CN115064674A - High-rate long-cycle ternary cathode material, and preparation method and application thereof - Google Patents
High-rate long-cycle ternary cathode material, and preparation method and application thereof Download PDFInfo
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- 239000010406 cathode material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011247 coating layer Substances 0.000 claims abstract description 33
- 239000011159 matrix material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 73
- 239000011572 manganese Substances 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 34
- 238000005245 sintering Methods 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 239000007774 positive electrode material Substances 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 229910052748 manganese Inorganic materials 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 159000000000 sodium salts Chemical class 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 abstract description 35
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 239000007772 electrode material Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910012888 LiNi0.6Co0.1Mn0.3O2 Inorganic materials 0.000 description 11
- 239000002243 precursor Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 229940078494 nickel acetate Drugs 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910004838 Na2/3Ni1/3Mn2/3O2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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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
- H01M4/48—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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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides a high-rate long-cycle ternary cathode material, and a preparation method and application thereof. The high-magnification long-cycle ternary cathode material comprises a ternary cathode material matrix and a coating layer coated on the surface of the ternary cathode material matrix; the chemical formula of the ternary cathode material matrix is LiNi x Co y Mn 1‑x‑y O 2 Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1; the chemical formula of the coating layer is Na m Ni n Mn 1‑n O 2 Wherein m is more than 0.3 and less than 1.0, and n is more than 0.3 and less than 0.95. The preparation method is simple and easy to realize large-scale production, the prepared ternary cathode material is used as the cathode material of the lithium ion battery,can effectively stabilize electrode/electrolyte interface, reduce DCR and increase, promote the circulation and the multiplying power performance of material, can also effectively completely cut off the direct contact of electrode material and electrolyte, reduce the DCR growth of battery in the circulation process.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrode materials, in particular to a high-rate long-cycle ternary cathode material, and a preparation method and application thereof.
Background
Due to the guidance and promotion of national new energy policies, the lithium ion battery is rapidly applied and popularized in the fields of 3C, power batteries, aerospace, electric tools and the like. In the field of electric automobiles, the cycle life and rate performance of a battery are two important indexes for evaluating the performance of the battery and materials. Among them, the positive electrode material in the battery system is a decisive factor, and in the existing positive electrode material system, the ternary material is widely used by virtue of its advantages of high specific energy density and good cycle performance. It is well known that the electrochemical performance of the positive electrode material in the battery is greatly degraded as the battery is charged and discharged, mainly due to the following factors: (1) in the continuous cyclic charge-discharge process, the DCR of the battery is continuously increased due to the interface reaction of the electrode/electrolyte, and the electrochemical performance of the electrode material is influenced; (2) the interface coating layer is corroded by HF in the electrolyte, and a new interface is continuously formed, further deteriorating the capacity and cycle performance of the battery.
In order to improve the interfacial stability of the battery, the primary sintered material is usually coated and secondarily sintered by a solid-phase mixed coating method using an inert nano inorganic oxide (such as aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, etc.). However, the solid-phase hybrid coating method has the following disadvantages: (1) the formed coating layer is usually distributed in a point or island shape, the interface thickness is not uniform, the coverage is incomplete, and the electrochemical performance of the battery is not good under extreme use conditions; (2) the conventional nano oxide coating layer has a loose structure and is easy to react with HF to form a new exposed interface, so that the dissolution of transition metal is caused, the degradation of the structure and the attenuation of the performance of the interface are caused continuously, and the cycle performance and the rate performance of the material are reduced.
For example, CN108767246A adopts a solid-phase mixed coating method to coat inorganic oxides such as alumina, magnesia, titania and zirconia on the surface of the ternary positive electrode material, so that the obtained product has a good layered structure, the specific mass capacity of the first charge and discharge can reach 200mAh/g, and the capacity attenuation after 50 cycles is small. But the rate capability of the product is poor, and the capacity fading condition of longer circulation still needs to be further optimized.
Disclosure of Invention
In view of this, the present invention aims to provide a high-rate long-cycle ternary positive electrode material, and a preparation method and an application thereof. The high-rate long-cycle ternary cathode material can effectively stabilize an electrode/electrolyte interface, reduce corrosion and structural damage of the material interface, reduce DCR (direct current resistance) increase and improve cycle and rate performance of the material when being used as a lithium ion battery cathode material.
In a first aspect, the invention provides a high-rate long-cycle ternary cathode material, which comprises a ternary cathode material substrate and a coating layer coated on the surface of the ternary cathode material substrate;
the chemical formula of the ternary cathode material matrix is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1; the chemical formula of the coating layer is Na m Ni n Mn 1-n O 2 Wherein m is more than 0.3 and less than 1.0, and n is more than 0.3 and less than 0.95.
Preferably, the mass ratio of the coating layer to the ternary cathode material matrix is (0.0001-0.02): 1.
Preferably, the thickness of the coating layer is 5-50 nm.
Preferably, the particle size of the ternary cathode material matrix is 4-15 μm.
In a second aspect, the invention provides a preparation method of the high-rate long-cycle ternary cathode material, which comprises the following steps:
(1) mixing a ternary positive electrode material matrix with sodium salt to obtain a base solution;
(2) and adding an aqueous solution containing nickel and manganese into the base solution to carry out in-situ coating precipitation, and then sequentially carrying out drying and sintering treatment to obtain the ternary cathode material.
Preferably, the sodium salt comprises sodium carbonate.
Preferably, the mass ratio of the ternary positive electrode material matrix to the sodium salt to the nickel element to the manganese element is 1 (0.002-0.5) to (0.001-1.0).
Preferably, the adding speed of the aqueous solution containing the nickel and the manganese elements is 0.4-0.6mL/min, and preferably 0.5 mL/min.
Preferably, the sintering temperature is 200-800 ℃, and the sintering time is 5-30 h.
In a third aspect, the invention provides a lithium ion battery, which comprises the high-rate long-cycle ternary cathode material or the high-rate long-cycle ternary cathode material prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention covers a layer of compact Na with electrochemical activity on the surface of a ternary cathode material matrix by a liquid-phase in-situ coating technology m Ni n Mn 1-n O 2 When the coating layer is used as the lithium ion battery anode material, on one hand, the coating layer can effectively stabilize an electrode/electrolyte interface, reduce corrosion and structural damage of the material interface, reduce DCR growth and improve the cycle and rate performance of the material; on the other hand, the direct contact between the electrode material and the electrolyte can be effectively isolated, the interface defect caused by HF corrosion is obviously improved, and the DCR growth of the battery in the circulating process is reduced;
(2)Na m Ni n Mn 1-n O 2 the coating layer has very good electrochemical activity, Na ions and ions are exchanged in the first cycle process, the electrochemical activation of an interface layer is realized, the increase of battery impedance caused by the conventional high-internal-resistance oxide coating layer is avoided, and the coating layer has higher strength and can be kept complete in the electrode rolling process;
(3) the preparation method provided by the invention is simple and is easy to realize large-scale production.
Drawings
Fig. 1 is an SEM image of the ternary cathode material obtained in example 1;
FIG. 2 is a graph comparing the cycle performance at 25 ℃ of the ternary cathode materials obtained in examples 1-2 and comparative examples 1-2;
FIG. 3 is a graph comparing rate performance of ternary cathode materials obtained in examples 1-2 and comparative examples 1-2.
Detailed Description
All the raw materials involved in the present invention are not particularly limited in their sources, and may be either commercially available or prepared according to conventional preparation methods well known to those skilled in the art.
The invention provides a high-rate long-cycle ternary cathode material, which comprises a ternary cathode material matrix and a coating layer coated on the surface of the ternary cathode material matrix;
the chemical formula of the ternary cathode material matrix is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1; the chemical formula of the coating layer is Na m Ni n Mn 1-n O 2 Wherein m is more than 0.3 and less than 1.0, and n is more than 0.3 and less than 0.95.
The invention coats a layer of Na with compact structure and electrochemical activity on the surface of a ternary cathode material matrix by a liquid-phase in-situ coating technology m Ni n Mn 1-n O 2 The coating layer can effectively stabilize an electrode/electrolyte interface, reduce corrosion and structural damage of the material interface, reduce DCR growth and improve the cycle and rate performance of the material; on the other hand, the direct contact between the electrode material and the electrolyte can be effectively isolated, the interface defect caused by HF corrosion is obviously improved, and the DCR growth of the battery in the circulating process is reduced. In addition, Na m Ni n Mn 1-n O 2 The coating layer has very good electrochemical activity, exchanges Na ions and ions in the first cycle process, realizes the electrochemical activation of an interface layer, avoids the increase of battery impedance caused by the conventional oxide coating layer with high internal resistance, has higher strength, can keep complete in the electrode rolling process,
in the present invention, the mass ratio of the coating layer to the ternary cathode material matrix is preferably (0.0001-0.02):1, and may be 0.0001:1, 0.0005:1, 0.001:1, 0.005:1, 0.01:1, 0.015:1 or 0.02:1, and other values within the above numerical range may be selected, and are not described in detail herein.
In the invention, the thickness of the coating layer is preferably 5-50nm, if the thickness of the coating layer is less than 5nm, the coating layer may not effectively play a role in isolating the electrode/electrolyte interface reaction, and if the thickness of the coating layer exceeds 50nm, the phenomenon of instability of the phase interface of the material is caused, which is not favorable for the electrochemical performance of the material to achieve the optimal effect.
The thickness of the coating layer can be 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm or 50nm, and other values in the above numerical range can be selected, and are not described in detail herein.
In the present invention, the particle size of the ternary positive electrode material matrix is 4 to 15 μm, and may be 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, or the like.
The invention also provides a preparation method of the high-rate long-cycle ternary cathode material, which comprises the following steps:
(1) mixing a ternary positive electrode material matrix with sodium salt to obtain a base solution;
(2) and adding an aqueous solution containing nickel and manganese into the base solution to carry out in-situ coating precipitation, and then sequentially carrying out drying and sintering treatment to obtain the ternary cathode material.
In the present invention, the ternary cathode material matrix may be prepared according to a conventional method well known to those skilled in the art. Illustratively, the ternary cathode material matrix can be prepared according to the following method:
and (3) uniformly mixing the precursor of the ternary cathode material matrix with a lithium source, and sintering in the atmosphere of oxygen and/or air.
The chemical formula of the precursor of the ternary cathode material matrix is Ni x Co y Mn 1-x-y (OH) 2 Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1. The sintering temperature is preferably selectedThe temperature is 400 ℃ and 1000 ℃, and the sintering time is preferably 8-30 h.
The sintering temperature can be 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃ or the like.
The sintering time can be 8h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h or 30h and the like.
Other point values within the above range can be selected, and are not described in detail herein.
In the invention, the sintering process preferably further comprises jaw crushing and crushing treatment, so that the particle size of the ternary cathode material matrix obtained after crushing is 4-15 μm.
In the present invention, step (1) is preferably to mix the ternary positive electrode material with sodium carbonate to obtain a base solution. Wherein, the sodium carbonate can be used as a precipitator to precipitate the added nickel element and manganese element.
In the invention, the mass ratio of the ternary cathode material matrix, the sodium salt, the nickel element and the manganese element is 1 (0.002-0.5) to (0.001-1.0), which can be 1:0.002:0.001:0.001, 1:0.01:0.001:0.001, 1:0.2:0.5:0.5, 1:0.3:0.02:0.5, 1:0.1:0.03:0.4, 1:0.02:0.01:0.01, 1:0.2:0.1:0.1 or 1:0.05:1, and the like, and other values in the above numerical value range can be selected, which is not repeated herein.
The aqueous solution containing nickel and manganese elements may be prepared according to a conventional method well known to those skilled in the art by dissolving soluble nickel and manganese salts in water. In the present invention, it is preferable to add soluble nickel salt and manganese salt to the aqueous solution in sequence, dissolve them completely, and then stand for 12 to 20 hours. The standing time is more than 12 hours to ensure that the nickel element and the manganese element are uniformly dispersed in the aqueous solution.
The aqueous solution containing the nickel element and the manganese element can be filled by adopting a conventional filling mode well known to a person skilled in the art, and in the invention, a peristaltic pump is preferably adopted for filling so as to effectively control the speed of introducing the nickel element and the manganese element into the base solution and ensure that the thickness of the coating layer is 5-50 nm. The addition rate of the aqueous solution containing nickel and manganese is preferably 0.4-0.6mL/min, and more preferably 0.5 mL/min.
The addition rate can be 0.4mL/min, 0.45mL/min, 0.5mL/min, 0.55mL/min, or 0.6mL/min, and other values in the above numerical range can be selected, and are not described in detail herein.
The drying method is not particularly limited in the present invention, and in the present invention, the product obtained after in-situ coating precipitation is preferably dried in a rotary evaporator at 80 ℃ for 5 hours.
In the present invention, the sintering temperature is preferably 200-.
The sintering temperature may be 200 deg.C, 300 deg.C, 400 deg.C, 500 deg.C, 600 deg.C, 700 deg.C or 800 deg.C.
The sintering time can be 5h, 10h, 15h, 20h, 25h or 30h, etc.
Other point values within the above range can be selected, and are not described in detail herein.
The preparation method provided by the invention is simple and is easy for large-scale production.
The invention also provides a lithium ion battery which comprises the high-rate long-cycle ternary cathode material or the high-rate long-cycle ternary cathode material prepared by the preparation method.
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
To further illustrate the present invention, the following examples are provided for illustration. The starting materials used in the following examples of the present invention, the sources of which are not particularly limited, may be commercially available or prepared according to conventional methods well known to those skilled in the art.
Example 1
This example provides a compound of formula LiNi 0.6 Co 0.1 Mn 0.3 O 2 @Na 2/3 Ni 1/3 Mn 2/3 O 2 The preparation method of the ternary cathode material comprises the following steps:
(1) ni with a particle size of 4 μm 0.6 Co 0.1 Mn 0.3 (OH) 2 Uniformly mixing the precursor and lithium hydroxide according to the Li/(Ni + Mn) molar ratio of 1.04, sintering at 940 ℃ for 15h in the oxygen atmosphere of a box furnace, and crushing by using a pair of rollers (the upper distance is 15cm and the lower distance is 5cm) to obtain a ternary anode calcined material LiNi 0.6 Co 0.1 Mn 0.3 O 2 ；
(2) Adding 1g of nickel acetate and 0.492g of manganese acetate into 60mL of pure water, stirring for 1h for dissolving, and standing for 12h to obtain a water-in-water covering liquid containing nickel and manganese elements;
(3) adding 25g of the ternary positive electrode calcined material obtained in the step (1) into 0.01mol/L sodium carbonate solution to prepare 200mL of base solution, introducing the water coating solution containing nickel and manganese into the base solution through a peristaltic pump (0.5mL/min), transferring the solution into a rotary evaporator after complete precipitation, and drying the solution at 80 ℃ for 5 hours to obtain a pre-coated product after treatment;
(4) sintering the pre-coated product at 450 ℃ for 20h in an air atmosphere to obtain LiNi 0.6 Co 0.1 Mn 0.3 O 2 @Na 2/3 Ni 1/3 Mn 2/3 O 2 A ternary positive electrode material.
The ternary cathode material obtained in example 1 is characterized in morphology by using a scanning electron microscope, and as a result, as shown in fig. 1, it can be seen that an obvious coating layer structure is formed on the surface of the ternary cathode material, the coating layer is uniform, and the overall coating effect is good.
Example 2
This example provides a compound of formula LiNi 0.6 Co 0.1 Mn 0.3 O 2 @Na 1/3 Ni 2/3 Mn 1/3 O 2 The preparation method of the ternary cathode material comprises the following steps:
(1) ni with a particle size of 4 μm 0.6 Co 0.1 Mn 0.3 (OH) 2 The precursor and lithium hydroxide are mixed according to the Li/(Ni + Mn) molar ratio of 1.04Mixing uniformly, sintering at 940 ℃ for 15h in oxygen atmosphere of a box furnace, and crushing by a pair of rollers (the upper spacing is 15cm and the lower spacing is 5cm) to obtain the ternary positive electrode burnable material LiNi 0.6 Co 0.1 Mn 0.3 O 2 ；
(2) Adding 1g of nickel acetate and 0.492g of manganese acetate into 100mL of pure water, stirring for 1h for dissolving, and standing for 12h to obtain a water-in-water solution containing nickel and manganese elements;
(3) adding 20g of the ternary positive electrode calcined material obtained in the step (1) into 0.01mol/L sodium carbonate solution to prepare 200mL of base solution, introducing the water-in-water coating solution containing nickel and manganese into the base solution through a peristaltic pump (0.5mL/min), transferring the solution into a rotary evaporator after complete precipitation, and drying the solution at 80 ℃ for 5 hours to obtain a pre-coated product;
(4) sintering the pre-coated product at 450 ℃ for 20h in an air atmosphere to obtain LiNi 0.6 Co 0.1 Mn 0.3 O 2 @Na 1/3 Ni 2/3 Mn 1/3 O 2 A material.
Example 3
This example provides a compound of formula LiNi 0.65 Co 0.07 Mn 0.28 O 2 @Na 1/3 Ni 2/3 Mn 1/3 O 2 The preparation method of the ternary cathode material comprises the following steps:
(1) ni with a particle size of 10 μm 0.65 Co 0.07 Mn 0.28 (OH) 2 Uniformly mixing the precursor and lithium hydroxide according to the Li/(Ni + Mn) molar ratio of 1.04, sintering at 940 ℃ for 15h in the oxygen atmosphere of a box furnace, and crushing by a pair of rollers (the upper distance is 15cm and the lower distance is 5cm) to obtain the ternary anode one-sintering material LiNi 0.65 Co 0.07 Mn 0.28 O 2 ；
(2) Adding 1g of nickel acetate and 0.985g of manganese acetate into 80mL of pure water, stirring for 1h for dissolving, and standing for 12h to obtain a water-in-water covering liquid containing nickel and manganese elements;
(3) adding 20g of the ternary positive electrode calcined material obtained in the step (1) into 0.12mol/L sodium carbonate solution to prepare 220mL of base solution, introducing the water-in-water coating solution containing nickel and manganese elements into the base solution through a peristaltic pump (0.5mL/min), transferring the solution into a rotary evaporator after complete precipitation, and drying the solution at 80 ℃ for 5 hours to obtain a pre-coated product after treatment;
(4) sintering the pre-coated product at 600 ℃ for 9h in an air atmosphere to obtain LiNi 0.65 Co 0.07 Mn 0.28 O 2 @Na 1/3 Ni 2/3 Mn 1/3 O 2 A material.
Example 4
This example provides a compound of formula LiN i0.8 Co 0.1 Mn 0.1 O 2 @Na 2/3 Ni 0.6 Mn 0.4 O 2 The preparation method of the ternary cathode material comprises the following steps:
(1) ni with a particle size of 10 μm 0.8 Co 0.1 Mn 0.1 (OH) 2 Uniformly mixing the precursor and lithium hydroxide according to the Li/(Ni + Mn) molar ratio of 1.04, sintering at 750 ℃ for 11h in the oxygen atmosphere of a box furnace, and crushing by a bipolar pair roller (the upper spacing is 15cm and the lower spacing is 5cm) to obtain a ternary positive electrode calcined material LiNi 0.8 Co 0.1 Mn 0.1 O 2 ；
(2) Adding 1g of nickel acetate and 0.657g of manganese acetate into 40mL of pure water, stirring for 1h for dissolving, and standing for 12h to obtain a water-in-water covering liquid containing nickel and manganese elements;
(3) adding 40g of the ternary positive electrode calcined material obtained in the step (1) into 0.05mol/L sodium carbonate solution to prepare 300mL of base solution, introducing the water coating solution containing nickel and manganese into the base solution through a peristaltic pump (0.5mL/min), transferring the solution into a rotary evaporator after complete precipitation, and drying the solution at 80 ℃ for 5 hours to obtain a pre-coated product after treatment;
(4) sintering the pre-coated product at 550 ℃ for 8h in an air atmosphere to obtain LiN i0.8 Co 0.1 Mn 0.1 O 2 @Na 2/3 Ni 0.6 Mn 0.4 O 2 A material.
Comparative example 1
This comparative example provides a composition of formula LiN i0.6 Co 0.1 Mn 0.3 O 2 Three positive ofThe preparation method of the cathode material (namely, the ternary cathode material is not modified) is as follows:
(1) ni with a particle size of 4 μm 0.6 Co 0.1 Mn 0.3 (OH) 2 Uniformly mixing the precursor and lithium hydroxide according to the Li/(Ni + Mn) molar ratio of 1.04, sintering at 940 ℃ for 15h in the oxygen atmosphere of a box furnace, and crushing by a bipolar pair roller (the upper distance is 15cm, and the lower distance is 5cm) to obtain a ternary positive electrode primary-fired material;
(4) sintering the ternary positive electrode calcined material for 15 hours at 450 ℃ in air atmosphere to obtain LiNi 0.6 Co 0.1 Mn 0.3 O 2 A ternary positive electrode material.
Comparative example 2
This comparative example provides a composition of formula LiNi 0.6 Co 0.1 Mn 0.3 O 2 @Al 2 O 3 The ternary cathode material is coated by adopting a traditional dry method, and the method comprises the following specific steps:
(1) ni with a particle size of 4 μm 0.6 Co 0.1 Mn 0.3 (OH) 2 Uniformly mixing the precursor and lithium hydroxide according to the Li/(Ni + Mn) molar ratio of 1.04, sintering for 15h at 940 ℃ in the oxygen atmosphere of a box furnace, and crushing by using a bipolar pair roller (the upper distance is 15cm, and the lower distance is 5cm) to obtain a ternary positive electrode primary-fired material;
(2) 2.5Kg of ternary positive electrode calcined material obtained in the step (1) is uniformly mixed with 8g of nano-alumina, and then sintered for 15h at 450 ℃ in the air atmosphere of a box furnace to obtain LiNi 0.6 Co 0.1 Mn 0.3 O 2 @Al 2 O 3 A ternary positive electrode material.
Comparative example 3
This comparative example provides a composition of formula LiNi 0.65 Co 0.07 Mn 0.28 O 2 @MnO 2 The ternary cathode material is coated by adopting a traditional dry method, and the method comprises the following specific steps:
(1) ni with a particle size of 4 μm 0.65 Co 0.07 Mn 0.28 (OH) 2 The precursor and lithium carbonate are uniformly mixed according to the Li/(Ni + Mn) molar ratio of 1.05, and thenSintering at 930 ℃ for 15h in an oxygen atmosphere of a box furnace, and crushing by using bipolar double rollers (the upper distance is 15cm, and the lower distance is 5cm) to obtain a ternary positive electrode primary sintering material;
(2) 2.5Kg of ternary positive electrode calcined material obtained in the step (1) is uniformly mixed with 10g of nano manganese dioxide, and then sintered for 15h at 450 ℃ in the air atmosphere of a box furnace to obtain LiNi 0.6 Co 0.1 Mn 0.3 O 2 @MnO 2 A ternary positive electrode material.
Comparative example 4
This comparative example provides a composition of formula LiNi 0.6 Co 0.2 Mn 0.2 O 2 @TiO 2 The ternary cathode material is coated by adopting a traditional dry method, and the method comprises the following specific steps:
(1) ni with a particle size of 4 μm 0.6 Co 0.2 Mn 0.2 (OH) 2 Uniformly mixing the precursor and lithium carbonate according to the Li/(Ni + Mn) molar ratio of 1.05, sintering at 930 ℃ for 15h in an oxygen atmosphere of a box furnace, crushing by using a bipolar pair roller (the upper distance is 15cm, and the lower distance is 5cm), and thus obtaining a ternary positive electrode primary-fired material;
(2) 2.5Kg of ternary positive electrode calcined material obtained in the step (1) is uniformly mixed with 10g of nano titanium oxide, and then the mixture is sintered for 15 hours at 450 ℃ in the air atmosphere of a box furnace to obtain LiNi 0.6 Co 0.1 Mn 0.3 O 2 @MnO 2 A ternary positive electrode material.
Performance testing
The ternary positive electrode materials obtained in examples 1 to 4 and comparative examples 1 to 4 were subjected to a performance test by the following method:
assembling the prepared ternary cathode material into a button cell, wherein the electrode material comprises 90 to 10 weight percent of conductive carbon black, NMP is used as a solvent, and the areal density of a cell pole piece is 1.2mg/cm 2 Under the voltage of 2.8-4.4V, charging and discharging at 25 deg.C and 55 deg.C with 0.1C/0.1C multiplying power for 1 circle, charging and discharging at 0.1C/1C, 0.2C/1C, 0.5C/1C, 1C/1C multiplying power, and then testing at 1C/1C multiplying power for 50 circles. The test results are shown in table 1 below:
TABLE 1
As can be seen from the data in the above table, the capacity and retention performance of comparative examples 2-4 are not significantly improved compared to comparative example 1. As can be seen from the data of examples 1-2, the present invention provides Na m Ni n Mn 1-n O 2 The charge and discharge capacity of the coated and modified ternary cathode material is improved by about 2mAh/g, and Na m Ni n Mn 1-n O 2 The cycle performance and rate performance of the coated and modified ternary cathode material at 25 ℃ and 55 ℃ are obviously improved, which shows that the preparation method provided by the embodiments 1-4 of the invention can form an effective and stable interface layer after coating the modified ternary cathode material, reduce the interface reaction of the electrode/electrolyte and obviously improve the electrochemical performance of the material.
The ternary positive electrode materials obtained in examples 1-2 and comparative examples 1-2 were subjected to cycle performance test at 25 ℃ and normal temperature, the test method was as follows:
assembling the prepared ternary cathode material into a button cell, wherein the electrode material comprises 90 to 10 weight percent of conductive carbon black, NMP is used as a solvent, and the areal density of a cell pole piece is 1.2mg/cm 2 Under the voltage of 2.8-4.4V, charging and discharging are carried out for 1 circle at the temperature of 25 ℃ at the rate of 0.1C/0.1C, and then the test is carried out for 50 circles at the rate of 1C/1C.
As shown in fig. 2, it can be seen that the cycle performance of the positive electrode material prepared by the preparation method provided in examples 1-2 is significantly better than that of comparative examples 1-2, which indicates that the coating modification method provided in the present application is significantly better than the existing coating modification method.
Rate performance tests at 0.1C, 0.2C, 0.5C, 1C, and 2C rates were performed on the ternary positive electrode materials obtained in examples 1-2 and comparative examples 1-2, the test methods being as follows:
assembling the prepared ternary cathode material into a button cell, wherein the electrode material comprises 90 to 10 weight percent of conductive carbon black, NMP is used as a solvent, and the areal density of a cell pole piece is 1.2mg/cm 2 Under the voltage of 2.8-4.4V and at 25 ℃, after charging and discharging for 1 circle at the multiplying factor of 0.1C/0.1C, the charging and discharging tests are respectively carried out at the multiplying factors of 0.1C/1C, 0.2C/1C, 0.5C/1C and 1C/1C.
The test results are shown in fig. 3, and it can be seen that the rate performance of the cathode material prepared by the preparation method provided by examples 1-2 is obviously better than that of comparative examples 1-2, which indicates that the coating modification method provided by the application is obviously better than the existing coating modification method.
In summary, Na is provided by the present application m Ni n Mn 1-n O 2 The method for coating the modified ternary cathode material comprises the step of coating a layer of Na with a compact structure and electrochemical activity on the surface of the ternary cathode material by a liquid-phase in-situ coating technology m Ni n Mn 1- n O 2 The coating layer can effectively stabilize an electrode/electrolyte interface, reduce corrosion and structural damage of the material interface, reduce DCR growth and improve the cycle and rate performance of the material; on the other hand, Na m Ni n Mn 1-n O 2 The coating layer can effectively isolate the direct contact of the electrode material and the electrolyte, obviously improve the interface defect caused by HF corrosion, reduce the increase of DCR of the battery in the circulating process, and has the advantages of simple process, strong equipment universality and easy large-scale production.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A high-magnification long-cycle ternary cathode material comprises a ternary cathode material matrix and a coating layer coated on the surface of the ternary cathode material matrix;
the chemical formula of the ternary cathode material matrix is LiNi x Co y Mn 1-x-y O 2 Wherein x is more than 0 and less than 1, and y is more than 0 and less than 1;
the coatingThe layer has the chemical formula of Na m Ni n Mn 1-n O 2 Wherein m is more than 0.3 and less than 1.0, and n is more than 0.3 and less than 0.95.
2. The high-rate long-cycle ternary cathode material according to claim 1, wherein the mass ratio of the coating layer to the ternary cathode material matrix is (0.0001-0.02): 1.
3. The high-rate long-cycle ternary cathode material according to claim 1, wherein the thickness of the coating layer is 5 to 50 nm.
4. The high-rate long-cycle ternary cathode material according to claim 1, wherein the particle size of the ternary cathode material matrix is 4-15 μm.
5. The preparation method of the high-rate long-cycle ternary cathode material according to any one of claims 1 to 4, comprising the following steps:
(1) mixing a ternary positive electrode material matrix with sodium salt to obtain a base solution;
(2) and adding an aqueous solution containing nickel and manganese into the base solution to carry out in-situ coating precipitation, and then sequentially carrying out drying and sintering treatment to obtain the ternary cathode material.
6. The method of claim 5, wherein the sodium salt comprises sodium carbonate.
7. The method according to claim 5, wherein the mass ratio of the ternary positive electrode material matrix to the sodium salt to the nickel element to the manganese element is 1 (0.002-0.5): 0.001-1.0.
8. The method according to claim 5, wherein the adding speed of the aqueous solution containing nickel and manganese elements is 0.4-0.6mL/min, preferably 0.5 mL/min.
9. The preparation method according to claim 5, wherein the sintering temperature is 200-800 ℃, and the sintering time is 5-30 h.
10. A lithium ion battery, which is characterized by comprising the high-rate long-cycle ternary cathode material of any one of claims 1 to 4 or the high-rate long-cycle ternary cathode material prepared by the preparation method of any one of claims 5 to 9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103915617A (en) * | 2014-04-18 | 2014-07-09 | 东莞市迈科科技有限公司 | Lithium-rich positive material and preparation method thereof |
| CN108511699A (en) * | 2018-01-19 | 2018-09-07 | 深圳市沃特玛电池有限公司 | A kind of preparation method of the ternary composite cathode material of lithium ion battery |
| CN110048100A (en) * | 2019-03-29 | 2019-07-23 | 桂林理工大学 | The method for improving nickelic tertiary cathode material chemical property by magnesium fluoride/sodium modified synergic |
| CN111029560A (en) * | 2019-12-03 | 2020-04-17 | 松山湖材料实验室 | Spinel structure positive active material doped with sodium ions in gradient manner and preparation method thereof |
| CN114361440A (en) * | 2022-01-07 | 2022-04-15 | 巴斯夫杉杉电池材料有限公司 | High-voltage ternary cathode material with core-shell structure and preparation method thereof |
| CN114620781A (en) * | 2022-05-13 | 2022-06-14 | 宜宾锂宝新材料有限公司 | High-voltage ternary cathode material and preparation method thereof |
-
2022
- 2022-06-28 CN CN202210743840.1A patent/CN115064674A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103915617A (en) * | 2014-04-18 | 2014-07-09 | 东莞市迈科科技有限公司 | Lithium-rich positive material and preparation method thereof |
| CN108511699A (en) * | 2018-01-19 | 2018-09-07 | 深圳市沃特玛电池有限公司 | A kind of preparation method of the ternary composite cathode material of lithium ion battery |
| CN110048100A (en) * | 2019-03-29 | 2019-07-23 | 桂林理工大学 | The method for improving nickelic tertiary cathode material chemical property by magnesium fluoride/sodium modified synergic |
| CN111029560A (en) * | 2019-12-03 | 2020-04-17 | 松山湖材料实验室 | Spinel structure positive active material doped with sodium ions in gradient manner and preparation method thereof |
| CN114361440A (en) * | 2022-01-07 | 2022-04-15 | 巴斯夫杉杉电池材料有限公司 | High-voltage ternary cathode material with core-shell structure and preparation method thereof |
| CN114620781A (en) * | 2022-05-13 | 2022-06-14 | 宜宾锂宝新材料有限公司 | High-voltage ternary cathode material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024066867A1 (en) * | 2022-09-27 | 2024-04-04 | 天津巴莫科技有限责任公司 | High-nickel ternary positive electrode material, preparation method therefor and use thereof, and lithium battery |
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