CN114975932A - Conductive oxide coated high-nickel ternary lithium ion battery positive electrode material and preparation method thereof - Google Patents
Conductive oxide coated high-nickel ternary lithium ion battery positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN114975932A CN114975932A CN202210616810.4A CN202210616810A CN114975932A CN 114975932 A CN114975932 A CN 114975932A CN 202210616810 A CN202210616810 A CN 202210616810A CN 114975932 A CN114975932 A CN 114975932A
- Authority
- CN
- China
- Prior art keywords
- nickel ternary
- conductive oxide
- lithium ion
- ion battery
- nickel
- 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.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 122
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 title claims description 40
- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical group O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000010405 anode material Substances 0.000 claims abstract description 44
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000010406 cathode material Substances 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000011572 manganese Substances 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 25
- 229910013716 LiNi Inorganic materials 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 19
- 229910021645 metal ion Inorganic materials 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 14
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 238000004729 solvothermal method Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000007772 electrode material Substances 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 8
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- OAWZTKNCHQQRKF-UHFFFAOYSA-L manganese(3+);4-[10,15,20-tris(4-carboxyphenyl)porphyrin-22,24-diid-5-yl]benzoic acid Chemical compound [Mn+3].C1=CC(C(=O)O)=CC=C1C(C1=CC=C([N-]1)C(C=1C=CC(=CC=1)C(O)=O)=C1C=CC(=N1)C(C=1C=CC(=CC=1)C(O)=O)=C1C=CC([N-]1)=C1C=2C=CC(=CC=2)C(O)=O)=C2N=C1C=C2 OAWZTKNCHQQRKF-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- H01M4/48—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
- H01M4/36—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
-
- 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
Abstract
The invention provides a high-nickel ternary lithium ion battery anode material coated by conductive oxides and a preparation method thereof, belonging to the technical field of lithium ion battery anode materials. The high-nickel ternary lithium ion battery anode material coated by the conductive oxide comprises a high-nickel ternary anode material and the conductive oxide coated on the surface of the high-nickel ternary anode material; the conductive oxide is antimony tin oxide and/or zinc stannate. According to the invention, the surface of the high-nickel ternary lithium ion battery anode material is coated with a layer of antimony tin oxide and/or zinc stannate, so that direct contact between an active electrode material and an electrolyte can be prevented, side reaction between the electrode material and the electrolyte and corrosion of a decomposition product of the electrolyte to the electrode material can be prevented, and the stability of the material in a circulating process can be improved; the conductive oxide has higher electronic and ionic conductivity, so that the discharge specific capacity and the rate capability of the high-nickel ternary lithium ion battery anode material can be improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a high-nickel ternary lithium ion battery anode material coated by conductive oxides and a preparation method thereof.
Background
Lithium Ion Batteries (LIBs) have dominated the energy storage field as an energy storage device that is different from conventional energy sources. In the modern portable application product market, lithium ion batteries are widely introduced in 3C digital products, mobile power sources, electric tools, wearable electronic products, and the like. In addition, as automobiles in China gradually become rigid requirements for people to go out, new energy automobiles are rapidly popularized due to light pollution and low energy consumption. The lithium ion battery has the advantages of high specific energy, low self-discharge, good cycle performance, no memory effect, environmental protection and the like, and is a high-efficiency secondary battery with the greatest development prospect and a chemical energy storage power source with the fastest development. The replacement of traditional fossil fuels by power lithium ion batteries has become the direction of intensive research in countries and large enterprises in the world.
High nickel ternary positive electrode material Li [ Ni ] (1-x-y) Co x Mn y ]O 2 (x+y<1) Due to the incorporation of LiCoO 2 、LiNiO 2 And LiMnO 2 The material has the advantages of high discharge specific capacity, good cycling stability and good safety performance, is favored by researchers, and gradually becomes one of the preferred anode materials of the next generation of high-energy lithium batteries. However, the high nickel ternary positive electrode material also has the following drawbacks: 1) an unstable interface due to side reactions can create certain safety issues; 2) corrosion of the active material and decomposition of the electrolyte can have a severe impact on the transfer of charge at the electrode and electrolyte interface.
In order to overcome the defects of the high-nickel ternary cathode material, one of the main technical means is surface coating, and the coating mainly comprises zirconium dioxide, aluminum phosphate, aluminum oxide, magnesium oxide and the like at present, so that the chemical reaction between the active electrode material and water and carbon dioxide in the air can be isolated, and the electrochemical inertia LiOH/Li is reduced 2 CO 3 And impurities are formed, so that the interface stability and the structural stability of the high-nickel ternary cathode material are improved. However, the existence of the above coating layer is not favorable for lithium ion transmission, and can affect the rate capability of the high-nickel ternary cathode material.
Disclosure of Invention
In view of the above, the present invention aims to provide a conductive oxide coated high nickel ternary lithium ion battery positive electrode material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-nickel ternary lithium ion battery anode material coated with conductive oxides, which comprises a high-nickel ternary anode material and conductive oxides coated on the surface of the high-nickel ternary anode material;
the chemical composition of the high-nickel ternary cathode material is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.5, and x + y is less than 1;
the conductive oxide is antimony tin oxide and/or zinc stannate.
Preferably, the mass ratio of the conductive oxide to the high-nickel ternary cathode material is 0.005-0.05: 1.
Preferably, the thickness of the conductive oxide is 1-5 nm;
the particle size of the conductive oxide coated high-nickel ternary lithium ion battery anode material is 1-10 mu m.
The invention provides a preparation method of the conductive oxide coated high-nickel ternary lithium ion battery anode material, which comprises the following steps:
(1) system for makingHas a chemical composition of LiNi x Co y Mn 1-x-y O 2 The high nickel ternary positive electrode material;
(2) ultrasonically mixing conductive oxide, a high-nickel ternary positive electrode material and a dispersion solvent to obtain a mixed solution;
drying and calcining the mixed solution in sequence to obtain a conductive oxide coated high-nickel ternary lithium ion battery anode material;
alternatively, the first and second electrodes may be,
mixing a preparation raw material of a conductive oxide, a high-nickel ternary positive electrode material and an organic solvent, and carrying out a solvothermal reaction to obtain a precursor of the positive electrode material of the lithium ion battery;
and drying and carrying out secondary calcination on the precursor of the lithium ion battery anode material to obtain the high-nickel ternary lithium ion battery anode material coated by the conductive oxide.
Preferably, the frequency of ultrasonic mixing is 40-60 kHz, and the time is 20-30 min.
Preferably, when the conductive oxide is antimony tin oxide, the raw materials for preparing the conductive oxide comprise antimony acetate and tin acetate, and the molar ratio of the antimony acetate to the tin acetate is 0.1-0.5: 1;
when the conductive oxide is zinc stannate, the preparation raw materials of the conductive oxide comprise zinc acetate and tin acetate, and the molar ratio of the zinc acetate to the tin acetate is 1-2: 1.
Preferably, the temperature of the solvothermal reaction is 180-210 ℃, and the heat preservation time is 6-24 h.
Preferably, the temperature of the first calcination and the second calcination is independently 400-700 ℃, and the heat preservation time is independently 4-6 h.
Preferably, the preparation method of the high-nickel ternary cathode material comprises the following steps:
mixing a soluble nickel source, a soluble cobalt source and a soluble manganese source with water to obtain a metal ion solution;
mixing the metal ion solution with a NaOH solution and an ammonia water solution, and sequentially stirring and aging to obtain a nickel-cobalt-manganese hydroxide precursor;
and mixing the nickel-cobalt-manganese hydroxide precursor with a lithium source, and sequentially performing presintering and sintering to obtain the high-nickel ternary cathode material.
Preferably, the pre-sintering temperature is 450-600 ℃, and the heat preservation time is 4-6 h;
the sintering temperature is 700-950 ℃, and the heat preservation time is 6-15 h.
The invention provides a high-nickel ternary lithium ion battery anode material coated with conductive oxides, which comprises a high-nickel ternary anode material and conductive oxides coated on the surface of the high-nickel ternary anode material; the chemical composition of the high-nickel ternary cathode material is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.5, and x + y is less than 1; the conductive oxide is antimony tin oxide and/or zinc stannate. According to the invention, the surface of the high-nickel ternary lithium ion battery anode material is coated with a layer of antimony tin oxide and/or zinc stannate, so that direct contact between an active electrode material and an electrolyte can be prevented, side reaction between the electrode material and the electrolyte and corrosion of a decomposition product of the electrolyte to the electrode material can be prevented, and the circulation stability in the material circulation process can be improved; the conductive oxide has higher electronic and ionic conductivity, so that the discharge specific capacity and the rate capability of the high-nickel ternary lithium ion battery anode material can be improved.
The invention provides a preparation method of the conductive oxide coated high-nickel ternary lithium ion battery anode material, and the conductive oxide coated high-nickel ternary lithium ion battery anode material is prepared by a wet chemical method or an in-situ synthesis method, so that the method is simple, the cost is low, the coating is uniform, and the industrial batch production is easy to realize.
Drawings
FIG. 1 is a TEM image of Mn-TCPP obtained in example 1;
FIG. 2 is a graph showing the rate capability of the antimony tin oxide ATO-coated high-nickel ternary cathode material and the uncoated high-nickel ternary cathode material obtained in example 1;
FIG. 3 is a graph showing the cycle performance of the antimony tin oxide ATO-coated high-nickel ternary cathode material and the uncoated high-nickel ternary cathode material obtained in example 1;
FIG. 4 is a graph of the rate capability of the zinc stannate ZTO-coated high nickel ternary positive electrode material and the uncoated high nickel ternary positive electrode material obtained in example 2;
FIG. 5 is a first charge-discharge curve diagram of the zinc stannate ZTO-coated high-nickel ternary positive electrode material and the uncoated high-nickel ternary positive electrode material obtained in example 2;
fig. 6 is a graph of the cycle performance of the zinc stannate ZTO-coated high-nickel ternary positive electrode material and the uncoated high-nickel ternary positive electrode material obtained in example 2.
Detailed Description
The invention provides a high-nickel ternary lithium ion battery anode material coated with conductive oxides, which comprises a high-nickel ternary anode material and conductive oxides coated on the surface of the high-nickel ternary anode material;
the chemical composition of the high-nickel ternary cathode material is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.5, and x + y is less than 1;
the conductive oxide is Antimony Tin Oxide (ATO) and/or zinc stannate (ZTO).
In the invention, the chemical composition of the high-nickel ternary cathode material is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.5, and preferably ranges from 0.6 to 0.8; y is preferably 0.1 to 0.2. Preferably, the chemical composition of the high-nickel ternary cathode material is LiNi 0.8 Co 0.1 Mn 0.1 O 2 、LiNi 0.75 Co 0.15 Mn 0.15 O 2 Or LiNi 0.6 Co 0.2 Mn 0.2 O 2 。
In the present invention, the conductive oxide is antimony tin oxide and/or zinc stannate. In the invention, when the conductive oxide is antimony tin oxide and zinc stannate, the mass ratio of the antimony tin oxide to the zinc stannate is preferably 0.01-1: 0.01-1, and more preferably 0.1-1: 0.1-1.
In the invention, the mass ratio of the conductive oxide to the high-nickel ternary positive electrode material is preferably 0.005-0.05: 1, more preferably 0.01-0.04: 1, and even more preferably 0.02-0.04: 1.
In the present invention, the thickness of the conductive oxide is preferably 1 to 5nm, and more preferably 3 to 4 nm. The particle size of the conductive oxide coated high-nickel ternary lithium ion battery positive electrode material is preferably 1-10 mu m, and more preferably 4-8 mu m.
The invention provides a preparation method of the conductive oxide coated high-nickel ternary lithium ion battery anode material, which comprises the following steps:
(1) the chemical composition of the preparation is LiNi x Co y Mn 1-x-y O 2 The high nickel ternary positive electrode material;
(2) ultrasonically mixing a conductive oxide, a high-nickel ternary positive electrode material and a dispersion solvent to obtain a mixed solution;
drying and calcining the mixed solution in sequence to obtain a conductive oxide coated high-nickel ternary lithium ion battery anode material;
alternatively, the first and second liquid crystal display panels may be,
mixing a preparation raw material of a conductive oxide, a high-nickel ternary positive electrode material and an organic solvent, and carrying out a solvothermal reaction to obtain a precursor of the positive electrode material of the lithium ion battery;
and drying and carrying out secondary calcination on the precursor of the lithium ion battery anode material to obtain the high-nickel ternary lithium ion battery anode material coated by the conductive oxide.
The invention firstly prepares the chemical composition LiNi x Co y Mn 1-x-y O 2 The high nickel ternary cathode material. In the present invention, the preparation method of the high-nickel ternary cathode material preferably includes the following steps:
mixing a soluble nickel source, a soluble cobalt source and a soluble manganese source with water to obtain a metal ion solution;
mixing the metal ion solution with a NaOH solution and an ammonia water solution, and sequentially stirring and aging to obtain a nickel-cobalt-manganese hydroxide precursor;
and mixing the nickel-cobalt-manganese hydroxide precursor with a lithium source, and sequentially performing presintering and sintering to obtain the high-nickel ternary cathode material.
The method mixes a soluble nickel source, a soluble cobalt source and a soluble manganese source with water to obtain the metal ion solution. In the invention, the soluble nickel source is preferably nickel sulfate, the soluble cobalt source is preferably cobalt sulfate, and the soluble manganese source is preferably manganese sulfate. In the invention, the molar ratio of Ni, Co and Mn elements in the soluble nickel source, the soluble cobalt source and the soluble manganese source is x: y:1-x-y, wherein x and y satisfy that x is more than or equal to 0.5, and x + y is less than 1. In the invention, the molar concentration of the total metal ions in the metal ion solution is preferably 1-3 mol/L, and more preferably 2 mol/L.
The invention does not require any particular mixing means, such as stirring, known to the person skilled in the art.
After the metal ion solution is obtained, the metal ion solution is mixed with a NaOH solution and an ammonia water solution, and stirring and aging are sequentially carried out to obtain the nickel-cobalt-manganese hydroxide precursor. In the present invention, the molar concentration of OH "in the NaOH solution to the molar concentration of total metal ions in the metal ion solution is 2: 1. In the invention, the concentration of the ammonia water solution is preferably 2-4 mol/L, and more preferably 3.5 mol/L.
In the invention, the volume ratio of the metal ion solution to the NaOH solution is preferably 2-4: 1, and more preferably 3: 1; the volume ratio of the metal ion solution to the ammonia water solution is preferably 2-4: 1, and more preferably 3: 1. In the invention, the pH value of the mixed solution of the metal ion solution, the NaOH solution and the ammonia water solution is preferably 9-12.
In the present invention, the stirring speed is preferably 600 to 800rpm, and more preferably 700 rpm. In the invention, the stirring temperature is preferably 45-65 ℃, and more preferably 50-60 ℃; the time is preferably 20-30 h, and more preferably 25 h.
The present invention preferably ages under standing conditions. In the invention, the aging temperature is preferably room temperature, and the aging time is preferably 1-3 h, and more preferably 2 h.
After the nickel-cobalt-manganese hydroxide precursor is obtained, the nickel-cobalt-manganese hydroxide precursor is mixed with a lithium source, and presintering and sintering are sequentially carried out to obtain the high-nickel ternary cathode material. In the present invention, the lithium source is preferably LiOH. In the invention, the molar ratio of the lithium element in the lithium source to the nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide precursor satisfies the following condition that n (Ni + Co + Mn) is 1.01-1.1: 1, preferably 1.05: 1.
In the present invention, the mixing is preferably performed by grinding. In the present invention, the pre-sintering and sintering are preferably performed under an oxygen atmosphere.
In the invention, the pre-sintering temperature is preferably 450-600 ℃, and more preferably 500-550 ℃; the heat preservation time is preferably 4-6 h, and more preferably 5 h. In the invention, the heating rate of heating to the pre-sintering junction temperature is preferably 3-10 ℃/min, and more preferably 5 ℃/min. According to the invention, through the pre-sintering, the prepared ternary precursor can be dehydrated, and the lithium source is dissolved, so that the lithium source can be embedded into the precursor.
In the invention, the sintering temperature is preferably 700-950 ℃, and more preferably 750-800 ℃; the heat preservation time is preferably 6-15 h, and more preferably 13-14 h. In the invention, the heating rate of heating to the sintering temperature is preferably 3-10 ℃/min, and more preferably 5 ℃/min. According to the invention, through the sintering, the lithium source and the precursor can be fully reacted, and the effect of lithium ion insertion into the ternary precursor layered structure is achieved.
Obtaining the chemical composition LiNi x Co y Mn 1-x-y O 2 After the high-nickel ternary cathode material is prepared, ultrasonically mixing a conductive oxide, the high-nickel ternary cathode material and a dispersion solvent to obtain a mixed solution;
and drying and calcining the mixed solution in sequence to obtain the conductive oxide coated high-nickel ternary lithium ion battery anode material.
In the present invention, the dispersion solvent is preferably an alcohol solvent, and more preferably isopropyl alcohol or ethanol.
In the invention, the frequency of the ultrasonic mixing is preferably 40-60 kHz, and more preferably 50 kHz; the time is preferably 20-30 min, and more preferably 25 min.
In the present invention, the conductive oxide and the dispersion solvent are preferably pre-ultrasonically mixed in advance in the present invention before the ultrasonic mixing. In the invention, the frequency of the pre-ultrasonic mixing is preferably 40-60 kHz, and more preferably 50 kHz; the time is preferably 50-60 min, and more preferably 55 min.
After the ultrasonic mixing, the present invention preferably performs magnetic stirring and mixing on the obtained mixed solution. The magnetic stirring mixing method is not particularly required, and the magnetic stirring mixing method known to those skilled in the art can be used.
In the present invention, the drying is preferably drying. In the invention, the drying temperature is preferably 70-110 ℃, and more preferably 80-100 ℃. In the invention, the dispersion solvent in the mixed solution is removed through the drying.
In the present invention, the first calcination is preferably performed under an oxygen atmosphere. In the invention, the temperature of the first calcination is preferably 400-700 ℃, and more preferably 500-600 ℃; the heat preservation time is preferably 4-6 h, and more preferably 5 h. In the invention, the heating rate of heating to the first calcination temperature is preferably 5 to 10 ℃/min, and more preferably 6 to 8 ℃/min. According to the invention, through the first calcination, the conductive oxide can be better coated on the surface of the positive electrode material.
After the first calcination, the present invention is preferably cooled to room temperature. In the present invention, the cooling is preferably natural cooling.
After the first calcination, the conductive oxide-coated high-nickel ternary lithium ion battery positive electrode material is preferably ground, and the ground particle size is preferably 1-10 μm, and more preferably 4-8 μm.
Or obtaining the chemical composition LiNi x Co y Mn 1-x-y O 2 After the high-nickel ternary cathode material is prepared, a preparation raw material of a conductive oxide, the high-nickel ternary cathode material and an organic solvent are mixed for solvothermal reaction to obtain a precursor of the lithium ion battery cathode material;
and drying and carrying out secondary calcination on the precursor of the lithium ion battery anode material to obtain the high-nickel ternary lithium ion battery anode material coated by the conductive oxide.
In the invention, when the conductive oxide is antimony tin oxide, the raw materials for preparing the conductive oxide preferably comprise antimony acetate and tin acetate, and the molar ratio of the antimony acetate to the tin acetate is preferably 0.1-0.5: 1, and more preferably 0.2-0.4: 1.
In the invention, when the conductive oxide is zinc stannate, the raw materials for preparing the conductive oxide preferably comprise zinc acetate and tin acetate, and the molar ratio of the zinc acetate to the tin acetate is preferably 1-2: 1.
In the present invention, the organic solvent is preferably ethanol or ethylene glycol.
In the present invention, the mixing is preferably: firstly, ultrasonically mixing the raw materials for preparing the conductive oxide, and then adding the high-nickel ternary positive electrode material for magnetic stirring.
In the invention, the frequency of the ultrasonic mixing is preferably 40-60 kHz, and more preferably 50 kHz; the time is preferably 20-30 min, and more preferably 25 min.
In the invention, the time of the magnetic stirring is preferably 20-30 min, and more preferably 25 min.
In the invention, the temperature of the solvothermal reaction is preferably 180-210 ℃, and more preferably 190-200 ℃; the heat preservation time is preferably 6-24 h, and more preferably 12-18 h.
After the solvothermal reaction, in the present invention, it is preferable to perform solid-liquid separation on the solvothermal reaction solution, and dry the obtained solid. In the present invention, the solid-liquid separation method is preferably suction filtration. In the invention, the drying temperature is preferably 70-110 ℃, and more preferably 80-100 ℃.
In the present invention, the second calcination is preferably performed under an oxygen atmosphere. In the invention, the temperature of the second calcination is preferably 400-700 ℃, and more preferably 500-600 ℃; the heat preservation time is preferably 4-6 h, and more preferably 5 h. In the invention, the heating rate of heating to the second calcination temperature is preferably 5-10 ℃/min, and more preferably 6-8 ℃/min. According to the invention, through the second calcination, the conductive oxide can be better coated on the surface of the anode material.
After the second calcination, the conductive oxide-coated high-nickel ternary lithium ion battery positive electrode material is preferably ground, and the ground particle size is preferably 1-10 μm, and more preferably 4-8 μm.
The conductive oxide coated high-nickel ternary lithium ion battery positive electrode material and the preparation method thereof provided by the invention are described in detail below with reference to the examples, but the invention is not to be construed as limiting the scope of the invention.
Example 1
(1) Preparing raw materials of nickel sulfate, cobalt sulfate and manganese sulfate, and preparing 750mL of solution A with metal ion concentration of 2mol/L according to the molar ratio of Ni, Co and Mn of 0.8:0.1: 0.1; according to metal ion and OH - Weighing NaOH according to the molar ratio of 1:2 and preparing 250mL of NaOH solution with the concentration of 4 mol/L; 250mL of ammonia solution B with the concentration of 3.5mol/L is prepared.
Slowly adding the solution A and the solution B into a reaction kettle at a feeding speed of 3:1, controlling the pH value of the reaction process to be 11.4-11.6, the temperature to be 55 ℃, the stirring speed to be 600 r/min by using a NaOH solution, ageing for 3h after reaction, performing suction filtration, and drying to obtain nickel-cobalt-manganese hydroxide precursor powder; grinding and mixing the prepared precursor powder with LiOH, wherein the amount ratio of LiOH to the ternary precursor substance is n (Li) n (Ni + Co + Mn) is 1.05; pre-sintering the mixture at 480 ℃ for 5h and at 750 ℃ for 12h in an oxygen atmosphere to obtain the LiNi with the chemical composition 0.8 Co 0.1 Mn 0.1 O 2 The high nickel ternary cathode material.
(2) Respectively weighing 0.0075g, 0.015g, 0.03g and 0.045g of nano antimony tin oxide ATO, adding the nano antimony tin oxide ATO into 40mL of isopropanol, carrying out ultrasonic treatment at 40kHz for 1h, and then taking 1.5g of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Adding into the solution, continuing to perform ultrasonic treatment for 0.5h, and stirring in a water bath at 60 deg.C for 6 h.
(3) Filtering the mixture, drying at 80 deg.C for 12 hr, heating to 480 deg.C at a rate of 5 deg.C/min, maintaining the temperature for 6 hr, cooling to room temperature, and grinding to obtain 0.5 wt%, 1 wt%, and,2 wt% and 3 wt% nano antimony tin oxide ATO coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 The materials of the positive electrode are marked as NCM811@ 0.5% ATO, NCM811@ 1% ATO, NCM811@ 2% ATO and NCM811@ 3% ATO.
Wherein, the transmission electron micrograph of NCM811@ 1% ATO is shown in FIG. 1. As can be seen from fig. 1, a coating layer having a uniform thickness is formed on the surface of the NCM811, and the layered structure of the inner NCM811 remains intact after coating, demonstrating that the coating of the conductive oxide does not destroy the layered structure of the NCM 811.
The antimony tin oxide ATO prepared by the method is coated with LiNi0.8Co0.1Mn0.1O 2 The button cell is assembled by the anode material, and the constant current charge and discharge test is carried out under the condition of constant temperature of 25 ℃, wherein the voltage range is as follows: 2.7-4.3V.
The rate performance graph of the antimony tin oxide ATO coated high-nickel ternary cathode material and the uncoated high-nickel ternary cathode material is shown in FIG. 2, and the cycle performance graph is shown in FIG. 3. As can be seen from FIGS. 2 and 3, the capacity retention of the materials NCM811, NCM811@ 0.5% ATO, NCM811@ 1% ATO, NCM811@ 2% ATO and NCM811@ 3% ATO after 100 cycles were 66.6%, 83.06%, 79.0%, 76.4% and 52.3%, respectively. After being coated by ATO, the discharge specific capacity of the NCM811@ 2% ATO material under 5C is 159.5 mAh.g -1 (fifth circle at 5C), while the pure sample has only 153.0mAh g -1 The specific capacity is improved by 6.5 mAh.g compared with that of a pure sample -1 . Therefore, the cycle retention rate of the NCM811 and the discharge specific capacity under different current densities can be effectively improved by coating the NCM811 with a proper amount of conductive oxide, and the cycle retention rate of the NCM811 is improved.
Example 2
(1) Preparation of LiNi having the chemical composition according to the procedure of step (1) of example 1 0.8 Co 0.1 Mn 0.1 O 2 The high nickel ternary cathode material.
(2) Weighing 0.0075g, 0.015g, 0.03g and 0.045g of zinc stannate ZTO into 40ml of ethanol, carrying out ultrasonic treatment for 1h, and then 1.5g of LiNi which is a high-nickel ternary cathode material synthesized in the step 1) 0.8 Co 0.1 Mn 0.1 O 2 Adding into the solution, continuing to perform ultrasonic treatment for 0.5h, stirring in water bath at 60 deg.C for 6h。
(3) Filtering the mixture, drying at 80 ℃ for 12h, heating to 480 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 6h, cooling to room temperature, and grinding to obtain 0.5 wt%, 1 wt%, 2 wt% and 3 wt% zinc stannate ZTO-coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 And (3) a positive electrode material.
The resulting ZTO-coated LiNi was subjected to the procedure of example 1 0.8 Co 0.1 Mn 0.1 O 2 And carrying out constant current charge and discharge test on the positive electrode material. The multiplying power performance diagram of the zinc stannate ZTO-coated high-nickel ternary positive electrode material and the uncoated high-nickel ternary positive electrode material is shown in figure 4, the first charge-discharge curve diagram is shown in figure 5, and the cycle performance diagram is shown in figure 6. As can be seen from FIGS. 4-6, after ZTO coating, the discharge specific capacity of the NCM811@ 2% ZTO material at 5C is 161.1mAh g -1 (fifth circle at 5C), while the pure sample has only 153.0mAh g -1 The specific capacity is improved by 8.1 mAh.g compared with that of a pure sample -1 . The cycle performance chart shows that the capacity retention of the materials NCM811, NCM811@ 0.5% ZTO, NCM811@ 1% ZTO, NCM811@ 2% ZTO and NCM811@ 3% ZTO after 100 cycles are 66.6%, 78.6%, 70.7%, 84.3% and 72.8% respectively. Therefore, the discharge specific capacity and the cycle retention rate of the sample after coating modification are obviously improved compared with those of an uncoated NCM811 pure sample, and the discharge specific capacity under different current densities is also obviously improved.
Example 3
(1) Preparation of LiNi having the chemical composition according to the procedure of step (1) of example 1 0.8 Co 0.1 Mn 0.1 O 2 The high nickel ternary cathode material.
(2) Selecting antimony acetate and tin acetate as raw materials, weighing a mixture of 0.0075g, 0.015g and 0.03g according to the molar ratio of Sb to Sn of 0.1:1, dissolving the mixture in ethylene glycol, adjusting the pH of the solution to be alkaline by NaOH, and adding 1.5g of high-nickel ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Then pouring the mixed solution into a reaction kettle, preserving heat for 6 hours at 180 ℃, filtering, drying, calcining for 6 hours at 450 ℃ in an oxygen-introducing tube furnace to prepare 0.5 wt%, 1 wt% and 2 wt% antimony tin oxide ATO coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 High nickel ternary positive electrode material.
The constant current charge and discharge test of the obtained ATO-coated high-nickel ternary cathode material is carried out according to the method of the embodiment 1, and compared with an uncoated NCM811 pure sample, the discharge specific capacity and the cycle retention rate of the ATO-coated high-nickel ternary cathode material are obviously improved.
Example 4
(1) Preparation of LiNi having the chemical composition according to the procedure of step (1) of example 1 0.8 Co 0.1 Mn 0.1 O 2 The high nickel ternary cathode material.
(2) Selecting zinc acetate and tin acetate as raw materials, weighing a mixture of 0.0075g, 0.015g and 0.03g according to the molar ratio of Zn to Sn of 2:1, dissolving the mixture in ethanol, and then adding 1.5g of the high-nickel ternary cathode material LiNi synthesized in the step (1) 0.8 Co 0.1 Mn 0.1 O 2 And then pouring the mixed solution into a reaction kettle, reacting for 24 hours at 200 ℃, filtering, drying, and calcining for 6 hours at 450 ℃ in an oxygen-introducing tube furnace to prepare the high-nickel ternary cathode material coated by 0.5 wt%, 1 wt% and 2 wt% of zinc stannate ZTO.
When the constant current charge-discharge test is carried out on the ZTO-coated high-nickel ternary cathode material according to the method in the embodiment 1, compared with an uncoated NCM811 pure sample, the discharge specific capacity and the cycle retention rate of the ZTO-coated high-nickel ternary cathode material are obviously improved.
Example 5
(1) Preparation of LiNi having the chemical composition according to the procedure of step (1) of example 1 0.8 Co 0.1 Mn 0.1 O 2 The high nickel ternary cathode material.
(2) Weighing a mixture of zinc stannate ZTO and antimony tin oxide ATO (the mass ratio of ATO to ZTO is 0.1:1) with the total mass of 0.0075g, 0.015g, 0.03g and 0.045g, adding the mixture into 40mL of ethanol, performing ultrasonic treatment for 1h, and then 1.5g of the high-nickel ternary cathode material LiNi synthesized in the step (1) 0.8 Co 0.1 Mn 0.1 O 2 Adding into the solution, continuing to perform ultrasonic treatment for 0.5h, and stirring in a water bath at 60 deg.C for 6 h.
(3) Filtering the mixture, drying at 80 deg.C for 12h, heating to 480 deg.C at a rate of 5 deg.C/min,keeping the temperature for 6h, cooling to room temperature, and grinding to obtain 0.5 wt%, 1 wt%, 2 wt%, 3 wt% ATO and ZTO co-coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 High nickel ternary positive electrode material.
The constant current charge-discharge test is carried out on the obtained ATO and ZTO co-coated high-nickel ternary cathode material according to the method of the embodiment 1, and compared with an uncoated NCM811 pure sample, the discharge specific capacity and the cycle retention rate of the material are obviously improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A high-nickel ternary lithium ion battery anode material coated by conductive oxides comprises a high-nickel ternary anode material and conductive oxides coated on the surface of the high-nickel ternary anode material;
the chemical composition of the high-nickel ternary cathode material is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than or equal to 0.5, and x + y is less than 1;
the conductive oxide is antimony tin oxide and/or zinc stannate.
2. The conductive oxide coated high-nickel ternary lithium ion battery positive electrode material as claimed in claim 1, wherein the mass ratio of the conductive oxide to the high-nickel ternary positive electrode material is 0.005-0.05: 1.
3. The conductive oxide coated high-nickel ternary lithium ion battery positive electrode material according to claim 1 or 2, wherein the thickness of the conductive oxide is 1-5 nm;
the particle size of the conductive oxide coated high-nickel ternary lithium ion battery anode material is 1-10 mu m.
4. The preparation method of the conductive oxide coated high-nickel ternary lithium ion battery positive electrode material of any one of claims 1 to 3, which comprises the following steps:
(1) the chemical composition of the preparation is LiNi x Co y Mn 1-x-y O 2 The high nickel ternary positive electrode material;
(2) ultrasonically mixing conductive oxide, a high-nickel ternary positive electrode material and a dispersion solvent to obtain a mixed solution;
drying and calcining the mixed solution in sequence to obtain a conductive oxide coated high-nickel ternary lithium ion battery anode material;
alternatively, the first and second electrodes may be,
mixing a preparation raw material of a conductive oxide, a high-nickel ternary positive electrode material and an organic solvent, and carrying out a solvothermal reaction to obtain a precursor of the positive electrode material of the lithium ion battery;
and drying and carrying out secondary calcination on the precursor of the lithium ion battery anode material to obtain the high-nickel ternary lithium ion battery anode material coated by the conductive oxide.
5. The method according to claim 4, wherein the ultrasonic mixing is performed at a frequency of 40 to 60kHz for 20 to 30 min.
6. The preparation method according to claim 4, wherein when the conductive oxide is antimony tin oxide, raw materials for preparing the conductive oxide comprise antimony acetate and tin acetate, and the molar ratio of the antimony acetate to the tin acetate is 0.1-0.5: 1;
when the conductive oxide is zinc stannate, the preparation raw materials of the conductive oxide comprise zinc acetate and tin acetate, and the molar ratio of the zinc acetate to the tin acetate is 1-2: 1.
7. The preparation method according to claim 4 or 6, wherein the temperature of the solvothermal reaction is 180-210 ℃, and the holding time is 6-24 h.
8. The preparation method according to claim 4, wherein the temperatures of the first calcination and the second calcination are 400-700 ℃ independently, and the holding time is 4-6 h independently.
9. The preparation method of claim 4, wherein the preparation method of the high-nickel ternary cathode material comprises the following steps:
mixing a soluble nickel source, a soluble cobalt source and a soluble manganese source with water to obtain a metal ion solution;
mixing the metal ion solution with a NaOH solution and an ammonia water solution, and sequentially stirring and aging to obtain a nickel-cobalt-manganese hydroxide precursor;
and mixing the nickel-cobalt-manganese hydroxide precursor with a lithium source, and sequentially performing presintering and sintering to obtain the high-nickel ternary cathode material.
10. The preparation method according to claim 9, wherein the pre-sintering temperature is 450-600 ℃, and the holding time is 4-6 h;
the sintering temperature is 700-950 ℃, and the heat preservation time is 6-15 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210616810.4A CN114975932B (en) | 2022-06-01 | 2022-06-01 | Conductive oxide coated high-nickel ternary lithium ion battery positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210616810.4A CN114975932B (en) | 2022-06-01 | 2022-06-01 | Conductive oxide coated high-nickel ternary lithium ion battery positive electrode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114975932A true CN114975932A (en) | 2022-08-30 |
| CN114975932B CN114975932B (en) | 2024-03-08 |
Family
ID=82960465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210616810.4A Active CN114975932B (en) | 2022-06-01 | 2022-06-01 | Conductive oxide coated high-nickel ternary lithium ion battery positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114975932B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012054062A (en) * | 2010-08-31 | 2012-03-15 | Sharp Corp | Positive electrode active material and nonaqueous secondary battery with positive electrode containing the same |
| CN103367736A (en) * | 2012-04-06 | 2013-10-23 | 协鑫动力新材料（盐城）有限公司 | Surface clad lithium ion battery positive material precursor, and preparation method and application thereof |
| KR20150065979A (en) * | 2013-12-05 | 2015-06-16 | (주)오렌지파워 | Manufacturing method of surface treated positive active material precusor for lithium rich rechargeable batteries, and positive active material precusor, positive active material made by the same |
| CN105489970A (en) * | 2016-01-06 | 2016-04-13 | 中南大学 | Porous zinc-tin alloy negative electrode material for zinc-air battery and preparation method of porous zinc-tin alloy negative electrode material |
| CN105742637A (en) * | 2014-12-12 | 2016-07-06 | 苏州宝时得电动工具有限公司 | Positive material and battery containing same |
| US20170170480A1 (en) * | 2014-08-26 | 2017-06-15 | Lg Chem, Ltd. | Surface coated positive electrode active material, preparation method thereof and lithium secondary battery including the same |
| CN108390039A (en) * | 2018-02-23 | 2018-08-10 | 成都新柯力化工科技有限公司 | A kind of nickelic anode material of lithium battery that double oxide coats altogether and preparation method |
| CN108767225A (en) * | 2018-05-30 | 2018-11-06 | 陕西煤业化工技术研究院有限责任公司 | A kind of preparation method of conductor oxidate cladding nickel cobalt lithium aluminate ternary material |
| CN109768248A (en) * | 2018-12-29 | 2019-05-17 | 桂林电器科学研究院有限公司 | Coating modification LiNi0.8Co0.1Mn0.1O2Tertiary cathode material and preparation method thereof and battery |
| CN110061213A (en) * | 2019-04-17 | 2019-07-26 | 中南大学 | Hollow spheres carbon coating zinc stannate composite negative pole material and preparation method thereof |
| CN112382738A (en) * | 2019-11-08 | 2021-02-19 | 陕西彩虹新材料有限公司 | Preparation method of high-performance lithium-rich single crystal multi-element cathode material |
| CN113213552A (en) * | 2021-03-20 | 2021-08-06 | 长沙理工大学 | Quasi-spherical porous nickel-cobalt-manganese precursor and preparation method thereof |
-
2022
- 2022-06-01 CN CN202210616810.4A patent/CN114975932B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012054062A (en) * | 2010-08-31 | 2012-03-15 | Sharp Corp | Positive electrode active material and nonaqueous secondary battery with positive electrode containing the same |
| CN103367736A (en) * | 2012-04-06 | 2013-10-23 | 协鑫动力新材料（盐城）有限公司 | Surface clad lithium ion battery positive material precursor, and preparation method and application thereof |
| KR20150065979A (en) * | 2013-12-05 | 2015-06-16 | (주)오렌지파워 | Manufacturing method of surface treated positive active material precusor for lithium rich rechargeable batteries, and positive active material precusor, positive active material made by the same |
| US20170170480A1 (en) * | 2014-08-26 | 2017-06-15 | Lg Chem, Ltd. | Surface coated positive electrode active material, preparation method thereof and lithium secondary battery including the same |
| CN105742637A (en) * | 2014-12-12 | 2016-07-06 | 苏州宝时得电动工具有限公司 | Positive material and battery containing same |
| CN105489970A (en) * | 2016-01-06 | 2016-04-13 | 中南大学 | Porous zinc-tin alloy negative electrode material for zinc-air battery and preparation method of porous zinc-tin alloy negative electrode material |
| CN108390039A (en) * | 2018-02-23 | 2018-08-10 | 成都新柯力化工科技有限公司 | A kind of nickelic anode material of lithium battery that double oxide coats altogether and preparation method |
| CN108767225A (en) * | 2018-05-30 | 2018-11-06 | 陕西煤业化工技术研究院有限责任公司 | A kind of preparation method of conductor oxidate cladding nickel cobalt lithium aluminate ternary material |
| CN109768248A (en) * | 2018-12-29 | 2019-05-17 | 桂林电器科学研究院有限公司 | Coating modification LiNi0.8Co0.1Mn0.1O2Tertiary cathode material and preparation method thereof and battery |
| CN110061213A (en) * | 2019-04-17 | 2019-07-26 | 中南大学 | Hollow spheres carbon coating zinc stannate composite negative pole material and preparation method thereof |
| CN112382738A (en) * | 2019-11-08 | 2021-02-19 | 陕西彩虹新材料有限公司 | Preparation method of high-performance lithium-rich single crystal multi-element cathode material |
| CN113213552A (en) * | 2021-03-20 | 2021-08-06 | 长沙理工大学 | Quasi-spherical porous nickel-cobalt-manganese precursor and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| MIN‑DAN ZHU ET AL., 《IONICS》 ENHANCED RATE CAPABILITY AND CYCLING STABILITY OF CONDUCTIVE OXIDE‑COATED LINI0.8CO0.1MN0.1O2 FOR LITHIUM‑ION BATTERIES, vol. 29, pages 1711 - 1720 * |
| XIAOSHU HE ET AL., 《ELECTROCHIMICA ACTA》 ELECTRONICALLY CONDUCTIVE SB-DOPED SNO2 NANOPARTICLES COATED LINI0.8CO0.15AL0.05O2 CATHODE MATERIAL WITH ENHANCED ELECTROCHEMICAL PROPERTIES FOR LI-ION BATTERIES, vol. 236, pages 273 * |
| 李奕达 等, 不同锂源制备及ZNO包覆改性LINI0.8CO0.1MN0.1O2正极材料性能研究, vol. 12, no. 4, pages 386 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114975932B (en) | 2024-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101335348B (en) | Preparing method of lithium ionic cell 5V anode material spherical LiNi0.5Mn1.5O4 | |
| CN109879331A (en) | The nickelic tertiary cathode material and preparation method of a kind of fast-ionic conductor cladding and its lithium ion battery being prepared | |
| CN101510606B (en) | Composite metal oxide coating spinelle type LiMn2O4 anode material and preparation method | |
| CN102637867B (en) | Chromium-doped lithium-nickel-manganese-oxygen material and preparation method thereof, and lithium ion battery containing chromium-doped lithium-nickel-manganese-oxygen material | |
| CN112928253B (en) | Nickel-manganese-titanium composite material and preparation method and application thereof | |
| CN110429268A (en) | A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof | |
| CN110233261B (en) | Preparation method of single crystal ternary lithium battery positive electrode material and lithium ion battery | |
| CN102983326A (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN104037412B (en) | The preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball | |
| CN104425809A (en) | Lithium ion battery positive electrode material, preparation method of lithium ion battery positive electrode material, lithium ion battery comprising lithium ion battery positive electrode material | |
| CN101704681B (en) | Method for preparing lithium titanate with spinel structure | |
| CN104112845A (en) | Positive electrode material of lithium ion battery and preparation method thereof | |
| CN102709525A (en) | Metal oxide coated lithium nickel manganese oxide material, preparation method of metal oxide coated lithium nickel manganese oxide material and lithium ion battery | |
| CN113517424A (en) | Cobalt-free positive electrode material of high-voltage lithium ion battery and preparation method thereof | |
| CN103367733A (en) | Lithium ion battery cathode material and preparation method thereof and lithium ion battery | |
| CN113845152A (en) | Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery | |
| CN114843469A (en) | MgFe 2 O 4 Modified P2/O3 type nickel-based layered sodium-ion battery positive electrode material and preparation method thereof | |
| CN116053444A (en) | Doped layered anode material and application thereof in sodium ion battery | |
| CN112777611B (en) | Rhombohedral phase Prussian blue derivative and preparation method and application thereof | |
| WO2019104948A1 (en) | Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery | |
| CN101894938B (en) | Cobalt-aluminum composite metal oxide-coated LiCoO2 anode material and preparation method thereof | |
| CN103456945A (en) | Preparation method of low-cost lithium ion battery anode material | |
| CN106025199A (en) | Preparation method of nanometer lithium lanthanum titanate coated 0.5Li2MnO3 0.5LiNi0.5Mn0.5O2 material | |
| CN108807971B (en) | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof | |
| WO2023060992A1 (en) | Method for synthesizing high-safety positive electrode material by recycling positive electrode leftover materials, and application |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |