II;
in the formula II, x is 0.6-1, y is 0-0.2, and z is 0-0.2;
m is selected from at least one element of Mn or Al;
r is selected from one or more of Al, ti, mg, zr, W, mo, ta, nb, Y, co, sr, B, ce, la.
In the present invention, in the formula II, x is preferably 0.7 to 0.9, more preferably 0.8; y is preferably 0.05 to 0.15, more preferably 0.08 to 0.12, most preferably 0.1; z is preferably 0.05 to 0.15, more preferably 0.08 to 0.12, most preferably 0.1.
In the invention, the granularity of the polycrystalline particles is preferably under the following conditions when the polycrystalline particles are tested by using a Markov MS 2000 laser particle sizer and deionized water as a dispersing agent:
dmax is less than or equal to 28 mu m and less than or equal to 35 mu m, dmin is less than or equal to 0.5 mu m and less than or equal to 2 mu m, and D50 is 8-13 mu m.
In the present invention, dmax of the polycrystalline particles is preferably 30 to 33. Mu.m, more preferably 31 to 32. Mu.m; dmin of the polycrystalline particles is preferably 1 to 1.5 μm, more preferably 1.2 to 1.3 μm; the D50 of the polycrystalline particles is preferably 9 to 12. Mu.m, more preferably 10 to 11. Mu.m.
In the present invention, the volume particle size distribution of the polycrystalline particles preferably satisfies the following conditions:
SPAN ((D90-D10)/D50) is 1.43 to 1.72, preferably 1.5 to 1.7, more preferably 1.6.
In the present invention, the specific surface area of the polycrystalline particles (using a specific surface area tester) is preferably 0.30 to 0.70m 2 Preferably 0.40 to 0.60m 2 Per g, most preferably 0.50m 2 /g。
In the present invention, free Li in the polycrystalline particles + Mass content (determination of CO by acid-base titration method) 3 2- /OH - Is converted to obtain free Li + Is preferably not more than 0.18% by weight.
In the invention, the polycrystalline particles are charged and discharged at room temperature and 0.2C, the initial charge capacity is preferably 200-215 mAh/g, more preferably 205-210 mAh/g, and most preferably 206-208 mAh/g.
In the present invention, the polycrystalline particles are preferably spheres of uniform size, smooth in surface, and free of additional protruding particles.
In the present invention, the method for preparing the polycrystalline particles preferably comprises:
mixing a hydroxide precursor, a doped compound and a lithium source, and then performing primary sintering to obtain a primary sintering product;
and mixing the primary sintering product with a cladding compound for secondary sintering to obtain polycrystalline particles.
In the present invention, the component formula of the hydrogen oxide precursor is preferably:
Ni x Co y M 1-x-y (OH) 2 a formula IV;
in the formula IV, x is 0.6-1, and y is 0-0.2;
m is selected from at least one element of Mn or Al.
In the present invention, in the formula IV, x is preferably 0.7 to 0.9, more preferably 0.8; y is preferably 0.05 to 0.15, more preferably 0.08 to 0.12, most preferably 0.1.
In the present invention, the doping compound is preferably selected from one or more of magnesium oxide, titanium oxide, tungsten oxide, molybdenum oxide, chromium oxide, zirconium oxide, strontium oxide, aluminum oxide, niobium oxide, and tantalum oxide.
In the present invention, the lithium source is preferably selected from one or more of lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium acetate, lithium oxalate, lithium acetate, and lithium oxide.
In the present invention, the mixing is preferably carried out uniformly in a high-speed mixer.
In the present invention, the molar ratio of the hydroxide precursor, doping element and lithium source is preferably 1: (0.001-0.003): 1, more preferably 1:0.002:1.
in the present invention, the lithium source is preferably used in an amount of 2 to 4% by mole, more preferably 2.5 to 3.5% by mole, most preferably 3% by mole, based on lithium.
In the present invention, the temperature of the primary sintering is preferably 600 to 750 ℃, more preferably 650 to 700 ℃, and most preferably 660 to 680 ℃; the time of the primary sintering is preferably 8 to 20 hours, more preferably 10 to 15 hours, and most preferably 12 to 13 hours; the primary sintering is preferably performed under an atmosphere of oxygen.
In the present invention, it is preferable that the primary sintered product is obtained further comprising:
crushing, washing and drying the primary sintering product, and mixing the primary sintering product with a coating compound for secondary sintering.
In the present invention, the washing is preferably performed in deionized water to which a lithium supplementing agent is added.
In the present invention, the capping compound is preferably selected from one or more of alumina, tantalum oxide, aluminum fluoride, boric acid, yttrium oxide, cobalt oxide, titanium oxide, tungsten oxide.
In the present invention, the amount of the covering compound added is preferably 500 to 3000ppm, more preferably 1000 to 2500ppm, and most preferably 1500 to 2000ppm of the primary sintered product.
In the present invention, the temperature of the secondary sintering is preferably 200 to 650 ℃, more preferably 300 to 600 ℃, more preferably 400 to 500 ℃, and most preferably 450 ℃; the secondary sintering time is preferably 8 to 20 hours, more preferably 10 to 15 hours, and most preferably 12 to 13 hours; the secondary sintering is preferably performed under an atmosphere of oxygen.
In the present invention, the secondary sintering preferably further comprises:
and (5) sieving the obtained sintered product with a 325-mesh sieve to obtain polycrystalline particles.
In the present invention, the single crystal grain preferably has a general formula:
LiNi x Co y M z R 1-x-y-z O 2 formula III;
in the formula III, x is 0.6-1, y is 0-0.1, and z is 0-0.15;
m is selected from at least one element of Mn or Al;
r is selected from one or more of Al, ti, mg, zr, W, mo, ta, nb, Y, co, sr, B, ce, la.
In the present invention, in the formula III, x is preferably 0.7 to 0.9, more preferably 0.8; y is preferably 0.02 to 0.08, more preferably 0.04 to 0.06, most preferably 0.05.
In the present invention, dmax of the single crystal particles is preferably 20 to 25. Mu.m, more preferably 21 to 24. Mu.m, most preferably 22 to 23. Mu.m; dmin of the single crystal particles is preferably 1 to 1.5 μm, more preferably 1.1 to 1.4 μm, and most preferably 1.2 to 1.3 μm; the D50 of the single crystal particles is preferably 3.0 to 4.5. Mu.m, more preferably 3.5 to 4.0. Mu.m, most preferably 3.6 to 3.8. Mu.m.
In the present invention, the volume distribution particle size of the single crystal particles preferably satisfies the following condition:
SPAN ((D90-D10)/D50) is 1.20 to 1.54, preferably 1.3 to 1.5, more preferably 1.4.
In the present invention, the single crystal particles preferably have a specific surface area (BET) of 0.60 to 1.20m 2 Preferably 0.70 to 1.10m 2 Preferably 0.80 to 1.00m 2 Per g, most preferably 0.90m 2 /g。
In the present invention, free Li in the single crystal particles + Mass content (determination of CO by acid-base titration method) 3 2- /OH - Is converted to obtain free Li + Is preferably not more than 0.16% by weight.
In the present invention, the single crystal grain is preferably an irregular block with smooth edges and corners.
In the present invention, the diameter of the single crystal particles preferably satisfies the following conditions:
the ratio of the longest diameter (La) to the shortest diameter (Lb) of the particles passing through the origin is 1 to 3, preferably 1.5 to 2.5, more preferably 2, with the center of the single crystal particle block as the origin.
In the present invention, the number of particles satisfying the above diameter condition in the single crystal particles is preferably 90% or more of the total number of particles, and if the diameter of the single crystal particles does not satisfy the above condition, the filling of the single crystal particles is not uniform, and if the edges and corners of the single crystal particles are clear, the polycrystalline particle sphere structure is easily broken during tabletting.
In the invention, the single crystal particles are charged and discharged at room temperature and 0.2C, and the initial charge capacity is preferably 195-205 mAh/g, more preferably 198-202 mAh/g, and most preferably 200mAh/g.
In the present invention, the method for producing single crystal particles preferably comprises:
mixing hydroxide, a lithium source and a doping compound, and then performing primary sintering to obtain a primary sintering product;
and mixing the primary sintering product with a coating compound for secondary sintering to obtain monocrystalline particles.
In the present invention, the hydroxide preferably has the formula:
Ni x Co y M 1-x-y (OH) 2 a formula V;
in the formula V, x is 0.6-1, and y is 0-0.1;
m is selected from at least one element of Mn or Al.
In the present invention, x in the formula V is preferably 0.7 to 0.9, more preferably 0.8; the y is preferably 0.02 to 0.08, more preferably 0.04 to 0.06, and most preferably 0.05.
In the present invention, the lithium source is preferably selected from one or more of lithium hydroxide monohydrate, lithium carbonate, lithium nitrate, lithium acetate, lithium oxalate, lithium acetate, and lithium oxide.
In the present invention, the doped compound is preferably one or more of magnesium oxide, titanium oxide, tungsten oxide, molybdenum oxide, chromium oxide, zirconium oxide, strontium oxide, aluminum oxide, niobium oxide, and tantalum oxide.
In the present invention, the molar ratio of the hydroxide, the doping element and the lithium source is preferably 1 (0.001 to 0.003): 1, more preferably 1:0.002:1.
in the present invention, the lithium source is preferably used in an amount of 2 to 4% by mole, more preferably 2.5 to 3.5% by mole, most preferably 3% by mole, based on lithium.
In the present invention, the mixing is preferably carried out uniformly in a high-speed mixer.
In the present invention, the temperature of the primary sintering is preferably 700 to 850 ℃, more preferably 750 to 800 ℃, and most preferably 760 to 780 ℃; the time of the primary sintering is preferably 8 to 20 hours, more preferably 10 to 15 hours, and most preferably 12 to 13 hours; the primary sintering is preferably performed under an atmosphere of oxygen.
In the present invention, the primary sintered product is preferably further included;
and (3) carrying out jet milling on the primary sintering product, and then adding cladding elements to mix for secondary sintering.
In the present invention, the capping compound is preferably selected from one or more of alumina, tantalum oxide, aluminum fluoride, boric acid, yttrium oxide, cobalt oxide, titanium oxide, tungsten oxide.
In the present invention, the amount of the coating element added is preferably 500 to 3000ppm, more preferably 1000 to 2500ppm, and most preferably 1500 to 2000ppm of the primary sintered product.
In the present invention, the secondary sintering is preferably performed under an oxygen atmosphere; the temperature of the secondary sintering is preferably 350-700 ℃, more preferably 400-600 ℃, more preferably 450-550 ℃, and most preferably 500 ℃; the time for the four times of sintering is preferably 8 to 20 hours, more preferably 10 to 15 hours, and most preferably 12 to 13 hours.
In the present invention, the secondary sintering preferably further comprises:
and (5) sieving the obtained sintered product with a 325-mesh sieve to obtain monocrystalline particles.
In the invention, the high nickel material is generally provided with a water washing process due to higher surface residual alkali, but the high nickel material can react with water to generate nickel-containing oxide to reduce the reactivity of the material after the water washing process, and the high nickel monocrystal is difficult to completely remove water in the material in the suction filtration process, so that the external pressure is required to be applied, the process is complicated, the water washing link is omitted in the process of preparing the monocrystal granular material, and a coating layer is formed on the surface of the material directly through the chemical reaction between the coating agent and residual lithium.
Meanwhile, the high-nickel monocrystal material enables the cobalt ratio to be further reduced by adjusting the proportion of nickel, cobalt and manganese, so that the initial capacity is slightly reduced, the tap density is improved, and the cost is saved under the condition that the overall performance of the material is not affected.
In the invention, the volume fraction of the polycrystalline particles in the ternary positive electrode material with high compaction and low cost is preferably more than or equal to 85%; the volume fraction of the monocrystalline particles in the ternary positive electrode material with high compaction and low cost is less than or equal to 15 percent.
In the present invention, the molar ratio of the polycrystalline particles to the single crystal particles is preferably (7 to 9): (3-1), more preferably (7.5-8.5): (1.5 to 2.5), most preferably 8:2.
in the invention, the compacted density of the ternary positive electrode material with high compaction and low cost is preferably 3.60-3.80 g/cm 3 More preferably 3.65 to 3.75g/cm 3 Most preferably 3.70g/cm 3 。
In the invention, the high-compaction low-cost ternary positive electrode material is charged and discharged at room temperature and 0.2C, and the initial charge capacity is preferably 200-210 mAh/g, more preferably 202-208 mAh/g, and most preferably 204-206 mAh/g.
The invention provides a preparation method of the ternary positive electrode material with high compaction and low cost, which comprises the following steps:
and mixing and sintering the polycrystalline particles and the monocrystalline particles to obtain the ternary anode material with high compaction and low cost.
In the present invention, the molar ratio of the polycrystalline particles to the monocrystalline particles is the same as that described in the above technical scheme, and will not be described again.
In the present invention, the sintering temperature is preferably 200 to 300 ℃, more preferably 220 to 280 ℃, and most preferably 240 to 260 ℃; the sintering time is preferably 5 to 10 hours, more preferably 6 to 9 hours, and most preferably 7 to 8 hours; according to the invention, lithium ions can be better transmitted in two materials through sintering, and meanwhile, the effect of removing moisture is achieved.
According to the invention, the size particles are mixed according to the difference of the granularity of the polycrystal and the granularity of the monocrystal, the compaction density of the anode material is improved while the high capacity is maintained, the compressive strength of the pole piece is improved, and the crushing phenomenon of the material in the circulation process is reduced.
According to the invention, the cobalt proportion (namely the total molar proportion of nickel, cobalt and manganese) in the high-nickel monocrystal is reduced by half in the monocrystal preparation process, the manganese proportion is increased by two times while the nickel content is slightly reduced, the monocrystal material with lower raw material cost is prepared, the dry coating is adopted in the preparation process, the water washing process is reduced, the generation of low-activity byproducts in the water washing process is avoided, and the low-cost material prepared by the method can completely replace the normal high-nickel monocrystal material, so that the preparation cost can be correspondingly reduced.
The invention controls the morphology and specific characteristics of the monocrystalline material (the monocrystal obtained by the preparation method tends to be ellipsoidal, no sharp edges and corners, the ratio of the long diameter to the short diameter is 1-3, the monocrystal can be well embedded into a gap when being mixed with secondary spheres (polycrystalline particles), the monocrystal is more fully filled than small-particle secondary spheres (polycrystalline particles), but has the pressure-resistant advantage of the monocrystal, the monocrystal is not easy to be mutually extruded and crushed in the rolling process, when the ratio is too large, the phenomenon that part of the material exceeds the gap to overlap with the secondary spheres (polycrystalline particles) partially exists in the mixing process, the lithium ion diffusion path is increased), and the relationship between the secondary spheres (polycrystalline particles) and the granularity of the monocrystal and the granularity of the positive electrode can obtain the positive electrode material with better performance.
The hydroxide precursor and the hydroxide composition used in the following examples of the present invention were Ni 0.85 Co 0.1 M 0.05 (OH) 2 Is provided for the Chinese Wei New Material Co., ltd.
Example 1
Large particle (10 μm) hydroxide precursor (Ni 0.85 Co 0.1 Mn 0.05 (OH) 2 ) And lithium hydroxide monohydrate, wherein 2500ppm of zirconia is placed in a high-speed mixer to be uniformly mixed, the molar ratio of the zirconia to the lithium is 2 percent (the molar ratio of the precursor to the lithium hydroxide is 1:1.02), and the mixture is sintered for 15 hours at 730 ℃ in an oxygen atmosphere to obtain a sintered product; crushing the obtained primary combustion product, washing with deionized water added with lithium hydroxide monohydrate, drying to obtain a dry productSintering the dried product and 1500ppm boric acid in an oxygen atmosphere at 300 ℃ for 10 hours, and sieving the mixture with a 325-mesh sieve to obtain a polycrystalline granular material LiNi 0.8482 Co 0.0998 Mn 0.0499 Zr 0.0018 B 0.0003 O 2 。
Small particles (3.2 microns) of hydroxide (Ni 0.85 Co 0.1 Mn 0.05 (OH) 2 ) And lithium hydroxide, 1500ppm strontium oxide element is put into a high-speed mixer to be mixed uniformly, the molar ratio of the lithium to the lithium is 2 percent (the molar ratio of the hydroxide to the lithium hydroxide is 1:1.02), and the mixture is sintered for 15 hours at 850 ℃ in an oxygen atmosphere to obtain a sintered product; jet-pulverizing the primary sintered product, adding 2000ppm nanometer aluminum oxide, sintering at 500 deg.C in oxygen atmosphere for 10 hr, and sieving with 325 mesh sieve to obtain monocrystal granular material LiNi 0.8480 Co 0.1000 Mn 0.0499 Sr 0.0013 Al 0.0011 O 2 。
And (3) weighing and uniformly mixing the prepared polycrystalline particle material and monocrystalline particle material according to the mol ratio of 7:3, sintering at 200 ℃ for 5 hours in an oxygen atmosphere, and sieving to obtain the anode material.
Example 2
Large particle (10 μm) hydroxide precursor (Ni 0.85 Co 0.1 Mn 0.05 (OH) 2 ) And lithium hydroxide monohydrate, 2000ppm of zirconia is placed in a high-speed mixer to be mixed uniformly, the molar ratio of the zirconia to the lithium is 2 percent (the molar ratio of the precursor to the lithium hydroxide is 1:1.02), and the mixture is sintered for 15 hours at 730 ℃ in an oxygen atmosphere to obtain a sintered product; crushing the obtained primary burned product, washing with deionized water added with lithium hydroxide monohydrate, drying, sintering the dried product with 1500ppm boric acid in oxygen atmosphere at 300 ℃ for 10 hours, and sieving with a 325-mesh sieve to obtain a polycrystalline granular material LiNi 0.8485 Co 0.0998 Mn 0.0499 Zr 0.0015 B 0.0003 O 2 。
Small particles (3.2 microns) of hydroxide (Ni 0.85 Co 0.1 Mn 0.05 (OH) 2 ) And lithium hydroxide, 1500ppm tungsten oxide element is put into a high-speed mixer to be mixed uniformly, the molar ratio of the lithium to the lithium is 2 percent (the molar ratio of the hydroxide to the lithium hydroxide is 1:1.02)) Sintering for 15 hours at 800 ℃ in an oxygen atmosphere to obtain a sintered product; pulverizing the obtained primary sintered product by air flow, adding 2000ppm nanometer aluminum oxide, sintering at 500 deg.C in oxygen atmosphere for 10h, sieving with 325 mesh sieve to obtain monocrystal granular material LiNi 0.8481 Co 0.0998 Mn 0.0499 W 0.0012 Al 0.0011 O 2 。
And uniformly mixing the prepared polycrystalline particle material and monocrystalline particle material according to the mol ratio of 8:2, sintering at 200 ℃ for 5 hours in an oxygen atmosphere, and sieving to obtain the anode material.
Example 3
Large particle (10 μm) hydroxide precursor (Ni 0.85 Co 0.1 Mn 0.05 (OH) 2 ) And lithium hydroxide monohydrate, namely placing 1500ppm of zirconia into a high-speed mixer to be uniformly mixed, wherein the molar ratio of the zirconia to the lithium is 2 percent (the molar ratio of the precursor to the lithium hydroxide is 1:1.02), and sintering the mixture for 15 hours at 730 ℃ in an oxygen atmosphere to obtain a sintered product; crushing the obtained primary burned product, washing with deionized water added with lithium hydroxide monohydrate, drying, sintering the dried product with 1500ppm boric acid in oxygen atmosphere at 300 ℃ for 10 hours, and sieving with a 325-mesh sieve to obtain a polycrystalline granular material LiNi 0.8488 Co 0.0999 Mn 0.0499 Zr 0.0011 B 0.0003 O 2 。
Small particles (3.1 microns) of hydroxide (Ni 0.85 Co 0.1 Mn 0.05 (OH) 2 ) And lithium hydroxide, 1500ppm titanium oxide element is put into a high-speed mixer to be mixed uniformly, the molar ratio of the lithium is 2 percent (the molar ratio of the precursor to the lithium hydroxide is 1:1.02), and the mixture is sintered for 15 hours at 750 ℃ in an oxygen atmosphere to obtain a sintered product; pulverizing the obtained primary sintered product by air flow, adding 2000ppm nanometer aluminum oxide, sintering at 500 deg.C in oxygen atmosphere for 10h, sieving with 325 mesh sieve to obtain monocrystal granular material LiNi 0.8487 Co 0.0999 Mn 0.0499 Ti 0.0004 Al 0.0011 O 2 。
Uniformly mixing the polycrystalline particle material and the monocrystalline particle material according to the mol ratio of 9:1, sintering at 200 ℃ for 5 hours in an oxygen atmosphere, and sieving to obtain the anode material.
Comparative example 1
The polycrystalline particulate material in example 1 was used as the positive electrode material.
Comparative example 2
The polycrystalline particulate material in example 2 was used as the positive electrode material.
Comparative example 3
The polycrystalline particulate material in example 3 was used as the positive electrode material.
Comparative example 4
The polycrystalline particles and the monocrystalline materials in the embodiment 1 are adopted as the positive electrode materials, the polycrystalline particles and the monocrystalline particles are weighed and mixed uniformly according to the mol ratio of 6:4, and are sintered for 5 hours at 200 ℃ in an oxygen atmosphere, and the positive electrode materials are obtained through sieving.
Comparative example 5
A large particle (10 μm) narrow distribution hydroxide precursor (Ni 0.85 Co 0.1 Mn 0.05 (OH) 2 ) And lithium hydroxide monohydrate, wherein 1000ppm of zirconia is placed in a high-speed mixer to be uniformly mixed, the molar ratio of the zirconia to the lithium is 2 percent (the molar ratio of the precursor to the lithium hydroxide is 1:1.02), and the mixture is sintered for 12 hours at 800 ℃ in an oxygen atmosphere to obtain a sintered product; crushing the obtained primary sintered product, washing with water in deionized water added with lithium hydroxide monohydrate, drying, sintering the obtained dry product with 1500ppm boric acid in oxygen atmosphere at 300 ℃ for 10 hours, and sieving with a 325-mesh sieve to obtain a polycrystalline granular material LiNi 0.8491 Co 0.0999 Mn 0.0499 Zr 0.0007 B 0.000 3 O 2 。
Narrow distribution of small particles (3 microns) of hydroxide (Ni 0.85 Co 0.1 Mn 0.05 (OH) 2 ) And lithium hydroxide, 3000ppm strontium oxide element is put into a high-speed mixer to be mixed uniformly, the molar ratio of lithium is 2 percent (the molar ratio of the hydroxide to the lithium hydroxide is 1:1.02), and the mixture is sintered for 15 hours at 900 ℃ in the oxygen atmosphere to obtain a sintered product; jet pulverizing the primary sintered product, adding 2000ppm nanometer aluminum oxide, sintering at 450 deg.C in oxygen atmosphere for 10 hr, and sieving with 325 mesh sieve to obtain monocrystal granular material LiNi 0.8470 Co 0.0996 Mn 0.0498 Sr 0.0025 Al 0.0011 O 2 。
And (3) weighing and uniformly mixing the prepared polycrystalline particle material and monocrystalline particle material according to the mol ratio of 6:4, sintering at 200 ℃ for 5 hours in an oxygen atmosphere, and sieving to obtain the anode material.
Performance detection
SEM (scanning electron microscope) detection is carried out on the polycrystalline particle material in the embodiment 1 of the invention, and the detection result is shown in figure 1, so that the appearance of polycrystalline particles is secondary spheres, the sphericity is high, the particle size distribution is relatively uniform, and the D50 is about 10 microns; SEM examination is carried out on the monocrystalline particle material in the embodiment 1 of the invention, and the examination result is shown in figure 2, and it can be seen that the morphology of the monocrystalline particle is monocrystalline, the monocrystalline has good dispersibility, the appearance is smooth and has no edges and corners, and the D50 is about 3.2 microns; SEM examination is carried out on the positive electrode material prepared in the embodiment 1 of the invention, and the examination result is shown in figure 3, so that after the polycrystalline particles and the monocrystalline particles are mixed, the compaction of material powder is obviously improved through filling part of gaps, the compressive strength is improved when the pole piece is prepared, and the problem of cracking balls in circulation is solved.
The polycrystalline particle material (secondary sphere), single crystal particle material, and SPAN (particle size distribution) of the positive electrode material, density after powder compaction, specific surface area, and 0.2C discharge capacity of the present examples and comparative examples were examined, and the results of the examination were as follows:
the invention obtains the high-compaction anode material by controlling the mixing of the polycrystalline grain size range and the monocrystalline grain size range. According to the invention, the size particles are mixed according to the difference of the granularity of the polycrystal and the granularity of the monocrystal, the compaction density of the anode material is improved while the high capacity is maintained, the compressive strength of the pole piece is improved, and the crushing phenomenon of the material in the circulation process is reduced. Meanwhile, the defects that the SPAN is too narrow and gaps cannot be filled by small-particle single crystals after the polycrystal is densely packed and compaction is small due to improper mixing proportion and improper particle size distribution of single crystals and polycrystal mixing can be found; if the SPAN distribution is too wide, too many single crystals still result in lower compaction after the gaps are filled, and meanwhile, the pole pieces are easier to break after rolling.
While the invention has been described and illustrated with reference to specific embodiments thereof, the description and illustration is not intended to limit the invention. It will be apparent to those skilled in the art that various changes may be made in this particular situation, material, composition of matter, substance, method or process without departing from the true spirit and scope of the invention as defined by the following claims, so as to adapt the objective, spirit and scope of the present application. All such modifications are intended to be within the scope of this appended claims. Although the methods disclosed herein have been described with reference to particular operations being performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form an equivalent method without departing from the teachings of the present disclosure. Thus, unless specifically indicated herein, the order and grouping of operations is not a limitation of the present application.
Claims (8)
1. A high-compaction low-cost ternary positive electrode material comprising:
polycrystalline particles and monocrystalline particles;
the mixing proportion, granularity and granularity distribution of the ternary positive electrode material with high compaction and low cost meet the following conditions:
SPAN (experience value) ＝X*SPAN (polycrystal) /(X+(1-X)/Y)+(1-X)*SPAN (Single crystal)
/(XY+1-X)，
0.9*SPAN (experience value) ≤SPAN≤1.4*SPAN (experience value) ，
X is the mole ratio of polycrystal blending, Y is D 50 (polycrystal) /D 50 (Single crystal) Is a ratio of (2);
x is 70-90%;
D 50 (polycrystal) Is the granularity of polycrystal particles;
D 50 (Single crystal) Is the granularity of single crystal particles;
SPAN is the particle size distribution of the ternary positive electrode material after blending;
SPAN (polycrystal) Is the particle size distribution of the polycrystalline particles;
SPAN (Single crystal) Is the particle size distribution of single crystal particles;
the Dmax of the polycrystalline particles is 28-35 mu m, the Dmin of the polycrystalline particles is 0.5-2.0 mu m, and the D50 of the polycrystalline particles is 8-13 mu m;
the volume particle size distribution of the polycrystalline particles satisfies the following conditions:
SPAN ((D90-D10)/D50) is 1.43-1.72;
the Dmax of the single crystal particles is 20-25 mu m, the Dmin of the single crystal particles is 1-1.5 mu m, and the D50 of the single crystal particles is 3.0-4.5 mu m;
the volume particle size distribution of the single crystal particles satisfies the following conditions:
SPAN ((D90-D10)/D50) is 1.20-1.54;
the monocrystal particles are charged and discharged at room temperature at 0.2C, and the initial charge capacity is 195-205 mAh/g.
2. The high compaction low cost ternary positive electrode material according to claim 1, wherein the polycrystalline particles have a composition formula:
LiNi x Co y M z R 1-x-y-z O 2 a formula II;
in the formula II, x is 0.6-1, y is 0-0.2, and z is 0-0.2;
m is selected from at least one element of Mn or Al;
r is selected from one or more of Al, ti, mg, zr, W, mo, ta, nb, Y, co, sr, B, ce, la.
3. The high-compaction low-cost ternary cathode material according to claim 1, wherein the polycrystalline particles have a specific surface area of 0.30 to 0.70m 2 /g；
Free Li in the polycrystalline grain + Quality ofThe content is less than or equal to 0.18wt%;
the polycrystalline particles are charged and discharged at room temperature and 0.2C, and the initial charge capacity is 200-215 mAh/g.
4. The high-compaction low-cost ternary cathode material according to claim 1, wherein the single crystal particles have a composition formula:
LiNi x Co y M z R 1-x-y-z O 2 formula III;
in the formula III, x is 0.6-1, y is 0-0.1, and z is 0-0.15;
m is selected from at least one element of Mn or Al;
r is selected from one or more of Al, ti, mg, zr, W, mo, ta, nb, Y, co, sr, B, ce, la.
5. The high-compaction low-cost ternary cathode material according to claim 1, wherein the single-crystal particles have a specific surface area of 0.60 to 1.20m 2 /g；
Free Li in the single crystal grain + The mass content is less than or equal to 0.16wt%;
the monocrystalline particles are irregular blocks, and the edges and corners are smooth;
the diameter of the single crystal particles satisfies the following conditions:
the center of the single crystal particle block is taken as an origin, and the ratio of the longest diameter to the shortest diameter of particles passing through the origin is 1-3.
6. The high-compaction low-cost ternary cathode material according to claim 1, wherein the molar ratio of polycrystalline particles to single crystal particles is (7-9): (3-1);
the volume fraction of the polycrystalline particles in the ternary positive electrode material with high compaction and low cost is more than or equal to 85 percent, and the volume fraction of the monocrystalline particles in the ternary positive electrode material with high compaction and low cost is less than or equal to 15 percent.
7. The high-compaction low-cost ternary positive electrode material according to claim 1, wherein,the high-compaction low-cost ternary positive electrode material has a compaction density of 3.60-3.80 g/cm 3 ；
The ternary positive electrode material with high compaction and low cost is charged and discharged at room temperature under 0.2C, and the initial charge capacity is 200-210 mAh/g.
8. A method of preparing the high-compaction low-cost ternary positive electrode material of claim 1, comprising:
mixing and sintering the polycrystalline particles and the monocrystalline particles to obtain a ternary anode material with high compaction and low cost;
the sintering temperature is 200-300 ℃.
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