CN115385391A - Preparation process of high-voltage single crystal positive electrode material of lithium ion battery - Google Patents
Preparation process of high-voltage single crystal positive electrode material of lithium ion battery Download PDFInfo
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- CN115385391A CN115385391A CN202210946593.5A CN202210946593A CN115385391A CN 115385391 A CN115385391 A CN 115385391A CN 202210946593 A CN202210946593 A CN 202210946593A CN 115385391 A CN115385391 A CN 115385391A
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- 239000013078 crystal Substances 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000007774 positive electrode material Substances 0.000 title claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 59
- 239000002243 precursor Substances 0.000 claims abstract description 51
- 238000005245 sintering Methods 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 36
- 239000000047 product Substances 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011572 manganese Substances 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 11
- 239000011029 spinel Substances 0.000 claims abstract description 11
- 239000013589 supplement Substances 0.000 claims abstract description 10
- 239000010406 cathode material Substances 0.000 claims abstract description 9
- 230000001502 supplementing effect Effects 0.000 claims abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 20
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 9
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- BLYYANNQIHKJMU-UHFFFAOYSA-N manganese(2+) nickel(2+) oxygen(2-) Chemical group [O--].[O--].[Mn++].[Ni++] BLYYANNQIHKJMU-UHFFFAOYSA-N 0.000 claims description 7
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 230000001788 irregular Effects 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 12
- 239000010405 anode material Substances 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 abstract description 3
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000002950 deficient Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 230000003313 weakening effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 21
- 238000009826 distribution Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002696 manganese Chemical class 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000009469 supplementation Effects 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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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
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/54—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]-, e.g. Li(NixMn2-x)O4, Li(MyNixMn2-x-y)O4
-
- 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
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation process of a high-voltage single crystal cathode material of a lithium ion battery, which comprises the following steps: mixing the precursor with a lithium-containing compound and sintering at one time, wherein the molar ratio of the lithium content in the lithium-containing compound to the total content of nickel and manganese elements in the precursor is (0.95-1): 1, then replenishing a lithium-containing compound and carrying out secondary sintering to obtain a finished product, wherein the molar ratio of the lithium content in the replenished lithium-containing compound to the total content of nickel and manganese elements in the precursor is (0.05-0.1): the method comprises the steps of 1, mixing a precursor with a lithium-containing compound in a lithium-deficient mode at the early stage, adding a small amount of lithium-containing compound at the later stage to supplement lithium, inhibiting the dissolution of manganese by improving the pH value, increasing the structural stability, neutralizing acid substances in an electrolyte, weakening the corrosion of the electrolyte on an anode material, improving the cycle performance of spinel single crystal nickel lithium manganate, supplementing lithium consumed by a cathode during the formation of an SEI film, and improving the capacity exertion and the capacity effective utilization rate of the spinel nickel manganese material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery preparation, and particularly relates to a preparation process of a high-voltage single crystal cathode material of a lithium ion battery.
Background
At present, in recent years, the development of high energy density lithium ion battery materials is motivated by the huge demand for energy, and at the same time, in the intense market competition environment, the lithium ion battery is required to have lower cost besides high quality. The positive electrode material accounts for more than 40% of the total cost of the battery, and therefore, the development of a high energy density and low cost positive electrode material is a current trend.
Wherein, the nickel lithium manganate (LiNi) with spinel structure 0.5 Mn 1.5 O 4 LNMO) material has the theoretical specific discharge capacity of 146.7 mA.h/g, and has the advantages of high voltage platform, stable crystal structure, low cost and the like, thereby becoming one of the most potential high-voltage anode materials. At present, the lithium nickel manganese oxide is still not commercially produced for two main reasons. One is decomposition of the electrolyte at high voltage and side reactions at the electrode/electrolyte interface, leading to degradation of the cell performance. The potential plateau of the lithium nickel manganese oxide is as high as 4.7V, but the stable potential window of the current commercial organic electrolyte is about 1-4.5V. The working potential of the lithium nickel manganese oxide material exceeds the stable window of the conventional electrolyte, and the oxidative decomposition of the electrolyte is inevitably caused, so that the problems of an electrode/electrolyte interface and an electrode/current collector interface are serious. On the other hand, mn is mainly generated from LiNi in the cycle process under the high-temperature condition 0.5 Mn 1.5 O 4 The surface dissolves into the electrolyte, with the structure of the surface distorting, resulting in faster cell capacity fade and poorer rate performance.
Disclosure of Invention
The invention provides a preparation process of a high-voltage single crystal cathode material of a lithium ion battery, which solves the problems.
A preparation process of a high-voltage single crystal anode material of a lithium ion battery is characterized by comprising the following steps: mixing the precursor with a lithium-containing compound, sintering for the first time to obtain a sample A, supplementing the lithium-containing compound, and sintering for the second time to obtain a finished product, wherein before the sintering for the first time, the molar ratio of the lithium content in the lithium-containing compound to the total nickel-manganese element content in the precursor is (0.95-1): 1, the molar ratio of the lithium content in the supplemented lithium-containing compound to the total content of nickel and manganese elements in the precursor is (0.05-0.1): 1.
in a preferred embodiment, the precursor is a nickel-manganese oxide, and the lithium-containing compound mixed with the precursor is one of lithium carbonate, lithium nitrate, lithium chloride, lithium oxalate and lithium hydroxide.
As a preferred embodiment, the temperature of the primary sintering is 800-1000 ℃, and the primary sintering time is 15-35h.
In a preferred embodiment, the lithium-containing compound is one of lithium carbonate, lithium nitrate, lithium chloride, lithium oxalate and lithium hydroxide.
As a preferred embodiment, before the second sintering, there is also an element doping step, and the element doping method is: and uniformly mixing the compound of the required doping element and the sample A after lithium supplement by a high-speed mixer, wherein the weight ratio of the compound of the required doping element to the precursor is 0.3-0.5%.
As a preferred embodiment, the compound of the required doping element is one or more of zirconium oxide, aluminum oxide, niobium oxide, antimony oxide, strontium oxide, barium oxide, yttrium oxide, chromium oxide, and boron oxide.
In a preferred embodiment, the temperature of the secondary sintering is 750-900 ℃, and the time of the secondary sintering is 5-15h.
In a preferred embodiment, the secondary sintering is followed by a coating step, wherein the coating is performed by mixing the mixture supplemented with the lithium-containing compound with one or more of titanium oxide, aluminum oxide, magnesium oxide, or beryllium oxide.
As a preferable embodiment, the coating is further provided with a heat treatment step, the heat treatment temperature is 450-750 ℃, the heat treatment time is 5-10h, and the finished product is obtained after the heat treatment.
As a preferred embodiment, the precursor is irregular-shaped particles formed by loose and aggregated nano-crystalline grains, and the precursor meets the conditions that the Dv50=0.5-3 mu m and the specific surface area is more than 12m 2 G, tap density less than 0.8g/cm 3 The finished product is spinel single crystal lithium nickel manganese oxide material with the grain diameter of 2-6 um.
After the technical scheme is adopted, the invention has the beneficial effects that:
according to the invention, when the precursor is mixed with lithium carbonate in the former stage, lithium is deficient, and a small amount of lithium hydroxide is added in the later stage for lithium supplement, so that on one hand, the dissolution of manganese is inhibited by improving the pH value, the structural stability is increased, on the other hand, acidic substances in the electrolyte are neutralized, the corrosion of the electrolyte to an anode material is weakened, and the cycle performance of spinel single crystal nickel lithium manganate is improved. Meanwhile, lithium consumed by the cathode in the SEI film formation process is supplemented, and the capacity exertion and the capacity effective utilization rate of the spinel nickel-manganese material are improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a comparison XRD plot;
FIG. 2 is a first SEM comparison view;
FIG. 3 is a comparison of a first particle size distribution;
FIG. 4 is a second SEM comparison view;
FIG. 5 is a comparison of a second particle size distribution;
FIG. 6 is a third particle size distribution plot;
FIG. 7 is a comparison of the first cycle;
FIG. 8 is a graph comparing long cycles of discharge versus capacity;
FIG. 9 is a graph comparing capacity retention rates.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Example 1
A preparation process of a high-voltage single crystal anode material of a lithium ion battery comprises the following steps:
mixing soluble nickel salt and manganese salt, adding pure water after mixing to obtain a solution, adding ammonia water into the solution for mixing to obtain a coprecipitate, and carrying out solid-liquid separation on the coprecipitate by adopting a centrifugal machine to obtain a precursor, wherein the precursor is nickel-manganese oxide.
The precursor adopted in the embodiment is irregular-shaped particles formed by loosely agglomerated nano-crystalline grains, the particle size of the precursor is 1.6um, and the specific surface area is more than 12m 2 The tap density is less than 0.8g/cm 3 Mixing the precursor with lithium carbonate, wherein the molar ratio of the content of lithium element in the lithium carbonate to the total content of nickel and manganese elements in the precursor is 0.95:1.
the temperature of the primary sintering is 800 ℃, and the time of the primary sintering is 15h. After the primary sintering is finished, obtaining a sample A, and supplementing lithium to the sample A, wherein the lithium supplementation adopts a mode of adding lithium hydroxide, and the molar ratio of the lithium content in the lithium hydroxide to the total content of nickel and manganese elements in the precursor is 0.05:1.
and doping elements, wherein the elements required to be doped in the embodiment are zirconium element, niobium element and antimony element, and the element doping step is to dope zirconium oxide, niobium oxide and antimony oxide to prepare a doping compound, wherein the doping compound and the sample A after lithium supplement are uniformly mixed, and the weight ratio of the doping compound to the precursor is 0.38%.
And (3) carrying out secondary sintering after element doping, wherein the temperature of the secondary sintering is 750 ℃, and the time of the secondary sintering is 5h.
After the secondary sintering is finished, the coating is carried out by mixing with titanium oxide and aluminum oxide.
And (4) carrying out heat treatment after the coating is finished, wherein the heat treatment temperature is 450 ℃, and the heat treatment time is 5h.
And after the heat treatment is finished, obtaining a final finished product, wherein the finished product is a spinel single crystal lithium nickel manganese oxide material with the particle size of 5.5 um.
Example 2
A preparation process of a high-voltage single crystal anode material of a lithium ion battery comprises the following steps:
mixing soluble nickel salt and manganese salt, adding pure water after mixing to obtain a solution, adding ammonia water into the solution for mixing to obtain a coprecipitate, and carrying out solid-liquid separation on the coprecipitate by using a centrifugal machine to obtain a precursor, wherein the precursor is nickel-manganese oxide.
The precursor adopted in the embodiment is irregular-shaped particles formed by loosely agglomerated nano-crystalline grains, the particle size of the precursor is 0.7um, and the specific surface area is more than 12m 2 G, tap density less than 0.8g/cm 3 Mixing the precursor with lithium nitrate, wherein the molar ratio of the content of lithium element in the lithium nitrate to the total content of nickel and manganese elements in the precursor is 0.97:1.
the temperature of the primary sintering is 900 ℃, and the time of the primary sintering is 25h. After the primary sintering is finished, obtaining a sample A, and supplementing lithium to the sample A, wherein the lithium supplementing adopts a mode of adding lithium nitrate, and the molar ratio of the lithium content in the lithium nitrate to the total content of nickel and manganese elements in the precursor is 0.08:1.
doping elements, wherein the elements required to be doped in the embodiment are antimony, strontium, aluminum and barium, and the doping step of the elements comprises doping antimony oxide, aluminum oxide, strontium oxide and barium oxide to prepare a doping compound, uniformly mixing the doping compound with the sample A after lithium supplement, wherein the weight ratio of the doping compound to the precursor is 0.3%.
And (3) performing secondary sintering after the element doping is finished, wherein the temperature of the secondary sintering is 820 ℃, and the time of the secondary sintering is 10h.
After the secondary sintering is finished, the coating is carried out by mixing with alumina and magnesia.
And (3) carrying out heat treatment after the coating is finished, wherein the heat treatment temperature is 600 ℃, and the heat treatment time is 7h.
And after the heat treatment is finished, obtaining a final finished product, wherein the finished product is a spinel single crystal lithium nickel manganese oxide material with the particle size of 2 um.
Example 3
A preparation process of a high-voltage single crystal anode material of a lithium ion battery comprises the following steps:
mixing soluble nickel salt and manganese salt, adding pure water after mixing to obtain a solution, adding ammonia water into the solution for mixing to obtain a coprecipitate, and carrying out solid-liquid separation on the coprecipitate by using a centrifugal machine to obtain a precursor, wherein the precursor is nickel-manganese oxide.
The precursor adopted in this embodiment is irregular-shaped particles formed by loosely agglomerated nano-crystalline grains, and the precursor has a particle size of 2.5um and a specific surface area of more than 12m 2 The tap density is less than 0.8g/cm 3 Mixing the precursor with lithium oxalate, wherein the molar ratio of the content of lithium element in the lithium oxalate to the total content of nickel and manganese elements in the precursor is 1:1.
the temperature of the primary sintering is 1000 ℃, and the time of the primary sintering is 35h. And after the primary sintering is finished, obtaining a sample A, and supplementing lithium to the sample A, wherein the lithium supplementation adopts a mode of adding lithium oxalate, and the molar ratio of the lithium content in the lithium oxalate to the total content of nickel and manganese elements in the precursor is 0.1:1.
and doping elements, wherein the required doped elements comprise yttrium element, chromium element and boron element, the doping of the elements comprises the steps of doping yttrium oxide, chromium oxide and boron oxide to prepare a doped compound, and the doped compound and the sample A after lithium supplement are uniformly mixed, wherein the weight ratio of the doped compound to the precursor is 0.5%.
And (3) carrying out secondary sintering after the element doping is finished, wherein the temperature of the secondary sintering is 900 ℃, and the time of the secondary sintering is 15h.
And after the secondary sintering is finished, the magnesium oxide and the beryllium oxide are mixed for coating.
And after the coating is finished, performing heat treatment at the temperature of 750 ℃ for 10h.
And after the heat treatment is finished, obtaining a final finished product, wherein the finished product is a spinel monocrystal lithium nickel manganese oxide material with the particle size of 6 um.
When the precursor is mixed with insufficient lithium carbonate, the reason that lithium carbonate is adopted but lithium hydroxide is not adopted is as follows: the lithium hydroxide batch production process is immature, high in cost, difficult to store for a long time, strong in corrosiveness and capable of influencing the quality of the prepared cathode material.
According to the invention, in the process of mixing the precursor and the lithium carbonate, lithium is in an insufficient state, and meanwhile, the lithium supplementing operation is carried out at the later stage, so that the capacity of the lithium battery is improved, the effect is proved by experimental data, and the experimental data are shown in a comparative example.
The invention carries out element doping to promote the growth of crystal grains.
The invention adopts lithium hydroxide to supplement lithium at the later stage, and the lithium supplement comprises two functions: 1. the pH is increased, the manganese dissolution is inhibited, and the structural stability is improved; 2. and (4) supplementing a lithium source.
Now, the effect of lithium supplement by lithium hydroxide will be described in detail, and when the operating voltage is higher than 4.5V, the lithium hexafluorophosphate in the electrolyte is decomposed to generate PF 5 And LiF. The HF generated by the reaction of LiF and trace water can dissolve manganese ions in the material and destroy the structure of the material, and meanwhile, the dissolved manganese can migrate to the negative electrode and deposit on the surface of the negative electrode, so that the impedance is increased, the polarization of the battery is increased, the capacity attenuation of the battery is caused, and the service life is shortened. Therefore, the pH value is properly increased, the dissolution of manganese can be inhibited, the structural stability is increased, and the long-circulating performance is improved.
In the circulation process, an SEI film is generated on the surface of the negative electrode, lithium ions are continuously consumed, and serious active lithium loss is caused. In addition, non-stoichiometric spinels containing a small excess of lithium are stable single-phase structures in the high potential region, in Li + The phase transformation can not occur during the separation, the cycle performance of the spinel is improved, and the cycle performance is further improved.
In the coating process, one or more of titanium oxide, aluminum oxide, magnesium oxide or beryllium oxide is adopted, so that a solid solution for fixing lithium can be formed on the surface of the lithium-containing nickel manganese oxide, and the lithium nickel manganese oxide can be protected from LiPF 6 Corrosion of HF generated by decomposition, thereby alleviating dissolution of MnAnd (4) solving.
Comparative example
The comparative example was prepared using the following process:
step a, mixing soluble nickel salt and manganese salt, adding pure water after mixing to obtain a solution, adding ammonia water into the solution for mixing to obtain a coprecipitate, and performing solid-liquid separation on the coprecipitate by using a centrifugal machine to obtain a precursor, wherein the precursor is nickel-manganese oxide;
b, mixing the precursor with lithium carbonate in a normal ratio, and heating to react to generate a sample A;
c, uniformly mixing a compound corresponding to the required doping element with the sample A by using a high-speed mixer, and sintering;
and d, coating after sintering, and performing heat treatment after coating to obtain the final required finished product of the comparative example.
The invention is compared with the product of example 1 using a comparison example:
the XRD pattern is adopted to compare the structure of the sintered lithium-supplementing alloy in example 1 with the structure of the sintered lithium-supplementing alloy in the normal lithium proportion in the comparative example, and as shown in figure 1, the structure of the sintered lithium-supplementing alloy is the same as that of the normal lithium proportion.
The particle sizes of the sample A in example 1 and the sample A in the comparative example are compared by SEM pictures, as shown in FIG. 2, the graph shows that the sample A in example 1 is single crystal, but the particle size of the sample A in example 1 is larger than that of the sample A in the comparative example, the left side picture is example 1, and the right side picture is the comparative example.
The particle size distribution of the sample A in example 1 and the particle size distribution of the sample A in the comparative example are compared by using the particle size distribution diagram, as shown in FIG. 3, it can be seen that the particle size distribution of the sample A in example 1 is larger than that of the sample A in the comparative example.
The grain sizes of the finished product in example 1 and the finished product in the comparative example are compared by adopting an SEM picture, as shown in figure 4, the grain sizes of the finished products in example 1 are both single crystals, but the grain size of the finished product in example 1 is larger than that of the finished product in the comparative example, the left picture is the example 1, the right picture is the comparative example, and the advantage of large grain size is as follows: the specific surface area is reduced, the contact between particles and electrolyte is reduced, and the high-temperature performance is improved.
The particle size distribution of the finished product of example 1 and the particle size distribution of the finished product of comparative example were compared by using the particle size distribution chart, as shown in fig. 5, it can be seen that the particle size distribution of the finished product of example 1 is larger than that of the finished product of comparative example.
The present invention uses a particle size distribution diagram to express the particle size distribution of the precursor in example 1, as shown in fig. 6.
The discharge specific capacity of the finished product in the example 1 and the discharge specific capacity of the finished product in the comparative example are compared by adopting a first-circle cycle chart, as shown in fig. 7, the discharge specific capacity of the finished product in the example 1 is larger than that of the finished product in the comparative example.
The invention adopts a discharge specific capacity long cycle diagram to compare the long cycle effects of the finished product in the example 1 and the finished product in the comparative example, as shown in figure 8, the long cycle effect of the finished product in the example 1 is better than that of the finished product in the comparative example.
The invention compares the long-cycle effect of the finished product in example 1 with that of the finished product in the comparative example by using a capacity retention rate chart, and as shown in fig. 9, the long-cycle effect of the finished product in example 1 is better than that of the finished product in the comparative example.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation process of a high-voltage single crystal cathode material of a lithium ion battery is characterized by comprising the following steps: mixing the precursor with a lithium-containing compound and sintering for the first time to obtain a sample A, then supplementing the lithium-containing compound and sintering for the second time to obtain a finished product, wherein before the first sintering, the molar ratio of the lithium content in the lithium-containing compound to the total content of nickel and manganese elements in the precursor is (0.95-1): 1, the molar ratio of the lithium content in the supplemented lithium-containing compound to the total content of nickel and manganese elements in the precursor is (0.05-0.1): 1.
2. the process according to claim 1, wherein the precursor is nickel-manganese oxide, and the lithium-containing compound mixed with the precursor is one of lithium carbonate, lithium nitrate, lithium chloride, lithium oxalate and lithium hydroxide.
3. The preparation process of the high-voltage single crystal cathode material of the lithium ion battery according to claim 1, wherein the temperature of the primary sintering is 800-1000 ℃, and the time of the primary sintering is 15-35h.
4. The process according to claim 1, wherein the additional lithium-containing compound is one of lithium carbonate, lithium nitrate, lithium chloride, lithium oxalate and lithium hydroxide.
5. The preparation process of the high-voltage single crystal cathode material of the lithium ion battery according to claim 1, wherein before the secondary sintering, an element doping step is further provided, and the element doping method comprises the following steps: and uniformly mixing the compound of the required doping element and the sample A after lithium supplement by a high-speed mixer, wherein the weight ratio of the compound of the required doping element to the precursor is 0.3-0.5%.
6. The process according to claim 5, wherein the compound of the doping element is one or more of zirconia, alumina, niobia, antimony oxide, strontium oxide, barium oxide, yttrium oxide, chromium oxide, and boron oxide.
7. The preparation process of the high-voltage single crystal cathode material of the lithium ion battery according to claim 1, wherein the temperature of the secondary sintering is 750-900 ℃, and the time of the secondary sintering is 5-15h.
8. The process according to claim 1, wherein the secondary sintering is followed by a coating step, wherein the coating step comprises mixing the mixture supplemented with the lithium-containing compound with one or more of titanium oxide, aluminum oxide, magnesium oxide, or beryllium oxide.
9. The preparation process of the high-voltage single crystal cathode material of the lithium ion battery according to claim 8, wherein the coating is followed by a heat treatment step, the heat treatment temperature is 450-750 ℃, the heat treatment time is 5-10h, and the finished product is obtained after the heat treatment.
10. The preparation process of the high-voltage single crystal positive electrode material of the lithium ion battery according to claim 1, wherein the precursor is irregular morphology particles formed by loose and aggregated nano-crystalline grains, and the precursor satisfies Dv50=0.5-3 μm and specific surface area > 12m 2 The tap density is less than 0.8g/cm 3 The finished product is spinel single crystal lithium nickel manganese oxide material with the grain diameter of 2-6 um.
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