CN110931745A - Method for reducing resistivity of ternary positive electrode material - Google Patents
Method for reducing resistivity of ternary positive electrode material Download PDFInfo
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- CN110931745A CN110931745A CN201911202350.5A CN201911202350A CN110931745A CN 110931745 A CN110931745 A CN 110931745A CN 201911202350 A CN201911202350 A CN 201911202350A CN 110931745 A CN110931745 A CN 110931745A
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 17
- 239000010406 cathode material Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 5
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 5
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 2
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000010405 anode material Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—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
- 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
-
- 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
- H01M4/624—Electric conductive fillers
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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
- 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
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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 Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to the field of lithium ion batteries, and discloses a method for reducing the resistivity of a ternary cathode material, which comprises the following steps: (1) mixing a ternary positive electrode material with hydroxide to obtain a mixture; (2) sintering the mixture, cooling and sieving to obtain the product. According to the invention, the hydroxide is adopted to coat the high-resistivity ternary cathode material, so that the resistivity of the ternary cathode material can be effectively reduced. Because the DCR and the cycle performance of the ternary cathode material in the battery can be influenced by higher resistivity, the increase of the internal resistance of the battery and the reduction of the cycle performance caused by higher resistivity of the material can be avoided by reducing the powder resistivity of the ternary cathode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a method for reducing the resistivity of a ternary cathode material.
Background
In recent years, countries have implemented a series of policies about new energy vehicles, which greatly promote the development of lithium ion batteries. The performance of the anode material directly influences the capacity, service life, storage and other performances of the lithium ion battery, so that the novel anode material occupies a core position in the next generation lithium ion battery technology.
The detection of the positive electrode material is also an important process of research and development, and because the battery performance test period of the positive electrode material is long, people are difficult to quickly identify the performance difference of the material so as to carry out optimization design. In order to accelerate the development progress, people are concerned about rapid electrical property tests related to the performance of batteries so as to screen out excellent positive electrode materials. Nowadays, the powder resistivity test of materials is a more applied item, and researchers consider that the powder resistivity of materials has a certain correlation with the DCR and the cycle performance. In order to improve a series of problems of the ternary cathode material along with the increase of the Ni content, the performance of the ternary cathode material is generally improved in a coating mode, however, the powder resistivity of the ternary cathode material is increased linearly along with the increase of the coating type and the coating amount, and the cycle performance of the ternary cathode material is restricted. Therefore, the preparation of the ternary cathode material with low resistivity is one of the ways for improving the performance of the material battery.
Disclosure of Invention
The invention aims to provide a method for improving the resistivity of a ternary cathode material. The method can reduce the resistivity of the ternary anode material and improve the cycle performance of the ternary anode material on the premise of not influencing the structure of the ternary anode material; the ternary cathode material coating scheme provided by the invention has the advantages of obvious effect, simplicity, easiness and easiness in industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for reducing the resistivity of a ternary cathode material comprises the following steps:
(1) mixing a ternary positive electrode material with hydroxide to obtain a mixture;
(2) sintering the mixture, cooling and sieving to obtain the product.
Preferably, the chemical formula of the ternary cathode material in the step (1) is LiNixCoyMn1-x-yO2In which 1 is>x≥0.5，0<y≤0.2。
Preferably, the hydroxide in the step (1) is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, cobalt hydroxide, nickel hydroxide and manganese hydroxide. More preferably, the hydroxide is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
Preferably, the weight ratio of the hydroxide and the ternary cathode material in the step (1) is 0.01-0.3: 1;
preferably, the resistivity of the ternary cathode material in the step (1) is 2000-100000 Ω -cm.
Preferably, the sintering temperature of the step (2) is 250-650 ℃, and the sintering time is 2-8 h.
Preferably, the cooling of step (2) is to room temperature.
Preferably, the sieving in the step (2) uses 100-200 meshes.
A ternary cathode material is prepared by the method.
Preferably, the resistivity of the ternary positive electrode material is measured at a pressure of 12Mpa using a four-probe method.
The invention has the advantages that:
1. according to the invention, the hydroxide is adopted to coat the high-resistivity ternary cathode material, so that the resistivity of the ternary cathode material can be effectively reduced.
2. Because the DCR and the cycle performance of the ternary cathode material in the battery can be influenced by higher resistivity, the increase of the internal resistance of the battery and the reduction of the cycle performance caused by higher resistivity of the material can be avoided by reducing the powder resistivity of the ternary cathode material.
3. According to the invention, the hydroxide is adopted to coat the high-resistivity ternary cathode material, so that the resistivity of the ternary cathode material can be effectively reduced, the products with unqualified resistivity are ensured to be reused by reworking, the production qualified rate is improved, and the enterprise cost is reduced.
Drawings
Fig. 1 is an SEM image of a ternary cathode material before coating in example 1;
FIG. 2 is an SEM image of the coated ternary cathode material of example 1;
FIG. 3 is an SEM image of a ternary cathode material of example 2 before coating;
fig. 4 is an SEM image of the coated ternary cathode material of example 2.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below with reference to the examples to further illustrate the features and advantages of the invention, and any changes or modifications that do not depart from the gist of the invention will be understood by those skilled in the art to which the invention pertains, the scope of which is defined by the scope of the appended claims.
Example 1
A method of improving the resistivity of a ternary positive electrode material, comprising the steps of:
(1) a ternary positive electrode material LiNi having a resistivity of 30000. omega. cm as measured at 12MPa by a four-probe method0.5Co0.2Mn0.3O2With sodium hydroxidePlacing the mixture in mixing equipment, and uniformly mixing to obtain a mixture, wherein the weight ratio of the sodium hydroxide to the ternary cathode material is 0.15: 1;
(2) and placing the obtained mixture in a kiln at the temperature of 550 ℃ for sintering for 6h, cooling to room temperature, and sieving to obtain the ternary cathode material with the resistivity of 1659 omega cm.
Example 2
A method of improving the resistivity of a ternary positive electrode material, comprising the steps of:
(1) a ternary positive electrode material LiNi with the resistivity of 17850 omega cm measured by a four-probe method under 12Mpa0.8Co0.1Mn0.1O2Uniformly mixing the lithium hydroxide and the lithium hydroxide in mixing equipment to obtain a mixture, wherein the weight ratio of the lithium hydroxide to the ternary cathode material is 0.06: 1;
(2) and placing the obtained mixture in a kiln at the temperature of 350 ℃ for sintering for 4h, cooling to room temperature, and sieving to obtain the ternary cathode material with the resistivity of 1445 omega cm.
Example 3
A method of improving the resistivity of a ternary positive electrode material, comprising the steps of:
(2) a ternary positive electrode material LiNi with the resistivity of 6440 omega cm measured at 12MPa by a four-probe method0.9Co0.05Mn0.05O2Placing the cobalt hydroxide and the cobalt hydroxide in a mixing device to be uniformly mixed to obtain a mixture, wherein the weight ratio of the cobalt hydroxide to the ternary cathode material is 0.03: 1;
(2) and placing the obtained mixture in a kiln at the temperature of 450 ℃ for sintering for 4h, cooling to room temperature, and sieving to obtain the ternary cathode material with the resistivity of 1032 omega cm.
TABLE 1
Table 1 shows the results of the powder resistivity and the decrease rate of the resistivity before and after coating of the ternary positive electrode materials of examples 1 to 3, and the maximum decrease rate of the resistivity after coating reached 94.58%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (7)
1. A method for reducing the resistivity of a ternary cathode material is characterized in that: the method comprises the following steps:
(1) mixing a ternary positive electrode material with hydroxide to obtain a mixture;
(2) sintering the mixture, cooling and sieving.
2. The method of claim 1, wherein: the chemical formula of the ternary cathode material in the step (1) is LiNixCoyMn1-x-yO2In which 1 is>x≥0.5，0<y≤0.2。
3. The method of claim 1, wherein: the hydroxide in the step (1) is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, cobalt hydroxide, nickel hydroxide and manganese hydroxide.
4. The method of claim 1, wherein: the weight ratio of the hydroxide to the ternary cathode material in the step (1) is 0.01-0.3: 1.
5. The method of claim 1, wherein: the sintering temperature in the step (2) is 250-650 ℃, and the sintering time is 2-8 h.
6. The method of claim 1, wherein: the resistivity of the ternary cathode material in the step (1) is 2000-100000 omega-cm.
7. A ternary positive electrode material characterized in that: prepared by the process of any one of claims 1 to 6.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911202350.5A CN110931745A (en) | 2019-11-29 | 2019-11-29 | Method for reducing resistivity of ternary positive electrode material |
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| CN201911202350.5A CN110931745A (en) | 2019-11-29 | 2019-11-29 | Method for reducing resistivity of ternary positive electrode material |
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| CN106207128A (en) * | 2016-08-31 | 2016-12-07 | 南开大学 | A kind of Zr (OH)4the preparation method of cladding nickel cobalt aluminum tertiary cathode material |
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| CN109428061A (en) * | 2017-08-28 | 2019-03-05 | 中国科学院宁波材料技术与工程研究所 | A kind of core-shell material |
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2019
- 2019-11-29 CN CN201911202350.5A patent/CN110931745A/en active Pending
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