CN114005986A - Modified ternary cathode material and preparation method and application thereof - Google Patents
Modified ternary cathode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114005986A CN114005986A CN202111247883.2A CN202111247883A CN114005986A CN 114005986 A CN114005986 A CN 114005986A CN 202111247883 A CN202111247883 A CN 202111247883A CN 114005986 A CN114005986 A CN 114005986A
- Authority
- CN
- China
- Prior art keywords
- cathode material
- lithium
- positive electrode
- ternary cathode
- modified ternary
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000010406 cathode material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 28
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 19
- 229910052796 boron Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- -1 lithium halide Chemical class 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 239000011247 coating layer Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 50
- 150000002500 ions Chemical group 0.000 abstract description 10
- 102000004310 Ion Channels Human genes 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000011572 manganese Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a modified ternary cathode material and a preparation method and application thereof2O‑B2O3Because the material has a highly disordered network structure and has a larger ion channel, when the material circulates, LiY enters the space between grids in an ion form to participate in lithium ion transmission, so that the material has good ion conductivity, and the improvement of the ion conductivity can improve the rate capability and capacity of the material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a modified ternary cathode material, and a preparation method and application thereof.
Background
At present, lithium ion batteries have been widely used in various fields such as mobile phones, notebook computers, electric bicycles and some electronic devices due to their advantages of high energy density, long cycle life, environmental friendliness, high safety and the like, and play a great role in human production and life. The anode material is an important component of the lithium ion battery and is an important factor for restricting the development of the lithium ion battery with high power and long service life. The ternary cathode material integrates the advantages of the nickel, the cobalt and the manganese and simultaneously also has the advantage of low cost, and is a cathode material with great development potential.
While the advantages of ternary materials are significant, there are some intrinsic problems, such as the generally low conductivity of the materials, resulting in poor rate performance of the battery; the high nickel material is not only easy to generate Li/Ni mixed-discharging phenomenon, but also easy to generate phase change from H2 to H3, directly influences the cycle performance of the material, and causes serious cycle attenuation. In addition, the residual alkali on the surface of the high nickel material is generally high, which is not favorable for the stability of the process and the safety of the battery; the nickel content in the medium nickel material is low, so the charge and discharge capacity is low.
CN103474628A discloses a preparation method of a carbon-coated ternary cathode material and the carbon-coated ternary cathode material, wherein the preparation method comprises the following steps: s1, preparing a ternary positive electrode material precursor by taking nickel salt, cobalt salt and manganese salt as raw materials; s2, preparing a conductive carbon dispersion system: dispersing conductive carbon in water containing an organic carbon source; s3, adding the ternary positive electrode material precursor and the lithium compound into the conductive carbon dispersion system, and uniformly mixing to obtain a mixture; s4, drying the mixture under a vacuum condition; and S5, carrying out high-temperature treatment on the dried mixture under a sealed condition or in an atmosphere protected by inert gas to obtain the carbon-coated ternary cathode material. The carbon-coated ternary cathode material is used, carbon coating only can play a role of a conductive agent and cannot realize large change in material performance, the carbon coating process has high requirement on coating amount, the small coating amount does not have an obvious effect on improving the conductivity of the material, and the large coating amount can hinder the deintercalation of lithium ions and seriously affect the exertion of material capacity.
CN110729466A discloses a boron oxide coated high-nickel ternary cathode material and a preparation method thereof, wherein liquid pentaborane is added in the preparation process, and the pentaborane can be rapidly hydrolyzed and released heat when meeting water on the surface of the material to form an oxide coating layer.
The ternary cathode material prepared by the scheme has the problems of low conductivity and poor rate capability, so that the development of the ternary cathode material with high conductivity and good rate capability is necessary.
Disclosure of Invention
The invention aims to provide a modified ternary cathode material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a modified ternary cathode material, which comprises a core and a coating layer, wherein the coating layer is a halogenated boride, and the halogenated boride comprises Li2O、B2X3And LiY, wherein X is S and/or O, and Y is any one or the combination of at least two of F, Cl, Br or I.
The surface of the modified ternary cathode material is provided with the halogenated boride coating layer, and the halogenated boride has a high disordered network structure and a large ion channel, so that the modified ternary cathode material has high ion mobility, and meanwhile, LiY enters grids in an ion form to participate in lithium ion transmission during circulation of the halogenated boride, so that the material has good ion conductivity, and the introduction of the LiY is mainly benefited. The improvement of the ionic conductivity can improve the rate capability of the material and improve the capacity of the material.
Preferably, the core has the formula LiNixCoyMnzA1-x-y-zO2Wherein x is more than or equal to 0.5<1, for example: 0.5, 0.6, 0.7, or 0.9, and the like, and y is more than or equal to 0 and less than or equal to 0.2, for example: 0. 0.05, 0.1, 0.15, or 0.2, etc., 0. ltoreq. z.ltoreq.0.3, for example: 0. 0.1, 0.15, 0.2, 0.25, 0.3, etc., A is any one or combination of at least two of Al, B, Ta, Zr, Nb, La, Sr, Mo, Y, W, Ba or Si.
Preferably, the particle size of the inner core is 2.6 to 4 μm, for example: 2.6 μm, 3 μm, 3.2 μm, 3.5 μm, 3.8 μm, 4 μm, or the like.
In a second aspect, the present invention provides a method for preparing the modified ternary cathode material according to the first aspect, wherein the method comprises the following steps:
(1) mixing an oxygen-containing lithium source, a boron source, lithium halide and a solvent to obtain a coating solution;
(2) and (2) mixing the ternary cathode material with the coating solution obtained in the step (1), evaporating the solvent, and sintering to obtain the modified ternary cathode material.
The ternary material is coated by the halogenated boride through a liquid phase method, and the amorphous halogenated boride has a highly disordered network structure and has a larger ion channel, so that the amorphous halogenated boride has higher ion mobility, and the introduction of LiY (Y ═ F, Cl, Br and I) is mainly benefited. The improvement of lithium ion mobility can improve the rate capability of the material and improve the capacity of the material.
Preferably, the oxygen-containing lithium source of step (1) comprises LiOH and/or Li2CO3。
Preferably, the boron source comprises H3BO3、B2O3Or B2S3Any one or a combination of at least two of them.
Preferably, the lithium halide comprises any one or a combination of at least two of LiF, LiCl, LiBr, or LiI.
Preferably, the solvent comprises deionized water.
Preferably, the molar ratio of the lithium element in the oxygen-containing lithium source, the boron element in the boron source and the lithium halide in the step (1) is (1.8-2.1): (0.8-1.1), for example: 1.8:2:0.9, 1.9:1.9:1, 1.9:1.8:1.1, 2:2:1 or 2.1:2.1:1.1, etc., preferably 2:2: 1.
Preferably, the temperature of the mixing in the step (1) is 30-45 ℃, for example: 30 ℃, 32 ℃, 35 ℃, 40 ℃ or 45 ℃ and the like.
Preferably, the mass ratio of the total mass of the oxygen-containing lithium source, the boron source and the lithium halide in the coating liquid in the step (2) to the ternary cathode material is 0.02-0.05: 1, for example: 0.02:1, 0.03:1, 0.04:1 or 0.05:1, etc.
Preferably, the mixing of step (2) is performed while stirring.
Preferably, the stirring speed is 15-25 r/s, such as: 15r/s, 18r/s, 20r/s, 22r/s or 25r/s, etc.
Preferably, the temperature of the mixing in the step (2) is 80-90 ℃, for example: 80 ℃, 82 ℃, 85 ℃, 88 ℃ or 90 ℃ and the like.
Preferably, the temperature of the sintering treatment in the step (2) is 450-700 ℃, for example: 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or 700 ℃, preferably 550-650 ℃.
Preferably, the time of the sintering treatment is 6-12 h, for example: 6h, 8h, 10h or 12h and the like.
Preferably, the temperature rise rate of the sintering treatment is 2-5 ℃/min, for example: 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min and the like.
In a third aspect, the invention provides a positive electrode plate, which comprises the modified ternary positive electrode material according to the first aspect.
In a fourth aspect, the invention provides a lithium ion battery, which comprises the positive electrode plate according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) when the modified ternary cathode material is circulated, lithium halide enters grids in an ion form to participate in lithium ion transmission, so that the material has good ionic conductivity, and the increase of the ionic conductivity can improve the rate capability and capacity of the material.
(2) The ternary material is coated by the halogenated boride through a liquid phase method, the preparation method is simple, the purity of the coating is high, the controllability of the coating amount is strong, a uniform coating layer is easy to form, the cost of the preparation method is low, and industrial mass production can be realized.
(3) The battery prepared from the modified ternary cathode material has the specific discharge capacity of 0.1C of more than 189.65mAh/g, the specific discharge capacity of 1C of more than 170.59mAh/g and the capacity retention rate of 1C of more than 96.5 percent.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a modified ternary cathode material, which is prepared by the following method:
(1) the ternary precursor Ni0.6Co0.1Mn0.3(OH)2And lithium salt in a molar ratio of 1: 1.04 and putting the mixture into a high-speed mixer, uniformly mixing, transferring the mixture into an atmosphere furnace, introducing oxygen, and sintering the mixture for 12 hours at 970 ℃. Cooling with the furnace, taking out the material, crushing, grinding and sieving the material to prepare the cathode material calcined LiNi product with the grain diameter of 3.2 mu m0.6Co0.1Mn0.3O2；
(2) Weighing LiOH and H according to the molar ratio of 2:2:13BO3And LiF, the total mass of which is 3.5 percent of the mass of the ternary anode one-fired product, dissolving the three raw materials in 100mL of deionized water, then placing the mixed solution in a water bath kettle, and stirring at a constant speed at 30 ℃ until the raw materials are completely dissolved to obtain a coating solution;
(3) keeping the stirring speed of 20r/s, slowly pouring the ternary positive electrode calcined product into the coating liquid, then placing the mixed liquid into a water bath, stirring at a constant speed at 80 ℃ until the solution is completely evaporated, and drying the evaporated material;
(4) and (3) putting the dried material into an atmosphere furnace, introducing air, and sintering for 8h at 550 ℃. And after furnace cooling, sieving the material to obtain the modified ternary cathode material.
Example 2
This embodiment provides a modified ternary cathode material, which is prepared by the following method:
(1) the ternary positive electrode precursor Ni0.65Mn0.28Al0.07(OH)2And lithium salt in a molar ratio of 1: 1.05 weighing and placing into a high-speed mixer, uniformly mixing, transferring into an atmosphere furnace, introducing oxygen, and sintering at 950 ℃ for 10 hours. Cooling with the furnace, taking out the material, crushing, grinding and sieving the material to prepare the cathode material calcined LiNi product with the grain diameter of 3.1 mu m0.65Mn0.28Al0.07O2；
(2) Weighing Li according to the molar ratio of 1:1:12CO3、B2O3And LiCl, the total mass of which is 3 percent of the mass of the ternary positive electrode one-burning product, dissolving the three raw materials in 100mL of deionized water, then placing the mixed solution in a water bath kettle, and stirring at a constant speed at 41 ℃ until the raw materials are completely dissolved to obtain a coating solution;
(3) keeping the stirring speed of 18r/s, slowly pouring the ternary positive electrode calcined product into the coating liquid, then placing the mixed liquid into a water bath, stirring at a constant speed at 85 ℃ until the solution is completely evaporated, and drying the evaporated material;
(4) and (3) putting the dried material into an atmosphere furnace, introducing air, and sintering for 5 hours at 650 ℃. After furnace cooling, the material is sieved to obtain Li2O-B2O3-LiCl coated ternary cathode material finished product.
Example 3
This embodiment provides a modified ternary cathode material, which is prepared by the following method:
(1) the ternary positive electrode precursor Ni0.7Co0.1Mn0.2(OH)2And lithium salt in a molar ratio of 1: 1.06 weighing and placing into a high-speed mixer, uniformly mixing, transferring into an atmosphere furnace, introducing oxygen, and sintering for 12h at 780 ℃. Cooling with the furnace, takingDischarging the material, crushing, grinding and sieving the material to prepare the positive electrode material-calcined LiNi product with the particle size of 2.9 mu m0.7Co0.1Mn0.2O2；
(2) The molar ratio of the raw materials is 2: 1:1 weighing LiOH and B2S3And LiBr, the total mass is 3% of the mass of the ternary positive electrode primary combustion product, the three raw materials are dissolved in 100mL of deionized water, then the mixed solution is placed in a water bath kettle, and the mixture is stirred at a constant speed at 37 ℃ until the raw materials are completely dissolved, so that the coating solution is prepared;
(3) keeping the stirring speed of 22r/s, slowly pouring the ternary positive electrode calcined product into the coating liquid, then placing the mixed liquid into a water bath, stirring at a constant speed at 90 ℃ until the solution is completely evaporated, and drying the evaporated material;
(4) and (3) putting the dried material into an atmosphere furnace, introducing air, and sintering for 6h at the temperature of 600 ℃. And (4) after furnace cooling, sieving the material to obtain the modified ternary cathode material finished product.
Example 4
This example differs from example 1 only in that the ternary positive electrode precursor is high nickel Ni0.8Co0.11Mn0.09(OH)2The materials, other conditions and parameters were exactly the same as in example 1.
Example 5
This example differs from example 1 only in that the ternary positive electrode precursor is ultra-high nickel Ni0.96Co0.02Mn0.02(OH)2The materials, other conditions and parameters were exactly the same as in example 1.
Example 6
The difference between the present example and example 1 is that the total mass of the solute in the coating solution is 1.5% of the mass of the ternary positive electrode calcined product, and the other conditions and parameters are completely the same as those in example 1.
Example 7
The difference between the present example and example 1 is that the total mass of the solute in the coating solution is 5.5% of the mass of the ternary positive electrode calcined product, and the other conditions and parameters are completely the same as those in example 1.
Example 8
This example is different from example 1 only in that the sintering temperature in step (4) is 500 ℃, and other conditions and parameters are exactly the same as those in example 1.
Example 9
This example is different from example 1 only in that the sintering temperature in step (4) is 700 ℃, and other conditions and parameters are exactly the same as those in example 1.
Comparative example 1
This comparative example differs from example 1 only in that, without addition of lithium halide, only conventional boron cladding is used, the other conditions and parameters being exactly the same as in example 1.
Comparative example 2
This comparative example differs from example 4 only in that, without addition of lithium halide, only conventional boron cladding is used, the other conditions and parameters being exactly the same as in example 4.
And (3) performance testing:
the finished products prepared in the above examples and comparative examples were mixed in a mass ratio of 92: 4: 4, a proper amount of NMP is added as a dispersing agent to prepare a positive pole piece, then a button half cell is assembled in an argon glove box, and the electrochemical performance of the button half cell is tested under the cut-off voltage of 4.2/4.3/4.4V (the test voltage of examples 1-3 and 6-9 is 4.4V, the test voltage of example 4 is 4.3V, and the test voltage of example 5 is 4.2V), and the test results are shown in Table 1:
TABLE 1
As can be seen from Table 1, in examples 1-9, the 0.1C specific discharge capacity of the battery prepared by using the modified ternary cathode material of the invention can reach more than 189.65mAh/g, the 1C specific discharge capacity can reach more than 170.59mAh/g, and the 1C capacity retention rate can reach more than 96.5%.
As can be seen from comparison between example 1 and examples 6 to 7, the mass ratio of the solute in the coating solution to the calcined material affects the performance of the modified ternary cathode material, and if the mass ratio of the solute in the coating solution to the calcined material is too high, the coating layer of the particles is too thick, the diffusion path of ions is prolonged, the barrier effect on the diffusion of lithium ions is increased, and the rate capability and capacity of the material are reduced. If the mass ratio of the solute in the coating liquid to the primary sintered material is too low, the coating effect is reduced, and part of naked particles appear, which increase the probability of side reaction with the electrolyte, thereby causing the reduction of the cycle performance of the material.
Compared with the examples 8 to 9, in the process of preparing the modified ternary cathode material, the sintering temperature affects the performance of the prepared modified ternary cathode material, and if the sintering temperature is too high, the particles of the coating agent grow and a compact coating layer is difficult to form, so that the migration path of lithium ions is prolonged, the isolation effect of the coating layer on the electrolyte is reduced, and the multiplying power and the cycle performance of the material are reduced. If the sintering temperature is too low, the coating formed on the particle surface is not tight enough, and the coating is easy to fall off during the circulation of the material, thereby causing the chemical corrosion of the electrolyte, causing the dissolution of the metal and the rapid reduction of the material circulation performance.
Compared with the examples 1 and 4 and the comparative examples 1 and 2, the invention adds the lithium halide on the basis of boride coating to form the halogenated boride, and the halogenated boride has a highly disordered network structure and has larger ion channels, so that the halogenated boride has higher ion mobility, and the introduction of LiY (Y ═ F, Cl, Br and I) is mainly benefited, and the improvement of the lithium ion mobility can improve the rate capability of the material and improve the capacity of the material.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The modified ternary cathode material is characterized by comprising a core and a coating layer, wherein the coating layer is a halogenated boride, and the halogenated boride comprises Li2O、B2X3And LiY, wherein X is S and/or O, and Y is any one or the combination of at least two of F, Cl, Br or I.
2. The modified ternary positive electrode material of claim 1, wherein the core has the formula LiNixCoyMnzA1-x-y-zO2Wherein x is more than or equal to 0.5<1, Y is more than or equal to 0 and less than or equal to 0.2, z is more than or equal to 0 and less than or equal to 0.3, A is any one or the combination of at least two of Al, B, Ta, Zr, Nb, La, Sr, Mo, Y, W, Ba or Si;
preferably, the particle size of the inner core is 2.6-4 μm.
3. A method for preparing the modified ternary positive electrode material according to claim 1 or 2, comprising the steps of:
(1) mixing an oxygen-containing lithium source, a boron source, lithium halide and a solvent to obtain a coating solution;
(2) and (2) mixing the ternary cathode material with the coating solution obtained in the step (1), evaporating the solvent, and sintering to obtain the modified ternary cathode material.
4. The method of claim 3, wherein the oxygen-containing lithium source of step (1) comprises LiOH and/or Li2CO3；
Preferably, the boron source comprises H3BO3、B2O3Or B2S3Any one or a combination of at least two of;
preferably, the lithium halide comprises any one or a combination of at least two of LiF, LiCl, LiBr, or LiI;
preferably, the solvent comprises deionized water.
5. The method according to claim 3 or 4, wherein the molar ratio of the lithium element in the oxygen-containing lithium source, the boron element in the boron source and the lithium halide in the step (1) is (1.8-2.1): (0.8-1.1), preferably 2:2: 1;
preferably, the mixing temperature in the step (1) is 30-45 ℃.
6. The preparation method according to any one of claims 3 to 5, wherein the mass ratio of the total mass of the oxygen-containing lithium source, the boron source and the lithium halide in the coating liquid in the step (2) to the ternary cathode material is 0.02 to 0.05: 1.
7. The method according to any one of claims 3 to 6, wherein the mixing in step (2) is carried out while stirring;
preferably, the stirring speed is 15-25 r/s;
preferably, the mixing temperature in the step (2) is 80-90 ℃.
8. The method according to any one of claims 3 to 7, wherein the sintering treatment in the step (2) is performed at a temperature of 450 to 700 ℃, preferably 550 to 650 ℃;
preferably, the sintering treatment time is 6-12 h;
preferably, the temperature rise speed of the sintering treatment is 2-5 ℃/min.
9. A positive electrode sheet comprising the modified ternary positive electrode material according to claim 1 or 2.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111247883.2A CN114005986A (en) | 2021-10-26 | 2021-10-26 | Modified ternary cathode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111247883.2A CN114005986A (en) | 2021-10-26 | 2021-10-26 | Modified ternary cathode material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114005986A true CN114005986A (en) | 2022-02-01 |
Family
ID=79924190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111247883.2A Pending CN114005986A (en) | 2021-10-26 | 2021-10-26 | Modified ternary cathode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114005986A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114583102A (en) * | 2022-02-21 | 2022-06-03 | 远景动力技术(江苏)有限公司 | Positive electrode active material, electrochemical device, and electronic device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1773753A (en) * | 2004-11-08 | 2006-05-17 | 深圳市比克电池有限公司 | Lithium ion battery anode material and producing method thereof |
| CN106299305A (en) * | 2016-09-29 | 2017-01-04 | 中国科学院新疆理化技术研究所 | A kind of fast-ionic conductor coating modification method of ternary cathode material of lithium ion battery |
| CN108206277A (en) * | 2016-12-20 | 2018-06-26 | 宁德时代新能源科技股份有限公司 | Modified high-nickel ternary cathode material, preparation method thereof and lithium ion battery |
-
2021
- 2021-10-26 CN CN202111247883.2A patent/CN114005986A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1773753A (en) * | 2004-11-08 | 2006-05-17 | 深圳市比克电池有限公司 | Lithium ion battery anode material and producing method thereof |
| CN106299305A (en) * | 2016-09-29 | 2017-01-04 | 中国科学院新疆理化技术研究所 | A kind of fast-ionic conductor coating modification method of ternary cathode material of lithium ion battery |
| CN108206277A (en) * | 2016-12-20 | 2018-06-26 | 宁德时代新能源科技股份有限公司 | Modified high-nickel ternary cathode material, preparation method thereof and lithium ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114583102A (en) * | 2022-02-21 | 2022-06-03 | 远景动力技术(江苏)有限公司 | Positive electrode active material, electrochemical device, and electronic device |
| CN114583102B (en) * | 2022-02-21 | 2023-08-15 | 远景动力技术(江苏)有限公司 | Positive electrode active material, electrochemical device, and electronic device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112242516B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN111106337B (en) | Carbon nano tube modified lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN113937286B (en) | Coated modified sodium ion battery positive electrode material, preparation method thereof and battery | |
| CN113651304A (en) | Organic carbon-coated lithium iron phosphate cathode material and preparation method thereof | |
| CN110148712B (en) | Composite coating modified lithium-manganese-rich cathode material and preparation method thereof | |
| CN112510192B (en) | Positive electrode slurry and application thereof | |
| CN113871605A (en) | Pre-lithiated silicon-based negative electrode material and preparation method and application thereof | |
| WO2014071724A1 (en) | Lithium-rich anode material, lithium battery anode, and lithium battery | |
| CN114005986A (en) | Modified ternary cathode material and preparation method and application thereof | |
| CN109216692B (en) | Modified ternary cathode material, preparation method thereof and lithium ion battery | |
| CN114597370B (en) | Air-stable high-voltage long-cycle-life sodium ion battery positive electrode material and preparation method thereof | |
| CN115072797B (en) | Preparation method and application of lithium ion battery anode material | |
| CN115275168A (en) | High-rate lithium ion battery negative electrode material and preparation method thereof | |
| CN114249310B (en) | Lithium ion battery composite anode material LiMn 1-x Fe x PO 4 Synthesis method of/C | |
| CN114927777A (en) | Ultrahigh lithium content material and self-supplementing lithium composite positive electrode material | |
| CN114906882A (en) | Preparation method and application of niobium-based bimetal oxide negative electrode material | |
| CN114079043A (en) | High-nickel positive electrode material, lithium ion battery and preparation method of high-nickel positive electrode material | |
| CN110783544A (en) | Carbon nanotube coated H 3PO 4Modified lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN117558905B (en) | Sodium-iron double-position doped polyanion positive electrode material and preparation method thereof | |
| CN109301205A (en) | A kind of dedicated anti-inflatable lithium titanate anode material of lithium battery and preparation method | |
| CN112678876B (en) | Application of LiFe4Mo5O20 in lithium ion battery cathode | |
| CN117691095B (en) | Lithium-rich all-solid-state battery positive electrode material, preparation method and application thereof | |
| CN114835100B (en) | Preparation method of lithium battery positive electrode material and lithium battery positive electrode material | |
| CN111092200A (en) | Li3Cr(MoO4)3Coating modified high-nickel ternary cathode material and preparation method thereof | |
| CN117393717A (en) | Lithium ion battery anode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220201 |