CN109888261B - Modified nickel-rich ternary composite electrode material and preparation method thereof - Google Patents
Modified nickel-rich ternary composite electrode material and preparation method thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 170
- 239000011206 ternary composite Substances 0.000 title claims abstract description 65
- 150000002815 nickel Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 240
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 121
- 230000004048 modification Effects 0.000 claims abstract description 48
- 238000012986 modification Methods 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 238000007580 dry-mixing Methods 0.000 claims description 85
- 238000005245 sintering Methods 0.000 claims description 65
- 238000010438 heat treatment Methods 0.000 claims description 64
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 41
- 229910052760 oxygen Inorganic materials 0.000 claims description 41
- 239000001301 oxygen Substances 0.000 claims description 41
- 238000000498 ball milling Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 20
- 229910019714 Nb2O3 Inorganic materials 0.000 claims description 17
- 238000006138 lithiation reaction Methods 0.000 claims description 10
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 9
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 9
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 9
- 229910007562 Li2SiO3 Inorganic materials 0.000 claims description 5
- 150000002642 lithium compounds Chemical class 0.000 abstract description 16
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 238000004090 dissolution Methods 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 239000010955 niobium Substances 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002238 attenuated effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000484 niobium oxide Inorganic materials 0.000 abstract description 2
- 230000008707 rearrangement Effects 0.000 abstract description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 abstract 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 16
- 229910001416 lithium ion Inorganic materials 0.000 description 16
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000010405 anode material Substances 0.000 description 8
- 229910009740 Li2GeO3 Inorganic materials 0.000 description 7
- 229910007822 Li2ZrO3 Inorganic materials 0.000 description 5
- 229910010092 LiAlO2 Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- -1 Lithium compound Chemical class 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 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 description 1
- 238000006479 redox reaction Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a modified nickel-rich ternary composite electrode material, which comprises a nickel-rich ternary electrode material doped with an oxide and a modification layer of a lithiated compound on the outer side, wherein the nickel-rich ternary electrode material is prepared from LiO, NiO, CoO, MnO and the doped oxide. The lithium compound modified by the invention can prevent the dissolution of metal ions in the nickel-rich ternary electrode material, and solves the problems that the material performance is rapidly attenuated due to the corrosion of electrolyte in the high current density circulation process of the battery, the doping of niobium or molybdenum oxide inhibits the rearrangement of lithium and nickel in the material, the circulation performance and the rate performance are improved, the stability is poor, and the capacity is rapidly attenuated.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a modified nickel-rich ternary composite electrode material and a preparation method thereof.
Background
Compared with the traditional battery, the lithium ion battery has the advantages of high working voltage, high energy density, small pollution, no memory effect and the like, and is widely applied to the fields of electronic products, mobile tools and the like. With the increasing attention of people to environmental pollution, green and environment-friendly electric vehicles using lithium ions as power or auxiliary power are advocated and paid attention to.
The ternary lithium ion battery positive electrode material is a novel lithium ion battery positive electrode material developed in recent years, compared with a lithium cobaltate material, the ternary lithium ion battery positive electrode material has the advantages of reducing the production cost, improving the safety performance, having higher capacity compared with a lithium manganate material, having better low-temperature performance compared with lithium iron phosphate, gradually showing the position in the positive electrode material, having high energy density, relatively longer endurance mileage and the like, so that the nickel-rich ternary positive electrode material has higher specific capacity compared with a common ternary material, nickel is a main redox reaction element, and the specific capacity of the battery can be effectively improved by improving the nickel content. From the point of view of the energy density of the battery and the endurance mileage of the electric vehicle, the nickel-containing ternary system has obvious advantages, in particular to the battery made of the nickel-rich ternary system material. And the Co content in the nickel-rich ternary material is lower, which means that the nickel-rich ternary material has better cost and energy density advantages. However, with the increase of nickel content, the cycle performance of the material is rapidly reduced, the stability is poor, the capacity fading is rapid, and the above defects restrict the commercial application of the material.
Disclosure of Invention
The invention aims to solve the technical problems that the modified nickel-rich ternary composite electrode material can prevent the dissolution of metal ions in the nickel-rich ternary electrode material after the nickel-rich ternary electrode material is modified by a lithium compound, the problem of rapid material performance attenuation caused by the erosion of an electrolyte on the anode material in the high-current density circulation process of a battery is solved, the problems of poor stability and rapid capacity attenuation of the nickel-rich ternary electrode material are solved, the lithium compound has excellent lithium ion conductivity, the diffusion rate of lithium ions in the anode material is effectively improved, and the cycle performance and the rate performance of the lithium ion battery are improved.
In order to solve the technical problems, the invention adopts the technical scheme that: the modified nickel-rich ternary composite electrode material comprises an oxide-doped nickel-rich ternary electrode material and a modification layer on the outer side of the nickel-rich ternary electrode material, wherein the thickness of the modification layer is 0.5-50 nm, the modification layer is made of lithium compounds, and the quality of the modification layer in the nickel-rich ternary composite electrode materialThe percentage is 1% -5%, the doped oxide of the nickel-rich ternary electrode material is Nb2O3Or MoO3Li in the nickel-rich ternary electrode material2The molar ratio of O, NiO, CoO, MnO and the doped oxide is (1.0-1.1): (0.7-0.9): (0.05-0.15): (0 to 0.01).
Preferably, Li in the nickel-rich ternary electrode material2The mol ratio of O, NiO, CoO, MnO and doped oxide is 1.04: 0.8: 0.1: 0.005.
preferably, the mass percentage of the modification layer in the nickel-rich ternary composite electrode material is 2%.
Preferably, the lithiate is Li2SiO3、Li2ZrO3、Li2GeO3And LiAlO2One or more than one of them.
The invention also provides a preparation method of the modified nickel-rich ternary composite electrode material, which comprises the following steps:
step one, Li2Mixing O, NiO, CoO, MnO and the doped oxide, and then carrying out dry-mixing ball milling to obtain an electrode material;
sintering the electrode material obtained in the step one in an oxygen atmosphere to obtain a nickel-rich ternary electrode material; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving the heat for 4h, heating the temperature to 700-900 ℃ at the heating rate of 5 ℃/min, sintering the temperature for 12-24 h, and finally naturally cooling the temperature to room temperature;
step three, mixing the nickel-rich ternary electrode material obtained in the step two with a lithiation compound, and then carrying out dry mixing and ball milling to obtain a precursor;
sintering the precursor obtained in the third step in an oxygen atmosphere to obtain a modified nickel-rich ternary composite electrode material; the sintering system comprises the following steps: and (3) heating the temperature from room temperature to 400-500 ℃ at a heating rate of 3 ℃/min, sintering for 5-10 h, and finally naturally cooling to room temperature.
Preferably, the ball-material ratio of the dry-mixing ball mill in the first step and the ball-material ratio of the dry-mixing ball mill in the fifth step are both 1:5, the rotating speed of the dry-mixing ball mill is 50 r/min-150 r/min, and the time of the dry-mixing ball mill is 5 h-15 h.
Preferably, the rotation speed of the dry mixing ball mill in the first step and the rotation speed of the dry mixing ball mill in the third step are both 100r/min, and the time of the dry mixing ball mill is both 10 h.
Preferably, the sintering temperature in the fourth step is 500 ℃, and the sintering time is 5 h.
Preferably, the introduction rate of the oxygen atmosphere in the second step and the fourth step is 0.01L/min-0.2L/min.
Compared with the prior art, the invention has the following advantages:
1. the invention modifies the nickel-rich ternary electrode material by using the doped oxide and the lithium compound, improves the thermal stability and the cycle performance, inhibits the rearrangement of lithium and nickel in the material by doping niobium or molybdenum in the doped oxide, reduces the mixed arrangement degree of cations, is favorable for improving the cycle performance and the rate performance of the material, and simultaneously coats the lithium compound on the surface of the nickel-rich ternary electrode material, thereby not only preventing the electrolyte from corroding the anode material in the high-current density cycle process of the battery, but also preventing the material performance of the nickel-rich ternary electrode material from being rapidly attenuated due to the dissolution of metal ions, resisting the corrosion of the electrolyte to the anode material, having excellent lithium ion conductivity, effectively improving the diffusion rate of the lithium ions in the anode material, being favorable for the transmission of the lithium ions, and greatly improving the cycle stability and the rate performance of the lithium ion battery, the problems of poor stability and rapid capacity fading of the nickel-rich ternary electrode material are solved, and one or more compounds are selected from the lithium compounds, so that the synergistic effect among the lithium compounds can better improve the stability and the cycle performance of the material.
2. The thickness of the modification layer of the lithium compound of the electrode material is only 0.5 nm-50 nm, and the too thick modification layer can reduce the surface impedance of the material, prevent the dissolution of metal ions in the material and enhance the stability of the composite electrode material, but the too thick modification layer can also weaken the electrochemical performance to a certain extent.
3. The invention is to dope oxide (Nb)2O3Or MoO3)、Li2The method selects oxides of Li, Ni, Co and Mn as raw materials, avoids the generation of impurities in the reaction process, has high Ni content in the ternary materials of Ni, Co and Mn, and has high energy density for preparing the modified nickel-rich ternary composite electrode material.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
Fig. 1 is a scanning electron microscope image of the modified nickel-rich ternary composite electrode material of example 1 of the present invention.
Fig. 2 is an X-ray diffraction pattern of the modified nickel-rich ternary composite electrode material of example 1 of the present invention.
Detailed Description
Example 1
The modified nickel-rich ternary composite electrode material comprises an oxide-doped nickel-rich ternary electrode material and a modification layer on the outer side of the nickel-rich ternary electrode material, wherein the thickness of the modification layer is 0.5-50 nm, and the modification layer is made of lithiated Li2SiO3The mass percentage of the modification layer in the nickel-rich ternary composite electrode material is 2 percent, and the doped oxide of the nickel-rich ternary electrode material is Nb2O3Li in the nickel-rich ternary electrode material2O, NiO, CoO, MnO and Nb2O3The molar ratio of (1.04: 0.8: 0.1): 0.005.
the embodiment also provides a method for preparing the modified nickel-rich ternary composite electrode material, which comprises the following steps:
step one, Li2O, NiO, CoO, MnO and Nb2O3Carrying out dry mixing and ball milling after mixing to obtain an electrode material; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 100r/min, and the time of the dry-mixing ball mill is 10 hours;
sintering the electrode material obtained in the step one in an oxygen atmosphere to obtain a nickel-rich ternary electrode material; the introduction rate of the oxygen atmosphere is 0.1L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving the heat for 4h, then heating the temperature to 800 ℃ at the heating rate of 5 ℃/min, sintering the temperature for 18h, and finally naturally cooling the temperature to room temperature;
step three, mixing the nickel-rich ternary electrode material obtained in the step two with a lithiation compound, and then carrying out dry mixing and ball milling to obtain a precursor; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 100r/min, and the time of the dry-mixing ball mill is 10 hours;
sintering the precursor obtained in the third step in an oxygen atmosphere to obtain a modified nickel-rich ternary composite electrode material; the introduction rate of the oxygen atmosphere is 0.1L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, sintering for 5h, and finally naturally cooling to room temperature.
Fig. 1 is a scanning electron microscope image of the nickel-rich ternary composite electrode material prepared in this example, and fig. 2 is an X-ray diffraction spectrum of the nickel-rich ternary composite electrode material prepared in this example, where a is a standard card corresponding to the nickel-rich ternary material, b is the nickel-rich ternary material, c is the nickel-rich ternary material modified by lithium zirconate niobium oxide, and analysis can be performed to obtain the nickel-rich ternary composite electrode material, and all spectra show a typical layered structure, and a synthesized positive electrode can be obtained from each diffraction peak. The degree of splitting of the (006)/(102) and (108)/(110) peaks of the synthesized samples indicates that the samples are well layered.
The nickel-rich ternary composite electrode material prepared in the embodiment has the first specific discharge capacity of 155mAh/g under the discharge rate of 1C, and the capacity retention rate of 85.5% after 100 cycles.
Comparative example 1
The nickel-rich ternary electrode material of the present comparative example consists of Li2O, NiO, CoO and MnO, and Li in the nickel-rich ternary electrode material2The molar ratio of O, NiO, CoO and MnO is 1.04: 0.8: 0.1.
The present comparative example also provides a method of preparing the nickel-rich ternary electrode material described above, comprising the steps of:
step one, Li2Mixing O, NiO, CoO and MnO, and then carrying out dry-mixing ball milling to obtain an electrode material; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 100r/min, and the time of the dry-mixing ball mill is 10 hours;
sintering the electrode material obtained in the step one in an oxygen atmosphere to obtain a nickel-rich ternary electrode material; the introduction rate of the oxygen atmosphere is 0.1L/min; the sintering system comprises the following steps: and (3) heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving the temperature for 4h, heating the temperature to 800 ℃ at the heating rate of 5 ℃/min, sintering the temperature for 18h, and naturally cooling the temperature to room temperature to obtain the nickel-rich ternary electrode material.
The nickel-rich ternary composite electrode material prepared by the comparative example has the specific discharge capacity of 150mAh/g at the first discharge rate of 1C, the capacity retention rate of 75% after 100 cycles, and poor performance compared with the example 1, and shows that the doped oxide Nb used in the example 1 is Nb2O3Lithium compound Li2SiO3The nickel-rich ternary electrode material is modified, so that the thermal stability and the cycle performance are improved.
Doped oxide Nb for this example2O3Lithium compound Li2SiO3The lithium compound is coated on the surface of the nickel-rich ternary electrode material, so that the anode material of the battery can be prevented from being corroded by electrolyte in the high-current density circulation process, the material performance of the nickel-rich ternary electrode material can be prevented from being rapidly attenuated due to the dissolution of metal ions, the corrosion of the electrolyte to the anode material can be resisted, the lithium compound has excellent lithium ion conductivity, the diffusion rate of lithium ions in the anode material is effectively improved, and the transmission of the lithium ions is facilitated, so that the circulation stability and the rate capability of the lithium ion battery can be greatly improved, and the problem of high-concentration ternary electrode material is solvedThe nickel ternary electrode material has the problems of poor stability and fast capacity fading, and the lithium compound is selected from one or more compounds, and the stability and the cycle performance of the material can be better improved due to the synergistic effect among the lithium compounds.
The thickness of the modification layer of the lithium compound of the electrode material of the embodiment is only 0.5nm to 50nm, and if the modification layer is too thick, the surface impedance of the material can be reduced, the dissolution of metal ions in the material can be prevented, and the stability of the composite electrode material can be enhanced, but the electrochemical performance of the composite electrode material can be weakened to a certain extent by the too thick modification layer.
This example uses a doped oxide Nb2O3、Li2The method selects oxides of Li, Ni, Co and Mn as raw materials, avoids the generation of impurities in the reaction process, has high Ni content in the ternary materials of Ni, Co and Mn, and has high energy density for preparing the modified nickel-rich ternary composite electrode material.
Example 2
The modified nickel-rich ternary composite electrode material comprises an oxide-doped nickel-rich ternary electrode material and a modification layer on the outer side of the nickel-rich ternary electrode material, wherein the thickness of the modification layer is 0.5-50 nm, and the modification layer is made of lithiated Li2ZrO3And Li2GeO3The nickel-rich ternary composite electrode material is prepared according to the mass ratio of 1:1, the mass percent of a modification layer in the nickel-rich ternary composite electrode material is 1%, and the doped oxide of the nickel-rich ternary electrode material is Nb2O3Li in the nickel-rich ternary electrode material2O, NiO, CoO, MnO and Nb2O3The molar ratio of (1.0: 0.7: 0.05): 0.005.
the embodiment also provides a method for preparing the modified nickel-rich ternary composite electrode material, which comprises the following steps:
step one, Li2O, NiO, CoO, MnO and Nb2O3Carrying out dry mixing and ball milling after mixing to obtain an electrode material; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 50r/min, and the time of the dry-mixing ball mill is 15 h;
sintering the electrode material obtained in the step one in an oxygen atmosphere to obtain a nickel-rich ternary electrode material; the introduction rate of the oxygen atmosphere is 0.01L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving the heat for 4h, then heating the temperature to 700 ℃ at the heating rate of 5 ℃/min, sintering the temperature for 24h, and finally naturally cooling the temperature to room temperature;
step three, mixing the nickel-rich ternary electrode material obtained in the step two with a lithiation compound, and then carrying out dry mixing and ball milling to obtain a precursor; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 50r/min, and the time of the dry-mixing ball mill is 15 h;
sintering the precursor obtained in the third step in an oxygen atmosphere to obtain a modified nickel-rich ternary composite electrode material; the introduction rate of the oxygen atmosphere is 0.01L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 400 ℃ at the heating rate of 3 ℃/min, sintering for 10h, and finally naturally cooling to room temperature.
The nickel-rich ternary composite electrode material prepared in the embodiment has a first discharge specific capacity of 148mAh/g under a 1C discharge rate, and the capacity retention rate reaches 80% after 100 cycles.
Example 3
The modified nickel-rich ternary composite electrode material comprises an oxide-doped nickel-rich ternary electrode material and a modification layer on the outer side of the nickel-rich ternary electrode material, wherein the thickness of the modification layer is 0.5-50 nm, and the modification layer is made of lithiated Li2ZrO3、Li2GeO3And LiAlO2According to the mass ratio of 1:1, the mass percent of the modification layer in the nickel-rich ternary composite electrode material is 2%, and the doped oxide of the nickel-rich ternary electrode material is MoO3Li in the nickel-rich ternary electrode material2O, NiO, CoO, MnO and MoO3In a molar ratio of 1.1: 0.9: 0.15∶0.15：0.01。
The embodiment also provides a method for preparing the modified nickel-rich ternary composite electrode material, which comprises the following steps:
step one, Li2O, NiO, CoO, MnO and MoO3Carrying out dry mixing and ball milling after mixing to obtain an electrode material; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 150r/min, and the time of the dry-mixing ball mill is 5 hours;
sintering the electrode material obtained in the step one in an oxygen atmosphere to obtain a nickel-rich ternary electrode material; the introduction rate of the oxygen atmosphere is 0.2L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving the heat for 4h, then heating the temperature to 900 ℃ at the heating rate of 5 ℃/min, sintering the temperature for 12h, and finally naturally cooling the temperature to room temperature;
step three, mixing the nickel-rich ternary electrode material obtained in the step two with a lithiation compound, and then carrying out dry mixing and ball milling to obtain a precursor; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 150r/min, and the time of the dry-mixing ball mill is 5 hours;
sintering the precursor obtained in the third step in an oxygen atmosphere to obtain a modified nickel-rich ternary composite electrode material; the introduction rate of the oxygen atmosphere is 0.2L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 450 ℃ at the heating rate of 3 ℃/min, sintering for 7.5h, and finally naturally cooling to room temperature.
The nickel-rich ternary composite electrode material prepared in the embodiment has a first discharge specific capacity of 154mAh/g under a 1C discharge rate, and the capacity retention rate of 85% after 100 cycles.
Example 4
The modified nickel-rich ternary composite electrode material comprises an oxide-doped nickel-rich ternary electrode material and a modification layer on the outer side of the nickel-rich ternary electrode material, wherein the thickness of the modification layer is 0.5-50 nm, and the modification layer is made of lithiated Li2ZrO3、Li2GeO3And LiAlO2According to the mass ratio of 1:1 is made ofThe mass percent of the modification layer in the nickel ternary composite electrode material is 1 percent, and the doped oxide of the nickel-rich ternary electrode material is MoO3Li in the nickel-rich ternary electrode material2O, NiO, CoO, MnO and MoO3The molar ratio of (1.1: 0.7: 0.05): 0.002.
the embodiment also provides a method for preparing the modified nickel-rich ternary composite electrode material, which comprises the following steps:
step one, Li2O, NiO, CoO, MnO and MoO3Carrying out dry mixing and ball milling after mixing to obtain an electrode material; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 100r/min, and the time of the dry-mixing ball mill is 10 hours;
sintering the electrode material obtained in the step one in an oxygen atmosphere to obtain a nickel-rich ternary electrode material; the introduction rate of the oxygen atmosphere is 0.15L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving the heat for 4h, then heating the temperature to 800 ℃ at the heating rate of 5 ℃/min, sintering the temperature for 24h, and finally naturally cooling the temperature to room temperature;
step three, mixing the nickel-rich ternary electrode material obtained in the step two with a lithiation compound, and then carrying out dry mixing and ball milling to obtain a precursor; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 100r/min, and the time of the dry-mixing ball mill is 10 hours;
sintering the precursor obtained in the third step in an oxygen atmosphere to obtain a modified nickel-rich ternary composite electrode material; the introduction rate of the oxygen atmosphere is 0.15L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 450 ℃ at the heating rate of 3 ℃/min, sintering for 10h, and finally naturally cooling to room temperature.
The nickel-rich ternary composite electrode material prepared in the embodiment has the specific discharge capacity of 151mAh/g at 1C discharge rate for the first time, and the capacity retention rate of 82% after 100 cycles.
Example 5
The modified nickel-rich ternary composite electrode material comprises nickel-rich ternary doped with oxideThe thickness of the modification layer is 0.5-50 nm, and the modification layer is made of lithium compound Li2GeO3The mass percentage of the modification layer in the nickel-rich ternary composite electrode material is 3 percent, and the doped oxide of the nickel-rich ternary electrode material is Nb2O3Li in the nickel-rich ternary electrode material2O, NiO, CoO, MnO and Nb2O3The molar ratio of (1.0: 0.7: 0.15): 0.01.
the embodiment also provides a method for preparing the modified nickel-rich ternary composite electrode material, which comprises the following steps:
step one, Li2O, NiO, CoO, MnO and Nb2O3Carrying out dry mixing and ball milling after mixing to obtain an electrode material; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 80r/min, and the time of the dry-mixing ball mill is 8 hours;
sintering the electrode material obtained in the step one in an oxygen atmosphere to obtain a nickel-rich ternary electrode material; the introduction rate of the oxygen atmosphere is 0.2L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving the heat for 4h, then heating the temperature to 800 ℃ at the heating rate of 5 ℃/min, sintering the temperature for 18h, and finally naturally cooling the temperature to room temperature;
step three, mixing the nickel-rich ternary electrode material obtained in the step two with a lithiation compound, and then carrying out dry mixing and ball milling to obtain a precursor; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 80r/min, and the time of the dry-mixing ball mill is 8 hours;
sintering the precursor obtained in the third step in an oxygen atmosphere to obtain a modified nickel-rich ternary composite electrode material; the introduction rate of the oxygen atmosphere is 0.2L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 400 ℃ at the heating rate of 3 ℃/min, sintering for 10h, and finally naturally cooling to room temperature.
The nickel-rich ternary composite electrode material prepared in the embodiment has the specific discharge capacity of 151mAh/g at 1C discharge rate for the first time, and the capacity retention rate of 82% after 100 cycles.
Example 6
The modified nickel-rich ternary composite electrode material comprises an oxide-doped nickel-rich ternary electrode material and a modification layer on the outer side of the nickel-rich ternary electrode material, wherein the thickness of the modification layer is 0.5-50 nm, and the modification layer is made of lithiated Li2GeO3And LiAlO2The nickel-rich ternary composite electrode material is prepared according to the mass ratio of 1:2, the mass percent of a modification layer in the nickel-rich ternary composite electrode material is 4%, and the doped oxide of the nickel-rich ternary electrode material is Nb2O3Li in the nickel-rich ternary electrode material2O, NiO, CoO, MnO and Nb2O3The molar ratio of (1.0: 0.9: 0.05: 0.15): 0.008.
the embodiment also provides a method for preparing the modified nickel-rich ternary composite electrode material, which comprises the following steps:
step one, Li2O, NiO, CoO, MnO and Nb2O3Carrying out dry mixing and ball milling after mixing to obtain an electrode material; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 150r/min, and the time of the dry-mixing ball mill is 5 hours;
sintering the electrode material obtained in the step one in an oxygen atmosphere to obtain a nickel-rich ternary electrode material; the introduction rate of the oxygen atmosphere is 0.02L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving the heat for 4h, then heating the temperature to 850 ℃ at the heating rate of 5 ℃/min, sintering the temperature for 18h, and finally naturally cooling the temperature to room temperature;
step three, mixing the nickel-rich ternary electrode material obtained in the step two with a lithiation compound, and then carrying out dry mixing and ball milling to obtain a precursor; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 150r/min, and the time of the dry-mixing ball mill is 5 hours;
sintering the precursor obtained in the third step in an oxygen atmosphere to obtain a modified nickel-rich ternary composite electrode material; the introduction rate of the oxygen atmosphere is 0.02L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 450 ℃ at the heating rate of 3 ℃/min, sintering for 7.5h, and finally naturally cooling to room temperature.
The nickel-rich ternary composite electrode material prepared in the embodiment has a first discharge specific capacity of 153mAh/g under a discharge rate of 1C, and the capacity retention rate of 85% after 100 cycles.
Example 7
The modified nickel-rich ternary composite electrode material comprises a nickel-rich ternary electrode material and a modification layer on the outer side of the nickel-rich ternary electrode material, wherein the thickness of the modification layer is 0.5-50 nm, and the modification layer is made of lithium compound Li2ZrO3And Li2GeO3The nickel-rich ternary composite electrode material is prepared according to the mass ratio of 1:4, the mass percent of a modification layer in the nickel-rich ternary composite electrode material is 2%, and Li in the nickel-rich ternary electrode material2The molar ratio of O, NiO, CoO and MnO is 1.05: 0.8: 0.05: 0.15.
The embodiment also provides a method for preparing the modified nickel-rich ternary composite electrode material, which comprises the following steps:
step one, Li2Mixing O, NiO, CoO and MnO, and then carrying out dry-mixing ball milling to obtain an electrode material; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 50r/min, and the time of the dry-mixing ball mill is 15 h;
sintering the electrode material obtained in the step one in an oxygen atmosphere to obtain a nickel-rich ternary electrode material; the introduction rate of the oxygen atmosphere is 0.18L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving the heat for 4h, then heating the temperature to 850 ℃ at the heating rate of 5 ℃/min, sintering the temperature for 18h, and finally naturally cooling the temperature to room temperature;
step three, mixing the nickel-rich ternary electrode material obtained in the step two with a lithiation compound, and then carrying out dry mixing and ball milling to obtain a precursor; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 50r/min, and the time of the dry-mixing ball mill is 15 h;
sintering the precursor obtained in the third step in an oxygen atmosphere to obtain a modified nickel-rich ternary composite electrode material; the introduction rate of the oxygen atmosphere is 0.18L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, sintering for 5h, and finally naturally cooling to room temperature.
The nickel-rich ternary composite electrode material prepared in the embodiment has a first discharge specific capacity of 148.5mAh/g under a discharge rate of 1C, and the capacity retention rate of 78% after 100 cycles.
Example 8
The modified nickel-rich ternary composite electrode material comprises an oxide-doped nickel-rich ternary electrode material and a modification layer on the outer side of the nickel-rich ternary electrode material, wherein the thickness of the modification layer is 0.5-50 nm, and the modification layer is made of lithiated LiAlO2The mass percentage of the modification layer in the nickel-rich ternary composite electrode material is 5%, and the doped oxide of the nickel-rich ternary electrode material is MoO3Li in the nickel-rich ternary electrode material2O, NiO, CoO, MnO and MoO3The molar ratio of (1.0: 0.8: 0.05: 0.1): 0.007.
the embodiment also provides a method for preparing the modified nickel-rich ternary composite electrode material, which comprises the following steps:
step one, Li2O, NiO, CoO, MnO and MoO3Carrying out dry mixing and ball milling after mixing to obtain an electrode material; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 100r/min, and the time of the dry-mixing ball mill is 10 hours;
sintering the electrode material obtained in the step one in an oxygen atmosphere to obtain a nickel-rich ternary electrode material; the introduction rate of the oxygen atmosphere is 0.06L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving the heat for 4h, then heating the temperature to 800 ℃ at the heating rate of 5 ℃/min, sintering the temperature for 24h, and finally naturally cooling the temperature to room temperature;
step three, mixing the nickel-rich ternary electrode material obtained in the step two with a lithiation compound, and then carrying out dry mixing and ball milling to obtain a precursor; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 100r/min, and the time of the dry-mixing ball mill is 10 hours;
sintering the precursor obtained in the third step in an oxygen atmosphere to obtain a modified nickel-rich ternary composite electrode material; the introduction rate of the oxygen atmosphere is 0.06L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 5000 ℃ at the heating rate of 3 ℃/min, sintering for 5h, and finally naturally cooling to room temperature.
The nickel-rich ternary composite electrode material prepared in the embodiment has the first specific discharge capacity of 156mAh/g under the discharge rate of 1C, and the capacity retention rate of 80% after 100 cycles.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (1)
1. The modified nickel-rich ternary composite electrode material is characterized by comprising an oxide-doped nickel-rich ternary electrode material and a modification layer on the outer side of the nickel-rich ternary electrode material, wherein the thickness of the modification layer is 0.5-50 nm, and the modification layer is Li2SiO3The mass percent of the modification layer in the nickel-rich ternary composite electrode material is 2 percent;
the doped oxide of the nickel-rich ternary electrode material is Nb2O3Li in the nickel-rich ternary electrode material2The mol ratio of O, NiO, CoO, MnO and doped oxide is 1.04: 0.8: 0.1: 0.005;
the method for preparing the modified nickel-rich ternary composite electrode material comprises the following steps:
step one, Li2O, NiO, CoO, MnO and Nb2O3Carrying out dry mixing and ball milling after mixing to obtain an electrode material; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 100r/min, and the time of the dry-mixing ball mill is 10 hours;
sintering the electrode material obtained in the step one in an oxygen atmosphere to obtain a nickel-rich ternary electrode material; the introduction rate of the oxygen atmosphere is 0.1L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, preserving the heat for 4h, then heating the temperature to 800 ℃ at the heating rate of 5 ℃/min, sintering the temperature for 18h, and finally naturally cooling the temperature to room temperature;
step three, mixing the nickel-rich ternary electrode material obtained in the step two with a lithiation compound, and then carrying out dry mixing and ball milling to obtain a precursor; the ball-material ratio of the dry-mixing ball mill is 1:5, the rotating speed of the dry-mixing ball mill is 100r/min, and the time of the dry-mixing ball mill is 10 hours;
sintering the precursor obtained in the third step in an oxygen atmosphere to obtain a modified nickel-rich ternary composite electrode material; the introduction rate of the oxygen atmosphere is 0.1L/min; the sintering system comprises the following steps: heating the temperature from room temperature to 500 ℃ at the heating rate of 3 ℃/min, sintering for 5h, and finally naturally cooling to room temperature.
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