CN111952554A - Ternary cathode material of lithium ion battery and preparation method thereof - Google Patents
Ternary cathode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN111952554A CN111952554A CN202010629330.2A CN202010629330A CN111952554A CN 111952554 A CN111952554 A CN 111952554A CN 202010629330 A CN202010629330 A CN 202010629330A CN 111952554 A CN111952554 A CN 111952554A
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- 239000010406 cathode material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 229910003327 LiNbO3 Inorganic materials 0.000 claims abstract description 19
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 claims abstract 3
- 239000000463 material Substances 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 7
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 7
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 35
- 238000000034 method Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 12
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 11
- 238000005245 sintering Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910003684 NixCoyMnz Inorganic materials 0.000 description 2
- 229910003678 NixCoyMnz(OH)2 Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 206010016766 flatulence Diseases 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 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
- 238000011056 performance test Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a ternary anode material of a lithium ion battery and a preparation method thereof, wherein the ternary anode material is LiNbO3Coated LiNixCoyMnzO2Wherein, 0<x<1,0<y<1，0<z<1, x + y + z is 1, and provides a preparation method of the ternary cathode material3Using LiNbO3Stability of itself, LiNbO3High lithium ion conductivity and LiNbO3Stability in medium electrolyteThe ternary cathode material is protected from being corroded by electrolyte, the surface residual alkali of the ternary cathode material is reduced, the stability and the safety performance of the ternary cathode material are improved, and therefore the cycle stability of the battery is improved.
Description
Technical Field
The invention relates to a ternary cathode material and a preparation method thereof, in particular to a ternary cathode material of a lithium ion battery and a preparation method thereof, and belongs to the technical field of manufacturing of the lithium ion battery cathode material.
Background
The positive electrode material is always a short plate of the lithium ion battery, and the energy density, the cycle life and the safety performance of the battery are directly influenced by the quality of the positive electrode material. The mainstream positive electrode materials in the current market are four types: lithium cobaltate, ternary lithium iron phosphate and lithium manganate. Among them, ternary materials are favored by the market due to advantages of relatively low cost advantage, high specific energy, etc. However, the ternary cathode materials themselves have some disadvantages, such as: high surface residual alkali, poor cycle life and the like. Therefore, modification is required to be performed on the conventional ternary positive electrode material. The conventional modification method mainly comprises surface coating, and the coated substances are generally selected from alumina, titanium oxide, zirconium oxide and the like. The coating method generally selects a solid phase method or a liquid phase method, the solid phase method has simple process and low cost, but the coating effect is not good; the liquid phase method has relatively complex process and high cost, but has better coating effect.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a ternary cathode material of a lithium ion battery, which can reduce the surface residual alkali of the ternary cathode material and improve the stability and safety performance of the ternary cathode material.
The technical scheme is as follows: the ternary anode material of the lithium ion battery is LiNbO3Cladding NixCoyMnz(OH)2Or NixCoyMnzCO3Wherein, 0<x<1,0<y<1，0<z<1，x+y+z＝1。
Further, NixCoyMnz(OH)2Or NixCoyMnzCO3And LiNbO3The mass ratio of (A) to (B) is 100: 1-3.
The preparation method of the ternary cathode material of the lithium ion battery comprises the following steps:
(1) dissolving ammonium niobium oxalate or niobium oxalate and an organic surfactant in water to prepare a coating solution;
(2) adding a ternary positive electrode material precursor into the coating solution, and stirring to prepare slurry;
(3) heating the slurry to 80-100 ℃, stirring, filtering and drying to obtain a dried ternary cathode material precursor;
(4) mixing the dried ternary positive electrode material precursor with lithium carbonate or lithium hydroxide monohydrate to prepare a mixed material, wherein the quantity ratio of Li to the sum of Ni, Co and Mn is 1.03-1.15;
(5) and heating the mixed material to 780-1000 ℃, and preserving heat and cooling to obtain the ternary cathode material of the lithium ion battery.
Further, in the step (1), the concentration of the solution of ammonium niobium oxalate or niobium oxalate is 0.1-150 g/L, preferably, the concentration of the solution of ammonium niobium oxalate or niobium oxalate is 5-20 g/L; the concentration of the organic surfactant is 0.1-10 g/L, preferably 1-5 g/L.
In the step (1), the amount of the organic surfactant accounts for 0.01-1.0 wt% of the mass ratio of the precursor.
In the step (2), the mass ratio of the coating liquid to the ternary anode material precursor is 102-125: 100.
Further, in the step (3), the filtered ternary cathode material is dried until the moisture content is reduced to 500ppm or less.
In the step (4), the dried ternary positive electrode material precursor is mixed with lithium carbonate or lithium hydroxide monohydrate until white lithium-containing compound particles cannot be observed by naked eyes.
In the step (5), the heating is heating by introducing air, and the oxygen content is increased or pure oxygen is introduced for heating aiming at the nickelic ternary cathode material.
When the coating amount is 2%, the electrochemical performance is excellent, compared with the uncoated anode material, the first discharge specific capacity is hardly attenuated at 25 ℃ and 1 ℃, the capacity retention rate after 500 cycles is improved by over 24%, the cycle performance is excellent, and the manufactured soft package battery basically has no flatulence phenomenon.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: when the lithium ion battery is made of ternary positive electrode materialLiNbO3When the coating amount is about 2 wt% (calculated by niobium element), compared with the uncoated ternary cathode material, the cycle performance is improved by 1 time, the safety performance is also obviously improved, and the nano LiNbO3The gram capacity of the ternary cathode material cannot be obviously reduced by the coating layer; nano LiNbO3The coating layer avoids direct contact between the ternary cathode material and electrolyte in the charging and discharging processes, the influence of factors such as environment humidity and the like on the ternary cathode material in the battery assembling process is avoided, the surface residual alkali of the material is obviously reduced, and the safety performance of the assembled ternary lithium battery is obviously improved; compared with the conventional coating process, the niobium element is precipitated in a heating mode, namely the niobium element (niobium hydroxide) is pre-coated on the precursor of the ternary cathode material, the niobium and the precursor have good compatibility, and the niobium element can be uniformly deposited on the surface of the precursor; the preparation method selects perovskite type LiNbO3The method is a coating agent, adopts a one-step lithiation method of pre-coating a precursor with niobium element, precipitating the niobium element by a liquid phase method and a high temperature method, and combining the precursor and the niobium element, so that the lithium niobate effectively and uniformly forms a nano protective layer on the surface of the ternary anode material of the lithium ion battery; in the sintering process of excessive lithium, the problem of lithium volatilization in the conventional secondary sintering process is effectively reduced by adopting a one-step sintering method, and the problem of energy consumption increase caused by a secondary sintering process is also avoided.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The ternary cathode material of the embodiment is LiNi0.8Co0.1Mn0.1O2@1wt％LiNbO3The preparation method comprises the following steps:
1g of ammonium niobium oxalate and 1g of organic surfactant are completely dissolved in 100mL of water, and then 100g of ternary cathode material precursor Ni0.8Co0.1Mn0.1(OH)2Adding into the mixture, magnetically stirring at 600rpm for 10min, placing into a water bath, heating to 90 deg.C and keepingThe temperature was kept for 1h, during which time a stirring rate of 600rpm was maintained. The slurry was then centrifuged at 4000rpm for 10min, and the precipitate was washed and dried in an oven at 100 ℃ until the moisture was reduced to 500 ppm. According to the proportion that the quantity ratio of Li to the sum of Ni, Co and Mn is 1.03, fully mixing the precipitate with lithium hydroxide monohydrate, heating the mixed material in oxygen to 800 ℃, preserving heat for 16h, and naturally cooling to room temperature to obtain the ternary cathode material.
Example 2
The ternary cathode material of the embodiment is LiNi0.8Co0.1Mn0.1O2@2wt％LiNbO3The preparation method comprises the following steps:
2g of ammonium niobium oxalate and 0.5g of organic surfactant are completely dissolved in 100mL of water, and then 100g of ternary cathode material precursor Ni0.8Co0.1Mn0.1(OH)2Pouring into the mixture, magnetically stirring at 600rpm for 10min, placing into a water bath, heating to 80 deg.C, and maintaining the temperature for 1h while maintaining the stirring speed at 600 rpm. The slurry was then centrifuged at 4000rpm for 10min, and the precipitate was washed and dried in an oven at 100 ℃ until the moisture was reduced to 490 ppm. According to the proportion that the quantity ratio of Li to the sum of Ni, Co and Mn is 1.03, fully mixing the precipitate with lithium hydroxide monohydrate, heating the mixed material in oxygen to 780 ℃, preserving heat for 16h, and naturally cooling to room temperature to obtain the ternary cathode material.
Example 3
The ternary cathode material of the embodiment is LiNi0.8Co0.1Mn0.1O2@3wt％LiNbO3The preparation method comprises the following steps:
completely dissolving 15g of ammonium niobium oxalate and 1g of organic surfactant in 100mL of water, and then dissolving 100g of ternary cathode material precursor Ni0.8Co0.1Mn0.1(OH)2Pouring into the mixture, magnetically stirring at 600rpm for 10min, placing into a water bath, heating to 100 deg.C, and maintaining the temperature for 1h while maintaining the stirring speed at 600 rpm. The slurry was then centrifuged at 4000rpm for 10min, and the precipitate was washed and dried in an oven at 100 ℃ until the moisture was reduced to 490 ppm. According toThe mass ratio of Li to the sum of Ni, Co and Mn is 1.03, the precipitate and lithium hydroxide monohydrate are fully mixed, the mixture is heated to 1000 ℃ in oxygen, the temperature is kept for 16h, and then the mixture is naturally cooled to room temperature, so that the ternary cathode material is prepared.
Example 4
LiNi of the present example0.5Co0.2Mn0.3O2@1wt％LiNbO3The preparation method of the cathode material comprises the following steps:
0.01g of ammonium niobium oxalate and 0.01g of organic surfactant are completely dissolved in 100mL of water, and then 100g of ternary cathode material precursor Ni is added0.5Co0.2Mn0.3(OH)2Pouring into the mixture, magnetically stirring at 600rpm for 10min, placing into a water bath, heating to 90 deg.C, and maintaining the temperature for 1h while maintaining the stirring speed at 600 rpm. The slurry was then centrifuged at 4000rpm for 10min, and the precipitate was washed and dried in an oven at 100 ℃ until the moisture was reduced to 490 ppm. According to the proportion that the quantity ratio of Li to the sum of Ni, Co and Mn is 1.05, fully mixing the precipitate with lithium carbonate, heating the mixed material in the air to 920 ℃, preserving the heat for 16 hours, and then naturally cooling to room temperature to obtain the ternary cathode material.
Example 5
LiNi of the present example0.5Co0.2Mn0.3O2@2wt％LiNbO3The preparation method comprises the following steps:
2g of ammonium niobium oxalate and 1g of organic surfactant are completely dissolved in 100mL of water, and then 100g of ternary cathode material precursor Ni is added0.5Co0.2Mn0.3(OH)2Pouring into the mixture, magnetically stirring at 600rpm for 10min, placing into a water bath, heating to 90 deg.C, and maintaining the temperature for 1h while maintaining the stirring speed at 600 rpm. The slurry was then centrifuged at 4000rpm for 10min, and the precipitate was washed and dried in an oven at 100 ℃ until the moisture was reduced to 490 ppm. According to the proportion that the quantity ratio of Li to the sum of Ni, Co and Mn is 1.15, fully mixing the precipitate with lithium carbonate, heating the mixed material in the air to 920 ℃, preserving the heat for 16 hours, and then naturally cooling to room temperature to obtain the ternary cathode material.
Example 6
LiNi of the present example0.5Co0.2Mn0.3O2@3wt％LiNbO3The preparation method comprises the following steps:
completely dissolving 3g of niobium oxalate and 1g of organic surfactant in 100mL of water, and then dissolving 100g of ternary cathode material precursor Ni0.5Co0.2Mn0.3(OH)2Pouring into the mixture, magnetically stirring at 600rpm for 10min, placing into a water bath, heating to 90 deg.C, and maintaining the temperature for 1h while maintaining the stirring speed at 600 rpm. The slurry was then centrifuged at 4000rpm for 10min, and the precipitate was washed and dried in an oven at 100 ℃ until the moisture was reduced to 490 ppm. According to the proportion that the quantity ratio of Li to the sum of Ni, Co and Mn is 1.05, fully mixing the precipitate with lithium carbonate, heating the mixed material in the air to 920 ℃, preserving the heat for 16 hours, and then naturally cooling to room temperature to obtain the ternary cathode material.
Comparative example 1
This comparative example was not LiNbO3Coated LiNi0.8Co0.1Mn0.1O2A ternary positive electrode material.
Comparative example 2
This comparative example was not LiNbO3Coated LiNi0.5Co0.2Mn0.3O2A ternary positive electrode material.
Comparative example 3
In the comparative example, the amount ratio of Li to the sum of Ni, Co and Mn is 1, and other raw materials, mixture ratio, preparation method and detection method are the same as those in example 1.
Comparative example 4
In the comparative example, the amount ratio of Li to the sum of Ni, Co and Mn was 1.3, and the other raw materials, compounding ratio, preparation method and detection method were the same as those in example 1.
Comparative example 5
In the comparative example, the mass of ammonium niobium oxalate was 0.5g, and the other raw materials, the mixture ratio, the preparation method and the detection method were the same as those in example 1.
Comparative example 6
In the comparative example, the mass of ammonium niobium oxalate is 1550g, and other raw materials, mixture ratio, preparation method and detection method are the same as those in example 1.
Comparative example 7
The mass of the organic surfactant in this comparative example was 0.5g, and the other raw materials, the compounding ratio, the preparation method and the detection method were the same as those in example 1.
Comparative example 8
The mass of the organic surfactant in the comparative example is 120g, and other raw materials, mixture ratio, preparation method and detection method are the same as those in example 1.
And (3) electrochemical performance testing:
the composite anode material prepared by the invention can be used for preparing an anode plate for a lithium ion battery by adopting a coating method. The specific operation is that active ingredients (samples and comparative examples in each embodiment), a conductive agent Super-Pcarbon and a binder NMP are mixed according to the mass ratio of 90:5:5, then the mixture is evenly coated on an aluminum foil, and the aluminum foil is dried in vacuum at 100 ℃ and then compacted under 10Mpa to obtain the electrode plate.
The materials prepared in the above examples and comparative examples are used as active components to prepare working electrodes, metal lithium is used as a reference electrode, Celgard2400 is used as a diaphragm, and 1mol/LLIPF is used6The EC/DEC/DMC (volume ratio of 1:1:1) solution of (A) is used as the electrolyte. And assembling the cell into a CR2032 button cell, and carrying out constant-current charge-discharge performance test on a cell test system. The charging voltage range is 3-4.3V, and the testing temperature is 25 ℃.
Table 1 shows experimental data for examples 1-6 in comparison to comparative examples 1-8, as can be seen in Table one: when the coating amount is 2 wt%, the cycle performance of the material is optimal, because the uniform coating of the lithium niobate enables the surface of the positive electrode material to form a protective film, the protective film is not completely contacted with electrolyte in the electrochemical reaction process, the generation of side reaction is avoided, the generation of by-products is reduced, and the electrochemical performance of the material is improved. As is clear from comparison of comparative examples 1-2 with example 1, LiNbO was not present3The coated ternary positive electrode material is contacted with electrolyte to generate side reaction, so that the generation of byproducts is increased, and the electrochemical performance is poor; in comparative example 3, the ratio of Li to the amount of Ni, Co, MnThe setting is 1, because lithium is easy to sublimate, the actual lithium content after sintering is lower than the set value, the specific discharge capacity of the material is seriously reduced, and the cycle performance is also reduced; in a comparative example 4, the quantity ratio of Li to the sum of Ni, Co and Mn is set to be 1.3, lithium sublimation is not enough to offset the surplus of lithium, so that the content of lithium in the material is too high, the excessive lithium has an auxiliary effect on a sintering process, and the material is caused to generate an over-burning phenomenon, namely the material is seriously agglomerated, particles are enlarged, dead lithium is enlarged, so that the first charge-discharge specific capacity of the material is seriously reduced, the residual alkali is seriously increased, and the battery is seriously inflated; in the comparative example 5, the material has no obvious modification effect due to the low content of the niobium element; in comparative example 6, since the content of niobium element in the material is too high, and since lithium niobate itself does not have the performance of allowing lithium ions to be extracted/inserted, the increase of the content thereof only reduces the content of the ternary cathode material, thereby causing the reduction of the electrochemical performance of the material; in comparative example 7, the material dispersion is not uniform due to the low surfactant content, and the material uniformity is poor, that is, the niobium element is not uniformly distributed in the ternary material system, so the electrochemical performance is not improved; in comparative example 8, the material was uniformly dispersed due to the use of a large amount of surfactant, and a large amount of organic surfactant was completely decomposed into water and carbon dioxide during the sintering of the material, which basically did not affect the electrochemical properties of the material much, but the use of a large amount of surfactant wasted resources and also increased the production cost.
TABLE 1 electrochemical Performance of examples 1-6 and comparative examples 1-8
| Sample (I) | Specific capacity of initial discharge | Multiplying power | Number of cycles | Capacity retention rate | Condition of flatulence |
| Example 1 | 176mA h g-1 | 1C | 500 | 80.9％ | Is not obvious |
| Example 2 | 175mA h g-1 | 1C | 500 | 81.1％ | Is not obvious |
| Example 3 | 174mA h g-1 | 1C | 500 | 80.9％ | Is not obvious |
| Example 4 | 154mA h g-1 | 1C | 500 | 86.6％ | Is not obvious |
| Example 5 | 153mA h g-1 | 1C | 500 | 86.7％ | Is not obvious |
| Example 6 | 152mA h g-1 | 1C | 500 | 80.3％ | Is not obvious |
| Comparative example 1 | 177mA h g-1 | 1C | 500 | 61.5％ | Is obvious |
| Comparative example 2 | 155mA h g-1 | 1C | 500 | 69.8％ | Is obvious |
| Comparative example 3 | 160mA h g-1 | 1C | 500 | 55.6％ | Is not obvious |
| Comparative example 4 | 154mA h g-1 | 1C | 500 | 54.1％ | Severe severity of disease |
| Comparative example 5 | 177mA h g-1 | 1C | 500 | 64.3％ | Is obvious |
| Comparative example 6 | 62mA h g-1 | 1C | 500 | 31.4％ | Is not obvious |
| Comparative example 7 | 176mA h g-1 | 1C | 500 | 70.7％ | Is obvious |
| Comparative example 8 | 176mA h g-1 | 1C | 500 | 80.7％ | Is not obvious |
Claims (10)
1. A ternary cathode material of a lithium ion battery is characterized in that: the ternary positive electrode material is LiNbO3Coated LiNixCoyMnzO2Wherein, 0<x<1，0<y<1，0<z<1，x+y+z＝1。
2. The lithium ion battery ternary cathode material of claim 1, wherein: the LiNixCoyMnzO2And LiNbO3The mass ratio of (A) to (B) is 100: 1-3.
3. The preparation method of the ternary cathode material of the lithium ion battery of claim 1 is characterized by comprising the following steps:
(1) dissolving ammonium niobium oxalate or niobium oxalate and an organic surfactant in water to prepare a coating solution;
(2) adding a ternary positive electrode material precursor into the coating solution, and stirring to prepare slurry;
(3) heating the slurry to 80-100 ℃, stirring, filtering and drying to obtain a dried ternary cathode material precursor;
(4) mixing the dried ternary positive electrode material precursor with lithium carbonate or lithium hydroxide monohydrate to prepare a mixed material, wherein the quantity ratio of Li to the sum of Ni, Co and Mn is 1.03-1.15;
(5) and heating the mixed material to 780-1000 ℃, and preserving heat and cooling to obtain the ternary cathode material of the lithium ion battery.
4. The preparation method of the ternary cathode material for the lithium ion battery according to claim 3, wherein the preparation method comprises the following steps: in the step (1), the concentration of the solution of ammonium niobium oxalate or niobium oxalate is 0.1-150 g/L.
5. The preparation method of the ternary cathode material for the lithium ion battery according to claim 3, wherein the preparation method comprises the following steps: in the step (1), the concentration of the organic surfactant is 0.1-10 g/L.
6. The preparation method of the ternary cathode material for the lithium ion battery according to claim 3, wherein the preparation method comprises the following steps: in the step (1), the amount of the organic surfactant accounts for 0.01-1.0 wt% of the mass ratio of the precursor.
7. The preparation method of the ternary cathode material for the lithium ion battery according to claim 3, wherein the preparation method comprises the following steps: in the step (2), the mass ratio of the coating liquid to the ternary cathode material precursor is 102-125: 100.
8. The preparation method of the ternary cathode material for the lithium ion battery according to claim 3, wherein the preparation method comprises the following steps: in the step (3), the filtered ternary cathode material is dried until the moisture content is reduced to below 500 ppm.
9. The preparation method of the ternary cathode material for the lithium ion battery according to claim 3, wherein the preparation method comprises the following steps: in the step (4), the dried ternary positive electrode material precursor is mixed with lithium carbonate or lithium hydroxide monohydrate until white lithium-containing compound particles cannot be observed by naked eyes.
10. The preparation method of the ternary cathode material for the lithium ion battery according to claim 3, wherein the preparation method comprises the following steps: in the step (5), the heating is heating by introducing air.
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| CN113437273A (en) * | 2021-06-28 | 2021-09-24 | 北京理工大学 | All-solid-state lithium ion battery positive electrode material with coating layer on outer layer and preparation method thereof |
| CN113611862A (en) * | 2021-07-29 | 2021-11-05 | 广州大学 | Preparation method of lithium niobate-coated positive electrode material, lithium niobate-coated positive electrode material and application |
| CN113921818A (en) * | 2021-08-26 | 2022-01-11 | 恒大新能源技术(深圳)有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN114725338A (en) * | 2022-03-17 | 2022-07-08 | 宁波容百新能源科技股份有限公司 | High-nickel multi-element positive electrode material, and preparation method and application thereof |
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| XUELEI LI等: ""LiNbO 3 -coated LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode with high discharge capacity and rate performance for all- solid- state lithium battery"", 《JOURNAL OF ENERGY CHEMISTRY》 * |
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| CN113437273A (en) * | 2021-06-28 | 2021-09-24 | 北京理工大学 | All-solid-state lithium ion battery positive electrode material with coating layer on outer layer and preparation method thereof |
| CN113437273B (en) * | 2021-06-28 | 2022-10-11 | 北京理工大学 | All-solid-state lithium ion battery positive electrode material with coating layer on outer layer and preparation method thereof |
| CN113611862A (en) * | 2021-07-29 | 2021-11-05 | 广州大学 | Preparation method of lithium niobate-coated positive electrode material, lithium niobate-coated positive electrode material and application |
| CN113921818A (en) * | 2021-08-26 | 2022-01-11 | 恒大新能源技术(深圳)有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN114725338A (en) * | 2022-03-17 | 2022-07-08 | 宁波容百新能源科技股份有限公司 | High-nickel multi-element positive electrode material, and preparation method and application thereof |
| WO2023174028A1 (en) * | 2022-03-17 | 2023-09-21 | 宁波容百新能源科技股份有限公司 | High-nickel multi-element positive electrode material, and preparation method therefor and use thereof |
| CN115360330A (en) * | 2022-08-18 | 2022-11-18 | 湘潭大学 | Preparation method of positive pole piece, positive pole piece and lithium ion battery |
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