CN114899381B - Nickel cobalt lithium manganate battery positive electrode material, and preparation method and application thereof - Google Patents
Nickel cobalt lithium manganate battery positive electrode material, and preparation method and application thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 38
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 238000000227 grinding Methods 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 14
- 239000010405 anode material Substances 0.000 claims abstract description 12
- AIJRZQRTCRIQFY-UHFFFAOYSA-N dilithium cobalt(2+) dioxido(dioxo)manganese nickel(2+) Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2].[Ni+2].[Li+].[Mn](=O)(=O)([O-])[O-].[Mn](=O)(=O)([O-])[O-] AIJRZQRTCRIQFY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 239000004570 mortar (masonry) Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 9
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims 1
- 239000010955 niobium Substances 0.000 abstract description 13
- 229910052758 niobium Inorganic materials 0.000 abstract description 13
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 13
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- DUSBUJMVTRZABV-UHFFFAOYSA-M [O-2].O[Nb+4].[O-2] Chemical compound [O-2].O[Nb+4].[O-2] DUSBUJMVTRZABV-UHFFFAOYSA-M 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000000035 biogenic effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- LDPWMGUFXYRDRG-UHFFFAOYSA-I niobium(5+) pentaacetate Chemical compound [Nb+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O LDPWMGUFXYRDRG-UHFFFAOYSA-I 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000013736 caramel Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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)
- Inorganic Chemistry (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a nickel cobalt lithium manganate lithium battery anode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding an organic solvent into NCM811 and a niobium source, stirring, evaporating the solvent, and grinding the rest materials into powder; carrying out two-stage sintering on the ground powdery material in an oxygen atmosphere, and then continuously grinding the sintered product into powder; adding an organic solvent into the powdery sintering product and a carbon source, uniformly mixing, evaporating the solvent, continuously grinding the rest materials into powder, sintering the powder materials in an oxygen atmosphere, and finally grinding the sintering product to obtain the product. The positive electrode material can effectively solve the problems of poor cycle performance and low multiplying power performance of the existing positive electrode material.
Description
Technical Field
The invention relates to the technical field of lithium battery anode materials, in particular to a nickel cobalt lithium manganate lithium battery anode material and a preparation method thereof.
Background
Lithium batteries operate primarily by virtue of movement of lithium ions between a positive electrode and a negative electrode. During charge and discharge, li + To-and-fro intercalation and deintercalation between two electrodes: during charging, li + De-intercalation from the positive electrode, and intercalation into the negative electrode through the electrolyte, wherein the negative electrode is in a lithium-rich state; the opposite is true when discharging. The lithium battery has the following characteristics: high voltage, high capacity, low consumption, no memory effect, no pollution, small volume, small internal resistance, less self discharge and more cycle times. Because of the above characteristics, lithium batteries have been widely used in many civil and military fields such as mobile phones, notebook computers, video cameras, digital cameras, electric vehicles, and the like. However, the conventional lithium battery cathode materials often have the problems of poor cycle performance and low rate performance.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nickel cobalt lithium manganate lithium battery positive electrode material and a preparation method thereof, and the positive electrode material can effectively solve the problems of poor cycle performance and low multiplying power performance of the existing positive electrode material.
In order to achieve the above purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
the preparation method of the nickel cobalt lithium manganate lithium battery anode material comprises the following steps:
(1) Adding an organic solvent into NCM811 and a niobium source, stirring, evaporating the solvent, and grinding the rest materials into powder;
(2) Carrying out two-stage sintering on the powdery material ground in the step (1) in an oxygen atmosphere, and then continuously grinding a sintered product into powder;
(3) Adding the powdery sintering product and the carbon source in the step (2) into an organic solvent, uniformly mixing, evaporating the solvent, continuously grinding the rest materials into powder, sintering the powder materials in an oxygen atmosphere, and finally grinding the sintering product to obtain the product.
Further, in the step (1), the niobium source is at least one of niobium pentoxide, lithium niobate, niobium trioxide and niobium ethoxide.
Further, the organic solvent in the step (1) is at least one of ethanol, ethylene glycol, isopropanol and acetone.
Further, the mass ratio of NCM811 to niobium source in step (1) is 1:0.03-0.07.
In the scheme, the mass ratio of NCM811 to the niobium source is too small, so that the mixing is uneven, and the doping effect cannot be reflected; the mass ratio is too large, so that the specific capacity of the positive electrode material is obviously reduced, and the material performance is deteriorated.
Further, in the step (1), magnetic stirring is performed for 1-10 hours, and then ultrasonic dispersing is performed for 1-5 minutes.
Further, the oxygen flux in the step (2) is 0.5-10L/h.
Further, the two-stage calcination in step (2) is specifically operated as: heating to 450-550 ℃ at the speed of 3-5 ℃/min and preserving heat for 4-8h, heating to 760-840 ℃ at the speed of 3-5 ℃/min and preserving heat for 8-14h, and naturally cooling to room temperature.
Further, the sintering temperature in the step (3) is 350-400 ℃.
In the scheme, the heating speed and the calcining temperature can influence the uniformity of solid-phase diffusion, and the heating speed is too high, so that the coating agent is not spread out as soon as the diffusion is performed, and further the first coulomb efficiency and the discharge capacity are lower; too low calcination temperature cannot guarantee the binding force of the coating layer, so that the coating layer is easy to fall off and break, the proportion of active materials is reduced, and the capacity is reduced.
Further, in the step (3), the mass ratio of the powder material to the carbon source is 1:0.01-0.1, and the carbon source is a low molecular organic matter including biogenic amine, glucose, sucrose and caramel.
In the scheme, the mass ratio of the powder material to the carbon source is too small, so that the mixing is uneven, and the doping effect cannot be reflected; the mass ratio is too large, so that the specific capacity of the positive electrode material is obviously reduced, and the material performance is deteriorated.
The beneficial effects of the invention are as follows:
the electrode material in the application adopts a double-layer coating mode, so that the interfacial tension between the electrolyte and the electrode material is improved, the polarization between the electrolyte and the electrode material is reduced, the electrolyte can wet the deep part of the electrode material, and the first coulomb efficiency and the discharge capacity are greatly improved; meanwhile, by adopting a double-layer coating mode, the combination effect between the carbon material and the matrix material can be improved, the stability of the active layer can be improved, the loss of the active material is reduced, and the specific capacity and the cycle stability are further improved.
Drawings
Fig. 1 is a comparison of discharge capacities of the positive electrode materials in examples 1 and 2 and comparative examples 1 and 2 at different rate currents;
fig. 2 is an initial charge-discharge curve of the positive electrode materials in examples 1, 2 and comparative examples 1, 2 at a current of 0.1C magnification;
fig. 3 is a graph showing the cycle capacity at 0.1C of the positive electrode materials in examples 1 and 2 and comparative examples 1 and 2;
fig. 4 is an ac impedance curve of the positive electrode materials in examples 1 and 2 and comparative examples 1 and 2.
Detailed Description
The following describes the embodiments of the present invention in detail with reference to the drawings.
Example 1
The preparation method of the nickel cobalt lithium manganate lithium battery anode material comprises the following steps:
(1) Adding ethanol into NCM811 and niobium pentoxide, wherein the mass ratio of the NCM811 to the niobium pentoxide is 1:0.05, magnetically stirring for 5 hours, performing ultrasonic dispersion for 3 minutes, evaporating the solvent at 60 ℃, and grinding the rest materials into powder by an agate mortar for 30 minutes;
(2) Carrying out two-stage sintering on the powder material ground in the step (1) under the oxygen atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min and preserving heat for 6 hours, then heating to 800 ℃ at the speed of 5 ℃/min and preserving heat for 12 hours, naturally cooling to room temperature, and then continuously grinding the sintered product into powder by an agate mortar;
(3) Adding ethanol into the powdery sintering product and glucose in the step (2) and uniformly mixing, wherein the mass ratio of the powdery sintering product to the carbon source is 1:0.05, evaporating the solvent, continuously grinding the rest materials into powder by an agate mortar, sintering the powder materials at 480 ℃ in an oxygen atmosphere, and finally grinding the sintering product by an agate mortar.
Example 2
The preparation method of the nickel cobalt lithium manganate lithium battery anode material comprises the following steps:
(1) Adding ethylene glycol into NCM811 and niobium trioxide, wherein the mass ratio of NCM811 to niobium trioxide is 1:0.03, magnetically stirring for 3 hours, performing ultrasonic dispersion for 5 minutes, evaporating the solvent at 60 ℃, and grinding the rest materials into powder by an agate mortar for 30 minutes;
(2) Carrying out two-stage sintering on the powder material ground in the step (1) under the oxygen atmosphere, firstly heating to 550 ℃ at the speed of 3 ℃/min and preserving heat for 8 hours, then heating to 840 ℃ at the speed of 4 ℃/min and preserving heat for 14 hours, naturally cooling to room temperature, and then continuously grinding the sintered product into powder by an agate mortar;
(3) Adding ethanol into the powdery sintering product and sucrose in the step (2) and uniformly mixing, wherein the mass ratio of the powdery sintering product to the carbon source is 1:0.02, evaporating the solvent, continuously grinding the rest materials into powder by an agate mortar, sintering the powder materials at the temperature of 490 ℃ in an oxygen atmosphere, and finally grinding the sintering product by an agate mortar.
Example 3
The preparation method of the nickel cobalt lithium manganate lithium battery anode material comprises the following steps:
(1) Adding isopropanol into NCM811 and niobium acetate, wherein the mass ratio of the NCM811 to the niobium acetate is 1:0.07, firstly magnetically stirring for 10 hours, then performing ultrasonic dispersion for 2 minutes, evaporating the solvent at 60 ℃, and grinding the rest materials into powder by an agate mortar for 30 minutes;
(2) Carrying out two-stage sintering on the powder material ground in the step (1) under the oxygen atmosphere, firstly heating to 45 ℃ at the speed of 5 ℃/min and preserving heat for 4 hours, then heating to 760 ℃ at the speed of 3 ℃/min and preserving heat for 8 hours, naturally cooling to room temperature, and then continuously grinding the sintered product into powder by an agate mortar;
(3) Adding ethanol into the powdery sintering product and biogenic amine in the step (2) and uniformly mixing, wherein the mass ratio of the powdery sintering product to the carbon source is 1:0.07, evaporating the solvent, continuously grinding the rest materials into powder by an agate mortar, sintering the powder materials at 500 ℃ in an oxygen atmosphere, and finally grinding the sintering product by an agate mortar.
Comparative example 1
The preparation method of the single-layer coated nickel cobalt lithium manganate lithium battery anode material comprises the following steps:
(1) Adding ethanol into NCM811 and niobium pentoxide, wherein the mass ratio of the NCM811 to the niobium pentoxide is 1:0.05, magnetically stirring for 5 hours, performing ultrasonic dispersion for 3 minutes, evaporating the solvent at 60 ℃, and grinding the rest materials into powder by an agate mortar for 30 minutes;
(2) And (3) carrying out two-stage sintering on the powder material ground in the step (1) under the oxygen atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min and preserving heat for 6 hours, then heating to 800 ℃ at the speed of 5 ℃/min and preserving heat for 12 hours, naturally cooling to room temperature, and then grinding the sintered product into powder by adopting an agate mortar.
Comparative example 2
The preparation method of the nickel cobalt lithium manganate lithium battery anode material comprises the following steps:
(1) Absolute ethyl alcohol is added into NCM811 and niobium pentoxide, the mass ratio of the NCM811 to the niobium pentoxide is 1:0.5, magnetic stirring is carried out for 5 hours, ultrasonic dispersion is carried out for 3 minutes, then solvent is evaporated at 60 ℃, and then the rest materials are ground into powder by an agate mortar for 30 minutes;
(2) Carrying out two-stage sintering on the powder material ground in the step (1) under the oxygen atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min and preserving heat for 6 hours, then heating to 800 ℃ at the speed of 5 ℃/min and preserving heat for 12 hours, naturally cooling to room temperature, and then continuously grinding the sintered product into powder by an agate mortar;
(3) Adding ethanol into the powdery sintering product and glucose in the step (2) and uniformly mixing, wherein the mass ratio of the powdery sintering product to the carbon source is 1:0.5, evaporating the solvent, continuously grinding the rest materials into powder by an agate mortar, sintering the powder materials at 480 ℃, and finally grinding the sintering product by an agate mortar to obtain the composite material.
Test examples
1. Battery assembly
Electrochemical performance testing was performed using CR2025 button cell, the specific procedure was: (1) and (3) baking: drying the positive electrode material in a vacuum drying oven at 120 ℃ for more than 12 hours; (2) stirring: dispersing a positive electrode material, a conductive agent and a binder PVDF (weight ratio of 8:1:1) by using a proper amount of NMP (N-methyl-2 pyrrolidone) as a solvent by using a high-speed refiner to prepare black uniform positive electrode paste; (3) coating: uniformly coating the positive electrode paste on the aluminum foil by using a film coater; (4) and (3) drying: drying the coated plate in a vacuum drying oven at 120 ℃ for more than 10 hours to remove NMP; (5) slicing: cutting the pole piece into a wafer electrode with the diameter of 1.4cm by using a slicer; (6) and (3) rolling: the pole piece is rolled, so that the compaction density and the binding force are improved; (7) weighing: the pole piece is weighed by using a ten-thousandth balance and recorded; (8) and (3) drying: continuously drying the pole piece in a vacuum drying oven at 120 ℃ for more than 8 hours; (9) assembling a battery: in a vacuum glove box (oxygen pressure, water pressure are lower than 0.1 ppm), assembling sequentially in the order of positive electrode shell-positive electrode plate-diaphragm-dropwise electrolyte solution-lithium plate-gasket-negative electrode shell, and sealing by using a sealing machine, wherein the electrolyte solution is Ethylene Carbonate (EC) and dimethyl carbonate (DMC) with the volume ratio of 1:1vol%, and the solute is 1 mol.L -1 LiPF of (a) 6 The method comprises the steps of carrying out a first treatment on the surface of the And (3) standing: the assembled battery was allowed to stand for 10 hours or more to allow the electrolyte to sufficiently infiltrate the electrode to be tested (the positive electrodes in examples 1-3 and comparative examples 1-2, respectivelyThe materials were prepared into cells and then the performance of each cell was tested).
2. Electrochemical performance test
The assembled button cell is a half cell, the positive electrode is a synthesized active substance, and the negative electrode is a lithium sheet, so that the electrochemical performance of the button cell can reflect the performance of a positive electrode material, and the electrochemical performance comprises a specific capacity test, a coulombic efficiency test, a multiplying power performance test, a cycle performance test, a cyclic voltammetry curve test and an alternating current impedance test. All performed at 25 ℃.
2.1 specific Capacity test
Specific charge-discharge capacity (C) o ) The ratio of the capacity obtained by constant current charge and discharge of the battery under a certain current to the mass of the active material can be calculated by the following formula:
C o ＝I*t/3600m
c in the formula o Specific charge-discharge capacity (mAh.g) of electrode material -1 )；
I-charge/discharge current (A);
t-charge/discharge time(s);
m-mass of electrode active material (g).
2.2 cycle Performance test
The cycle performance of the lithium ion battery refers to a method for testing constant-current charge-discharge cycle of the battery with a certain charge-discharge current, and the cycle current used by the invention is 0.1 ℃.
The test results in examples 1-2 and comparative examples 1-2 are shown in FIGS. 1-4;
as can be seen from fig. 1, the material of example 1 subjected to double-layer coating has higher discharge capacity at different multiplying powers; example 2 shows a lower rate capability due to the higher niobium source content, which affects ion transport efficiency; in the comparative example 1, only a single-layer niobium coating is adopted, so that the non-polar electrolyte has poor wetting effect on the surface of the polar coating layer, and the capacity cannot be effectively exerted; in comparative example 2, the niobium source ratio is too high, and the carbon source coating heat treatment temperature is low, so that the niobium coating layer and the carbon coating layer cannot effectively cooperate, resulting in a low rate capability.
As can be seen from fig. 2, the material subjected to double-layer coating in example 1 has a higher specific capacity for initial discharge of 204.9mAh/g; example 2 shows lower first efficiency and specific capacity due to higher niobium source content, which affects ion transport efficiency; the comparative example 1 only adopts a single-layer niobium coating, inhibits the electrolyte from wetting to reduce the first efficiency, and has the lowest capacity; in comparative example 2, the carbon source is not completely pyrolyzed due to the excessively high niobium source proportion and the lower carbon source cladding heat treatment temperature, so that the electrolyte is excessively strongly adsorbed, and the efficiency and the capacity are lower.
As can be seen from fig. 3, the embodiment 1 has higher cycle stability by double-layer coating, and the material is protected from electrolyte corrosion without reducing the ion transmission efficiency; in example 2, the niobium coating layer protects the electrode from the electrolyte, but the carbon source proportion is low, so that effective electric contact between material particles and the conductive agent cannot be ensured, and an island is formed in the circulation process to lose reversible capacity, so that poor circulation performance is presented; neither comparative example 1 nor comparative example 2 functions as a carbon coating layer, resulting in lower cycle performance.
As can be seen from fig. 4, example 1 has the smallest load transfer resistance and CEI membrane resistance, corresponding to its better electrochemical activity and stability; comparative examples 1 and 2 have a large load transfer resistance and film resistance, corresponding to poor rate performance and cycle performance; example 2 has the smallest membrane resistance, but has a larger load transfer resistance, and lithium ion transfer inside the particles is more difficult.
Claims (3)
1. The preparation method of the nickel cobalt lithium manganate lithium battery anode material is characterized by comprising the following steps of:
(1) Adding ethanol into NCM811 and niobium pentoxide, wherein the mass ratio of the NCM811 to the niobium pentoxide is 1:0.05, magnetically stirring for 5 hours, performing ultrasonic dispersion for 3 minutes, evaporating the solvent at 60 ℃, and grinding the rest materials into powder by an agate mortar for 30 minutes;
(2) Carrying out two-stage sintering on the powder material ground in the step (1) under the oxygen atmosphere, firstly heating to 500 ℃ at the speed of 4 ℃/min and preserving heat for 6 hours, then heating to 800 ℃ at the speed of 5 ℃/min and preserving heat for 12 hours, naturally cooling to room temperature, and then continuously grinding the sintered product into powder by an agate mortar;
(3) Adding ethanol into the powdery sintering product and glucose in the step (2) and uniformly mixing, wherein the mass ratio of the powdery sintering product to the carbon source is 1:0.05, evaporating the solvent, continuously grinding the rest materials into powder by an agate mortar, sintering the powder materials at 480 ℃ in an oxygen atmosphere, and finally grinding the sintering product by an agate mortar.
2. A lithium nickel cobalt manganese oxide positive electrode material for a lithium battery, which is characterized by being prepared by the method of claim 1.
3. The use of the nickel cobalt lithium manganate lithium battery anode material according to claim 2 in the preparation of a lithium battery anode material.
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