CN112054172B - Preparation method of core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material - Google Patents
Preparation method of core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 75
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000011258 core-shell material Substances 0.000 title claims abstract description 50
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 73
- 239000013078 crystal Substances 0.000 claims abstract description 50
- 238000005245 sintering Methods 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims abstract description 16
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013067 intermediate product Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000001694 spray drying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 36
- 239000012792 core layer Substances 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- XKGIZIQMMABGJQ-UHFFFAOYSA-N [Mn](=O)(=O)([O-])[O-].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [Mn](=O)(=O)([O-])[O-].[Mn+2].[Co+2].[Ni+2].[Li+] XKGIZIQMMABGJQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 7
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 229910013716 LiNi Inorganic materials 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 17
- 230000008569 process Effects 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000000889 atomisation Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- FUECGUJHEQQIFK-UHFFFAOYSA-N [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] FUECGUJHEQQIFK-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- 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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- 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
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The invention discloses a preparation method of a core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material, which comprises the following steps: 1) using a specific nickel cobalt manganese hydroxide precursor (Ni)xCoyMn1‑x‑y(OH)2) Mixing with a lithium source, sintering in an oxygen atmosphere, and granulating to prepare granular high-nickel single-crystal nickel cobalt lithium manganate; 2) specific nickel cobalt lithium manganate (Li)b(NirCosMnt)O2) Adding water to prepare nano nickel cobalt lithium manganate slurry; 3) adding high-nickel monocrystal nickel cobalt lithium manganate and an additive containing a metal element into the nano nickel cobalt lithium manganate slurry to prepare a uniform mixture, spray-drying to obtain an intermediate product, and sintering in an oxygen atmosphere to prepare the lithium nickel cobalt manganese oxide intermediate; the metal element is one or more selected from Mg, Al, Zr, Ti and W; the cathode material prepared by the method has excellent first charge-discharge efficiency and high capacity retention rate, and can still exert excellent cycle performance and safety performance at high temperature.
Description
The invention relates to divisional application of Chinese patent application with the application date of 2019, 6 and 12, the application number of 2019105042003 and the name of 'a core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material and a preparation method and application thereof'.
Technical Field
The invention belongs to the field of lithium ion battery electrode materials, relates to a positive electrode material, and particularly relates to a preparation method of a core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material.
Background
The nickel cobalt lithium manganate (NCM) ternary cathode material is widely researched since the first report in 1999, and combines the advantages of three materials, namely lithium cobaltate, lithium nickelate and lithium manganate, through the synergistic effect of Ni-Co-Mn: the lithium ion battery positive electrode material has the characteristics of high capacity of lithium nickelate, high safety performance and low cost of lithium manganate and good cycle performance of lithium cobaltate, and has become the most rapidly developed lithium ion battery positive electrode material in recent years.
The current ternary cathode material of NCM is mainly of a secondary spherical particle structure, however, the above conventional secondary spherical particle structure has some problems as follows: 1. the mechanical strength of the particle structure is poor, and secondary ball crushing is easily caused in the pole piece compacting process; 2. the internal gaps are many, the structural defects are obvious, the unit pole piece is easy to break in the rolling process, the capacity of the battery is attenuated in the later period, the compaction density is greatly limited, the processing difficulty is increased, and the improvement of the energy density is limited; 3. because the internal pores are large and difficult to coat, the active material is in contact with the electrolyte and can be corroded by HF and the like at high temperature to damage the interface structure, so that the transition metals Ni, Co and Mn are dissolved in the electrolyte, and the transition metals are in contact with the electrolyte to cause increased side reactions, generate a large amount of gas, increase the gas pressure of a battery core and expand the battery, thereby causing serious potential safety hazards; 4. the surface of the particles has more defects and side reactions are easy to occur.
In view of the above problems, a person skilled in the art can effectively improve the problems of high mechanical strength and surface side reaction activity of secondary particles and the like by making a ternary cathode material into a single crystal shape and simply coating an extremely thin coating layer on the outer surface of the single crystal type material, especially a high nickel single crystal ternary material, and compared with a high nickel polycrystalline ternary material, the advantages of high compaction, long cycle stability and the like of the high nickel single crystal ternary material are receiving more and more attention, and the single crystallization of the high nickel cathode material can possibly become the development trend of the cathode material of the lithium battery in the future. However, researches show that the single-crystal high nickel-cobalt-manganese ternary cathode material has the problems of low first-time charge-discharge efficiency, serious capacity loss, high-temperature cycle, safety performance and the like, and needs to be further improved.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a core-shell type high nickel single crystal lithium nickel cobalt manganese oxide positive electrode material, in order to overcome the problems in the prior art, and the positive electrode material prepared by the method has excellent first charge-discharge efficiency and capacity exertion, and simultaneously has excellent cycle performance at a high temperature of more than 45 ℃.
In order to solve the technical problems, the invention adopts a technical scheme as follows:
a core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material comprises a core layer and a shell layer arranged on the outer surface of the core layer, wherein the core layer and the shell layer form a core-shell structure; wherein, the material of the core layer is a compound shown in the following general formula (I): lia(NixCoyMn1-x-y)O2(I) in the formula, a is more than or equal to 1.0 and less than or equal to 1.15 and 0.6<x is less than or equal to 0.95, y is less than or equal to 0.01 and less than or equal to 0.2, 1-x-y is more than 0, and the material of the nuclear layer is a single crystal type; the shell layer is made of a compound shown as the following general formula (II): lib(NiiCojMnkM1-i-j-k)O2(II), wherein M is selected from one or more of Mg, Al, Zr, Ti and W, b is more than or equal to 0.9 and less than or equal to 1.05, i is more than or equal to 0.2 and less than or equal to 0.5, j is more than or equal to 0.15 and less than or equal to 0.5, k is more than or equal to 0.15 and less than or equal to 0.5, and 1-i-j-k is more than or equal to 0.
According to some preferred and specific aspects of the invention, in formula (I), 0.65. ltoreq. x.ltoreq.0.9, 0.05. ltoreq. y.ltoreq.0.2.
According to some preferred and specific aspects of the present invention, in formula (II), 0.3. ltoreq. i.ltoreq.0.5, 0.17. ltoreq. j.ltoreq.0.4, and 0.2. ltoreq. k.ltoreq.0.4.
According to some preferred and specific aspects of the present invention, in the core-shell structure, the mass ratio of the core layer to the shell layer is 10-200: 1, preferably 10-180: 1, more preferably 20-100: 1, and further preferably 30-80: 1.
According to some specific aspects of the invention, the core layer has an average particle size of 1 to 8 microns.
The invention provides another technical scheme that: the preparation method of the core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material comprises the following steps:
(1) mixing a nickel-cobalt-manganese hydroxide precursor with a lithium source, sintering in an oxygen atmosphere, and granulating to prepare granular high-nickel single-crystal nickel-cobalt-manganese lithium manganate, wherein the nickel-cobalt-manganese hydroxide precursor is a compound shown in the following formula: nixCoyMn1-x-y(OH)2，0.6<x≤0.95，0.01≤y≤0.2，1-x-y＞0；
(2) Adding water into the nickel cobalt lithium manganate to prepare slurry, and then sanding the slurry to prepare nano nickel cobalt lithium manganate slurry, wherein the nickel cobalt lithium manganate is a compound shown in the following formula: lib(NirCosMnt)O2，0.9≤b≤1.05，0.2≤r≤0.5，0.15≤s≤0.5，0.15≤t≤0.5，r+s+t＝1；
(3) Adding the high-nickel single-crystal nickel cobalt lithium manganate prepared in the step (1) and an additive containing a metal element into the nano nickel cobalt lithium manganate slurry prepared in the step (2), stirring to obtain a uniform mixture, spray-drying to obtain an intermediate product, and sintering the intermediate product in an oxygen atmosphere to prepare the core-shell high-nickel single-crystal nickel cobalt lithium manganate positive electrode material; wherein the metal element is one or more selected from Mg, Al, Zr, Ti and W.
According to the core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material prepared by the method, the core is a monocrystal-shaped high-nickel ternary positive electrode material, and the high gram specific capacity can be exerted under 4.2V; meanwhile, the inner core is of a single-crystal morphology structure, so that the material crushing phenomenon of the material in the processing process can be effectively avoided, the compaction density of the material is improved, the generation of a new surface of the material is reduced, and the side reaction of the anode material and the electrolyte is effectively reduced; and thirdly, after the nickel cobalt lithium manganate with lower nickel content is subjected to nanocrystallization, the nickel cobalt lithium manganate is mixed with a doping additive in a solution, so that the mixing uniformity of the coating materials is ensured, and then the coating can be completely coated on the surface of the anode material in a spray drying mode to form a uniform shell layer.
According to some specific aspects of the present invention, in the step (1), the particle size D of the nickel-cobalt-manganese hydroxide precursor50Is 1 to 8 μm.
According to some specific aspects of the present invention, in step (1), the lithium source is lithium hydroxide or lithium carbonate or a combination of both.
According to some preferred aspects of the present invention, in the step (1), the oxygen content in the oxygen atmosphere is 85% or more.
According to some preferred aspects of the present invention, in the step (1), a molar ratio of lithium in the lithium source to a sum of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide precursor is 1.00 to 1.15: 1.
According to some preferred and specific aspects of the present invention, in step (1), the sintering is performed at 400-1100 ℃.
According to some specific aspects of the present invention, in the step (1), the sintering includes the steps of: presintering for 3-8 h within the range of 300-500 ℃, then sintering for 4-12 h within the range of 600-800 ℃, then sintering for 4-12 h within the range of 800-1000 ℃, and finally sintering for 3-8 h within the range of 600-800 ℃.
According to some specific aspects of the invention, in the step (1), after the sintering, cooling is carried out, the cooling is carried out to be below 80 ℃, and then jaw crushing, roll rolling and crushing are carried out to obtain the granular high-nickel single-crystal nickel cobalt lithium manganate.
According to some specific aspects of the invention, in the step (2), the particle size D of the nickel cobalt lithium manganate added into water50Is 4 to 30 μm.
According to some preferred aspects of the invention, in the step (2), after grinding, the particle size D of the nickel cobalt lithium manganate in the nano nickel cobalt lithium manganate slurry50Is 50 to 180 nm.
According to some specific aspects of the invention, in the step (2), the sanding time is 4-8 h, the grinding bodies are zirconia balls with the particle size of 0.1-0.8 mm, and the sanding speed is 800-3000 rpm.
According to some preferred aspects of the present invention, in the step (2), the solid content of the slurry prepared is controlled to be 10 to 45%.
According to some specific aspects of the present invention, in the step (2), the water is deionized water.
According to some specific and preferred aspects of the present invention, in the step (3), the additive containing a metal element is a combination of one or more selected from a compound of Mg, a compound of Al, a compound of Zr, a compound of Ti, and a compound of W, such as magnesium oxide, aluminum oxide, zirconium oxide, tungsten oxide, magnesium nitrate, aluminum nitrate, zirconium nitrate, tungsten nitrate, and the like.
According to some preferred aspects of the present invention, in the step (3), the additive containing a metal element is added in a nano size.
According to some preferred aspects of the invention, in the step (3), the feeding molar ratio of the metal element contained in the additive to the sum of the nickel, cobalt and manganese elements in the nickel cobalt lithium manganate is 0.01-0.10: 1.
According to some preferred aspects of the invention, in step (3), the temperature of the sintering is 750-1000 ℃.
According to some preferred aspects of the present invention, in the step (3), the sintering time is 5 to 15 hours.
According to some preferred aspects of the present invention, in the step (3), the oxygen content in the oxygen atmosphere is 85% or more.
According to some preferred aspects of the invention, in the step (3), the mass ratio of the core layer to the shell layer in the core-shell type high-nickel single-crystal lithium nickel cobalt manganese oxide positive electrode material is controlled to be 10-200: 1.
According to some specific aspects of the invention, in step (3), the blend is controlled to be a slurry with a solid content of 10-45% by adding deionized water.
According to some specific aspects of the invention, in the step (3), after the sintering, cooling is carried out, the cooling is carried out to be below 80 ℃, and then jaw crushing, roll crushing and crushing are carried out so as to disperse the bonded particles, so as to obtain the core-shell type high-nickel single-crystal nickel cobalt lithium manganate positive electrode material.
According to some specific aspects of the invention, in the step (3), the spray drying is performed by using a spray drying device, wherein the atomization frequency of the spray drying device is 30-45 Hz, the air inlet temperature is 250-350 ℃, and the air outlet temperature is 80-100 ℃.
The invention provides another technical scheme that: the application of the core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material in a lithium ion battery is provided.
In the present invention, "Ni" of the core layerxCoyMn1-x-yWhen x in (1) is more than 0.6, the nickel is high, which means that the nickel content is high.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, the core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material is adopted, and a specific compound is combined to be used as a shell layer material, so that the prepared positive electrode material has excellent first charge-discharge efficiency and high capacity retention rate, can still keep the surface structure stable at high temperature (above 45 ℃), can greatly inhibit the surface oxygen loss activity of the ternary material, and can improve the cycle performance and inhibit the flatulence phenomenon (safety performance) of the material under the high-temperature condition.
Drawings
FIG. 1 shows LiNi, a core-shell type high-nickel single crystal obtained in example 10.83Co0.11Mn0.06O2@LiNi0.49Co0.196Mn0.294Al0.02O2Scanning electron microscope images of;
FIG. 2 is a single-crystal LiNi of comparative example 10.83Co0.11Mn0.06O2Scanning electron microscope images of;
FIG. 3 is a graph showing the charge and discharge cycles at 2.75-4.2V/1C (45 ℃ C.) for example 1 and comparative example 1;
FIG. 4 is a graph showing the charge and discharge cycles at 2.75-4.2V/1C (45 ℃) for example 2 and comparative example 2;
FIG. 5 is a graph showing the charge and discharge cycles at 2.75 to 4.2V/1C (45 ℃ C.) for example 3 and comparative example 3.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings. It is to be understood that these examples are for further illustration of the invention and are not intended to limit the scope of the invention. In addition, it should be understood that the following claims are illustrative of the present invention and are not to be construed as limiting the invention in any way. In the following, all starting materials are commercially available unless otherwise specified.
Example 1
The embodiment provides a core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material, which comprises a core layer and a shell layer arranged on the outer surface of the core layer, wherein the core layer and the shell layer form a core-shell structure; the material of the core layer is a compound shown as the following formula: LiNi0.83Co0.11Mn0.06O2The material of the core layer is a single crystal type; the shell layer is made of a compound shown as the following formula: LiNi0.49Co0.196Mn0.294Al0.02O2(ii) a With LiNi0.83Co0.11Mn0.06O2@LiNi0.49Co0.196Mn0.294Al0.02O2The preparation method of the core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material comprises the following steps:
(1) preparation of granular high-nickel single-crystal nickel cobalt lithium manganate LiNi0.83Co0.11Mn0.06O2
Ni as precursor of nickel-cobalt-manganese hydroxide with particle size of 3-6 mu m0.83Co0.11Mn0.06(OH)2And battery grade lithium hydroxide with the average grain diameter of 4-15 mu m according to the ratio of Li to Ni0.83Co0.11Mn0.06Uniformly mixing the components in a molar ratio of 1.05:1 by using a high-speed mixer, then putting the mixture into a sagger, putting the sagger into an oxygen atmosphere furnace (with the oxygen content of about 90 percent), presintering the mixture for 6 hours at a temperature of between 350 and 450 ℃, then sintering the mixture for 8 hours at a temperature of between 600 and 700 ℃, then sintering the mixture for 12 hours at a temperature of between 750 and 900 ℃, and finally sintering the mixture for 6 hours at a temperature of between 650 and 750 ℃. Crushing the sintered block material by a jaw, a pair of rollers and air flow to obtain granular high-nickel monocrystal nickel cobalt lithium manganate (process product S831106) (high-nickel monocrystal LiNi with the grain diameter of about 3-6 mu m)0.83Co0.11Mn0.06O2)；
(2) Preparation of nano nickel cobalt lithium manganate LiNi0.5Co0.2Mn0.3O2Slurry material
The micron-sized LiNi with the granularity of 5-12 mu m0.5Co0.2Mn0.3O2Adding deionized water, adjusting to obtain slurry with the solid content of 23 +/-1%, stirring for 0.5h, then grinding for 6h by using a sand mill, wherein a grinding body is a zirconia ball with the particle size of 0.2mm, the grinding rotation speed is 2500rpm, and grinding is carried out to obtain the nano-scale LiNi with the average particle size of about 80-180 nm0.5Co0.2Mn0.3O2Then the nano nickel cobalt lithium manganate LiNi is prepared0.5Co0.2Mn0.3O2Sizing agent;
(3) preparation of core-shell type high-nickel single crystal nickel cobalt lithium manganate LiNi0.83Co0.11Mn0.06O2@LiNi0.49Co0.196Mn0.294Al0.02O2
Adding the process product S831106 prepared in the step (1) and the additive nano aluminum oxide into the nano LiNi prepared in the step (2)0.5Co0.2Mn0.3O2In the slurry, Ni + Co + Mn (from the nano LiNi prepared in the step (2)) is added0.5Co0.2Mn0.3O2Slurry) to Al (from alumina) at a molar ratio of 0.98:0.02, where LiNi0.49Co0.196Mn0.294Al0.02O2And LiNi0.83Co0.11Mn0.06O2The weight ratio of the components is 2:100, the prepared solution is fully stirred and added with deionized water to be adjusted to the solid content of 43 +/-1% of slurry is sprayed and dried under the conditions that the atomization frequency of spray drying equipment is 35Hz, the air inlet temperature is 300 ℃ and the air outlet temperature is 85 ℃ to prepare an intermediate product, the intermediate product is placed in an oxygen atmosphere furnace (the oxygen content is about 90%) to be sintered for 8 hours at the temperature of 350-800 ℃, cooled to the temperature below 80 ℃, and subjected to jaw crushing, roll pair and crushing to obtain the core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material (LiNi)0.83Co0.11Mn0.06O2@LiNi0.49Co0.196Mn0.294Al0.02O2) Abbreviated as S831106-523.
Example 2
The embodiment provides a core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material, which comprises a core layer and a shell layer arranged on the outer surface of the core layer, wherein the core layer and the shell layer form a core-shell structure; the material of the core layer is a compound shown as the following formula: LiNi0.88Co0.06Mn0.06O2The material of the core layer is a single crystal type; the shell layer is made of a compound shown as the following formula: LiNi0.49Co0.196Mn0.294Al0.02O2(ii) a With LiNi0.88Co0.06Mn0.06O2@LiNi0.49Co0.196Mn0.294Al0.02O2The preparation method of the core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material comprises the following steps:
(1) preparation of granular high-nickel single-crystal nickel cobalt lithium manganate LiNi0.88Co0.06Mn0.06O2
Ni as precursor of nickel-cobalt-manganese hydroxide with particle size of 3-6 mu m0.88Co0.06Mn0.06(OH)2And battery grade lithium hydroxide with the average grain diameter of 4-15 mu m according to the ratio of Li to Ni0.88Co0.06Mn0.06Uniformly mixing the components in a molar ratio of 1.05:1 by using a high-speed mixer, then putting the mixture into a sagger, putting the sagger into an oxygen atmosphere furnace (with the oxygen content of about 90 percent), presintering the mixture for 6 hours at a temperature of between 350 and 450 ℃, then sintering the mixture for 8 hours at a temperature of between 600 and 700 ℃, then sintering the mixture for 12 hours at a temperature of between 700 and 850 ℃, and finally sintering the mixture at a temperature of between 650 and 750 DEG CAnd 6 h. Crushing the sintered block material by a jaw, double rollers and air flow to obtain a granular high nickel single crystal nickel cobalt lithium manganate (process product S880606 for short) (high nickel single crystal LiNi with the grain diameter of about 3-6 mu m)0.88Co0.06Mn0.06O2)；
(2) Preparation of nano nickel cobalt lithium manganate LiNi0.5Co0.2Mn0.3O2Slurry material
The micron-sized LiNi with the granularity of 5-12 mu m0.5Co0.2Mn0.3O2Adding deionized water, adjusting to obtain slurry with the solid content of 22 +/-1%, stirring for 0.5h, then grinding for 6h by using a sand mill, wherein a grinding body is a zirconia ball with the particle size of 0.2mm, the grinding rotation speed is 2500rpm, and grinding is carried out to obtain the nano-scale LiNi with the average particle size of about 80-180 nm0.5Co0.2Mn0.3O2Then the nano nickel cobalt lithium manganate LiNi is prepared0.5Co0.2Mn0.3O2Sizing agent;
(3) preparation of core-shell type high-nickel single crystal nickel cobalt lithium manganate LiNi0.88Co0.06Mn0.06O2@LiNi0.49Co0.196Mn0.294Al0.02O2
Adding the process product S880606 prepared in the step (1) and the additive nano alumina into the nano LiNi prepared in the step (2)0.5Co0.2Mn0.3O2In the slurry, Ni + Co + Mn (from the nano LiNi prepared in the step (2)) is added0.5Co0.2Mn0.3O2Slurry) to Al (from alumina) at a molar ratio of 0.98:0.02, where LiNi0.49Co0.196Mn0.294Al0.02O2And LiNi0.88Co0.06Mn0.06O2The weight ratio of the components is 2:100, the prepared solution is fully stirred, deionized water is added to prepare slurry with the solid content of 43 +/-1%, the slurry is spray-dried under the conditions that the atomization frequency of spray-drying equipment is 35Hz, the air inlet temperature is 300 ℃ and the air outlet temperature is 85 ℃ to prepare an intermediate product, the intermediate product is placed in an oxygen atmosphere furnace (the oxygen content is about 90 percent) to be sintered for 8 hours at the temperature of 350-800 ℃, the intermediate product is cooled to the temperature below 80 ℃, and the intermediate product is crushed by a jaw crusher, a pair roller and a crusher to obtain the productThe core-shell type high nickel single crystal nickel cobalt lithium manganate anode material (LiNi)0.88Co0.06Mn0.06O2@LiNi0.49Co0.196Mn0.294Al0.02O2) Abbreviated as S880606-523.
Example 3
The embodiment provides a core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material, which comprises a core layer and a shell layer arranged on the outer surface of the core layer, wherein the core layer and the shell layer form a core-shell structure; the material of the core layer is a compound shown as the following formula: LiNi0.65Co0.15Mn0.20O2The material of the core layer is a single crystal type; the shell layer is made of a compound shown as the following formula: LiNi0.327Co0.327Mn0.326Al0.02O2(ii) a With LiNi0.65Co0.15Mn0.20O2@LiNi0.327Co0.327Mn0.326Al0.02O2The preparation method of the core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material comprises the following steps:
(1) preparation of granular high-nickel single-crystal nickel cobalt lithium manganate LiNi0.65Co0.15Mn0.20O2
Ni as precursor of nickel-cobalt-manganese hydroxide with particle size of 3-6 mu m0.65Co0.15Mn0.20(OH)2And battery grade lithium hydroxide with the average grain diameter of 4-15 mu m according to the ratio of Li to Ni0.65Co0.15Mn0.20Uniformly mixing the components in a molar ratio of 1.05:1 by using a high-speed mixer, then putting the mixture into a sagger, putting the sagger into an oxygen atmosphere furnace (with the oxygen content of about 90 percent), presintering the mixture for 6 hours at a temperature of between 350 and 450 ℃, then sintering the mixture for 8 hours at a temperature of between 600 and 700 ℃, then sintering the mixture for 12 hours at a temperature of between 800 and 1000 ℃, and finally sintering the mixture for 6 hours at a temperature of between 650 and 750 ℃. Crushing the sintered block material by a jaw, a pair of rollers and airflow to obtain granular high-nickel monocrystal nickel cobalt lithium manganate (process product S651520 for short) (high-nickel monocrystal LiNi type LiNi with the grain diameter of about 3-6 mu m)0.65Co0.15Mn0.20O2)；
(2) Preparation of nano nickel cobalt manganeseLithium LiNi1/3Co1/3Mn1/3O2Slurry material
The micron-sized LiNi with the granularity of 5-12 mu m1/3Co1/3Mn1/3O2Adding deionized water, adjusting to obtain slurry with the solid content of 23 +/-1%, stirring for 0.5h, then grinding for 6h by using a sand mill, wherein a grinding body is a zirconia ball with the particle size of 0.2mm, the grinding rotation speed is 2500rpm, and grinding is carried out to obtain the nano-scale LiNi with the average particle size of about 80-180 nm1/3Co1/3Mn1/3O2Then the nano nickel cobalt lithium manganate LiNi is prepared1/3Co1/3Mn1/3O2Sizing agent;
(3) preparation of core-shell type high-nickel single crystal nickel cobalt lithium manganate LiNi0.65Co0.15Mn0.20O2@LiNi0.327Co0.327Mn0.326Al0.02O2
Adding the process product S651520 prepared in the step (1) and the additive nano-alumina into the nano-LiNi prepared in the step (2)1/3Co1/3Mn1/3O2In the slurry, Ni + Co + Mn (from the nano LiNi prepared in the step (2)) is added0.5Co0.2Mn0.3O2Slurry) to Al (from alumina) at a molar ratio of 0.98:0.02, where LiNi0.327Co0.327Mn0.326Al0.02O2And LiNi0.65Co0.15Mn0.20O2The weight ratio of the core-shell type high-nickel single-crystal nickel cobalt lithium manganate positive electrode material to the core-shell type high-nickel single-crystal material is 2:100, the prepared solution is fully stirred, deionized water is added to prepare slurry with the solid content of 40-45%, an intermediate product is prepared under the conditions that the atomization frequency of spray drying equipment is 35Hz, the air inlet temperature is 300 ℃ and the air outlet temperature is 85 ℃, the intermediate product is placed in an oxygen atmosphere furnace (the oxygen content is about 90%) to be sintered for 8 hours at the temperature of 350-800 ℃, the sintering time is cooled to the temperature below 80 ℃, and the intermediate product is subjected to jaw crushing, roll pair and crushing to obtain the core-shell type high-nickel single-crystal nickel cobalt lithium manganate positive electrode material (LiNi I)0.65Co0.15Mn0.20O2@LiNi0.327Co0.327Mn0.326Al0.02O2) Abbreviated as S651520-333.
Comparative example 1
The process sample S831106 prepared in example 1 was coated with 1000ppm nano alumina and sintered at 600. + -. 20 ℃ for 8 hours in an oxygen atmosphere to obtain a comparative sample S831106-Al.
Comparative example 2
The process sample S880606 prepared in example 2 was coated with 1000ppm nano alumina and sintered at 600 ± 20 ℃ for 8h under an oxygen atmosphere to obtain a comparative sample S880606-Al.
Comparative example 3
The process sample S651520 prepared in example 3 was coated with 1000ppm nano alumina and sintered at 600. + -. 20 ℃ for 8 hours in an oxygen atmosphere to obtain a comparative sample S651520-Al.
Performance testing
The positive electrode materials obtained in the above examples 1 to 3 and comparative examples 1 to 3 were subjected to the following tests and experiments, and the specific results are shown in tables 1 and 2.
TABLE 1 physical Properties data Table for the final products of examples 1-3 and comparative examples 1-3
TABLE 2 TABLE 1C HIGH TEMPERATURE 45 deg.C (2.75-4.20V) CYCLIC PERFORMANCE DATA FOR THE FINISHED PRODUCTS IN EXAMPLES 1-3 AND COMPARATIVE EXAMPLES 1-3
According to the data, the first gram capacity of various same base materials in examples 1-3 and comparative examples 1-3 is not obviously different, but under the high temperature condition of 45 ℃, the cycle retention rate is 500 weeks, the retention rate of example 1 is 4.3% higher than that of comparative example 1, the retention rate of example 2 is 7.1% higher than that of comparative example 2, and the retention rate of example 3 is 3.8% higher than that of comparative example 3, for a lithium ion battery, the rise degree of about 5% can obviously improve the cycle service performance of the lithium ion battery, the performance of the core-shell structure type high-nickel single crystal material is obviously superior to that of a common cladding type high-nickel single crystal material, the surface structure can still be kept stable at the high temperature (45 ℃), the surface oxygen loss activity of a ternary material can be greatly inhibited, and the cycle performance and other performances of the material under the high temperature condition can be improved.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (10)
1. A preparation method of a core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material is characterized by comprising the following steps:
(1) mixing a nickel-cobalt-manganese hydroxide precursor with a lithium source, sintering in an oxygen atmosphere, and granulating to prepare granular high-nickel single-crystal nickel-cobalt-manganese lithium manganate, wherein the nickel-cobalt-manganese hydroxide precursor is a compound shown in the following formula: nixCoyMn1-x-y(OH)2，0.6<x is less than or equal to 0.95, y is less than or equal to 0.01 and less than or equal to 0.2, and 1-x-y is more than 0; wherein, the oxygen content in the oxygen atmosphere is more than or equal to 85 percent, and the sintering comprises the following stages: presintering within the range of 300-500 ℃, then sintering within the range of 600-800 ℃, then sintering within the range of 700-1000 ℃, and finally sintering within the range of 600-800 ℃;
(2) adding nickel cobalt lithium manganate into water to prepare slurry, then sanding the slurry to prepare nano nickel cobalt lithium manganate slurry, wherein the solid content of the nano nickel cobalt lithium manganate slurry prepared by the method is controlled to be 10-45%, and the nickel cobalt lithium manganate is a compound shown in the following formula: lib(NirCosMnt)O2，0.9≤b≤1.05，0.2≤r≤0.5，0.15≤s≤0.5，0.15≤t≤0.5，r+s+t＝1；
(3) Adding the high-nickel single-crystal nickel cobalt lithium manganate prepared in the step (1) and an additive containing a metal element into the nano nickel cobalt lithium manganate slurry prepared in the step (2), stirring to obtain a uniform mixture, spray-drying to obtain an intermediate product, and sintering the intermediate product in an oxygen atmosphere to prepare the core-shell high-nickel single-crystal nickel cobalt lithium manganate positive electrode material; wherein the metal element is one or more selected from Mg, Al, Zr, Ti and W;
the prepared core-shell type high-nickel monocrystal nickel cobalt lithium manganate positive electrode material comprises a core layer and a shell layer arranged on the outer surface of the core layer, wherein the core layer and the shell layer form a core-shell structure; wherein, the material of the core layer is a compound shown in the following general formula (I): lia(NixCoyMn1-x-y)O2(I) in the formula, a is more than or equal to 1.0 and less than or equal to 1.15 and 0.6<x is less than or equal to 0.95, y is less than or equal to 0.01 and less than or equal to 0.2, 1-x-y is more than 0, and the material of the nuclear layer is a single crystal type; the shell layer is made of a compound shown as the following general formula (II): lib(NiiCojMnkM1-i-j-k)O2(II), wherein M is selected from one or more of Mg, Al, Zr, Ti and W, b is more than or equal to 0.9 and less than or equal to 1.05, i is more than or equal to 0.2 and less than or equal to 0.5, j is more than or equal to 0.15 and less than or equal to 0.5, k is more than or equal to 0.15 and less than or equal to 0.5, and 1-i-j-k is more than or equal to 0.
2. The method for preparing the core-shell type high-nickel single-crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein in the step (1), the particle size D of the nickel cobalt manganese hydroxide precursor501-8 microns; the lithium source is lithium hydroxide or lithium carbonate or a combination of the lithium hydroxide and the lithium carbonate, and the molar ratio of lithium in the lithium source to the sum of nickel, cobalt and manganese elements in the nickel-cobalt-manganese hydroxide precursor is 1.00-1.15: 1.
3. The method for preparing the core-shell type high-nickel single-crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein in the step (1), the sintering comprises the following stages: presintering at 350-450 ℃, then sintering at 600-700 ℃, then sintering at 750-900 ℃, and finally sintering at 650-750 ℃; or the like, or, alternatively,
presintering at 350-450 ℃, then sintering at 600-700 ℃, then sintering at 700-850 ℃, and finally sintering at 650-750 ℃; or the like, or, alternatively,
presintering at 350-450 ℃, then sintering at 600-700 ℃, then sintering at 800-1000 ℃, and finally sintering at 650-750 ℃.
4. The method for preparing the core-shell type high-nickel single-crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein in the step (1), after the sintering, the core-shell type high-nickel single-crystal lithium nickel cobalt manganese oxide positive electrode material is cooled to be below 80 ℃, and then subjected to jaw crushing, roll-to-roll crushing and crushing to prepare the granular high-nickel single-crystal lithium nickel cobalt manganese oxide.
5. The method for preparing the core-shell type high-nickel single-crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein in the step (2), the particle diameter D of the lithium nickel cobalt manganese oxide added into water50Is 4-30 microns, and after grinding, the particle diameter D of the nickel cobalt lithium manganate in the nano nickel cobalt lithium manganate slurry50Is 50 to 180 nm.
6. The method for preparing the core-shell type high-nickel single-crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein in the step (2), the sanding time is 4-8 h, the grinding body is zirconia balls with the particle size of 0.1-0.8 mm, and the sanding speed is 800-3000 rpm.
7. The method for preparing the core-shell type high-nickel single-crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein in the step (3), the additive containing the metal element is one or more selected from a group consisting of a compound of Mg, a compound of Al, a compound of Zr, a compound of Ti and a compound of W, and the feeding molar ratio of the metal element contained in the additive to the sum of nickel, cobalt and manganese elements in the nano lithium nickel cobalt manganese oxide slurry prepared in the step (2) is 0.01-0.10: 1.
8. The method for preparing the core-shell type high-nickel single-crystal nickel cobalt lithium manganate positive electrode material as claimed in claim 1, wherein in the step (3), the sintering temperature is 750-1000 ℃, and the sintering time is 5-15 h.
9. The method for preparing the core-shell type high-nickel single crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein in the step (3), the oxygen content in the oxygen atmosphere is greater than or equal to 85%; and/or in the step (3), deionized water is added to control the mixed material to be slurry with the solid content of 10-45%.
10. The method for preparing the core-shell type high-nickel single-crystal lithium nickel cobalt manganese oxide positive electrode material according to claim 1, wherein in the step (3), the mass ratio of the core layer to the shell layer in the core-shell type high-nickel single-crystal lithium nickel cobalt manganese oxide positive electrode material is controlled to be 10-200: 1.
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| JP5132727B2 (en) * | 2010-07-12 | 2013-01-30 | シャープ株式会社 | Positive electrode active material, positive electrode and non-aqueous electrolyte secondary battery |
| KR101689212B1 (en) * | 2011-12-07 | 2016-12-26 | 삼성에스디아이 주식회사 | Positive active material for lithium secondary, method for preparing thereof, and lithium secondary battery containing the same |
| CN103515606B (en) * | 2012-06-21 | 2016-09-14 | 中国科学院宁波材料技术与工程研究所 | Lithium ion battery with high energy density oxide anode material and preparation method thereof |
| CN103151520B (en) * | 2013-03-20 | 2015-06-17 | 东莞市力嘉电池有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN103811744B (en) * | 2014-02-13 | 2016-09-21 | 北大先行科技产业有限公司 | A kind of preparation method of ternary cathode material of lithium ion battery |
| CN104409716A (en) * | 2014-10-30 | 2015-03-11 | 中国科学院过程工程研究所 | Nickel lithium ion battery positive material with concentration gradient, and preparation method thereof |
| CN107546373A (en) * | 2016-06-29 | 2018-01-05 | 万向二三股份公司 | A kind of nickel-cobalt lithium manganate material for the method and gained for coating nickle cobalt lithium manganate |
| CN106532035A (en) * | 2016-12-16 | 2017-03-22 | 无锡晶石新型能源有限公司 | Ternary cathode material for lithium ion battery and preparation method thereof |
| CN106505193B (en) * | 2017-01-12 | 2020-07-14 | 宁波容百新能源科技股份有限公司 | Single crystal nickel cobalt lithium manganate positive electrode material, preparation method thereof and lithium ion battery |
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