CN115745023A - High-voltage nickel-cobalt-manganese hydroxide, preparation method thereof, positive electrode material and lithium ion battery - Google Patents
High-voltage nickel-cobalt-manganese hydroxide, preparation method thereof, positive electrode material and lithium ion battery Download PDFInfo
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- CN115745023A CN115745023A CN202211444495.8A CN202211444495A CN115745023A CN 115745023 A CN115745023 A CN 115745023A CN 202211444495 A CN202211444495 A CN 202211444495A CN 115745023 A CN115745023 A CN 115745023A
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- 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 title claims abstract description 126
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 162
- 229910052751 metal Inorganic materials 0.000 claims abstract description 87
- 239000002184 metal Substances 0.000 claims abstract description 87
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 239000011572 manganese Substances 0.000 claims abstract description 61
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 58
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 44
- 239000006185 dispersion Substances 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- 239000011247 coating layer Substances 0.000 claims abstract description 27
- 238000000975 co-precipitation Methods 0.000 claims abstract description 25
- 150000001298 alcohols Chemical class 0.000 claims abstract description 5
- 239000012670 alkaline solution Substances 0.000 claims abstract description 5
- 150000004760 silicates Chemical class 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 114
- 238000003756 stirring Methods 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 32
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 30
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 30
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 22
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 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 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 241000080590 Niso Species 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- -1 silicate ester Chemical class 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 26
- 238000000576 coating method Methods 0.000 abstract description 12
- 239000011248 coating agent Substances 0.000 abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 33
- 235000011121 sodium hydroxide Nutrition 0.000 description 32
- 239000010406 cathode material Substances 0.000 description 28
- 239000002585 base Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 229910052715 tantalum Inorganic materials 0.000 description 10
- 239000003513 alkali Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000010405 anode material Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 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 description 2
- 230000008901 benefit Effects 0.000 description 2
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 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
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- BBYVCDCBDWMUGX-UHFFFAOYSA-L [OH-].[OH-].[Mn].[Co++].[Ni] Chemical compound [OH-].[OH-].[Mn].[Co++].[Ni] BBYVCDCBDWMUGX-UHFFFAOYSA-L 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002345 surface coating layer Substances 0.000 description 1
- 150000003481 tantalum Chemical class 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a high-voltage nickel-cobalt-manganese hydroxide, a preparation method thereof, a positive electrode material and a lithium ion battery, wherein the preparation method comprises the following steps: adding a metal solution A containing Ni, co and Mn, a metal solution B containing Ta and an alkaline solution into the base solution in a concurrent flow manner, and carrying out a coprecipitation reaction to obtain a Ta-doped nickel-cobalt-manganese hydroxide matrix dispersion solution; and adding alcohols into the Ta doped nickel cobalt manganese hydroxide matrix dispersion liquid, adding silicates, and reacting to obtain the nickel cobalt manganese hydroxide. The invention utilizes the alkaline environment of the doping stage to carry out the coating reaction, constructs the coating layer on the surface of the Ta-doped nickel-cobalt-manganese hydroxide matrix and can enhance the structural stability of the material.
Description
Technical Field
The invention belongs to the technical field of anode materials, and relates to a high-voltage nickel-cobalt-manganese hydroxide, a preparation method thereof, an anode material and a lithium ion battery.
Background
Lithium ion batteries are widely used in the fields of notebook computers, mobile phones and all-electric automobiles, and are receiving more and more attention. At present, the ternary cathode material LiNi x Co y Mn 1-x-y O 2 (NCM), wherein x is more than or equal to 0.6, becomes the focus of attention, has higher practical capacity under relatively higher voltage, and has obvious advantage in the aspect of long driving range. However, as the Ni content and voltage increase, the positive electrode material faces the difficulties of thermal instability and severe degradation of cycle stability. The layered cathode material generally causes the layered R-3m phase to be converted into the spinel Fd-3m phase due to Li/Ni mixing, and finally is the rock salt Fm-3m phase, which is harmful to the cycle stability. Raising the cut-off voltage is effective in increasing the energy density, however it is considered to be an aggressive way, and when the charge cut-off voltage is excessively raised, the capacity of the NCM is also significantly reduced. Inherent problems with NCM anodes include surface structure phase transitions, electrochemical polarization, lattice mismatch, and grain cracking, among others.
At present, various modification methods such as element doping, surface modification, concentration gradient design and the like are provided to solve the problems of capacity fading and cycle stability of the high-nickel ternary cathode material. Cationic doping is one of the effective methods, and the doping elements are typically Mg, al, ti, ce, zr, and Nb. First, cationic doping can be achieved by increasing Ni 2+ To inhibit Li/Ni mixing; secondly, since the metal-oxygen bond energy is stronger than that of the Ni-O bond, the structural stability of the nickel-rich cathode is enhanced and the oxygen release is suppressed. CN112670506BDiscloses a nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by a fast ion conductor and a preparation method thereof, and the preparation method comprises the following steps: taking lithium salt and tantalum salt for pulverization treatment, and then mixing with a precursor of a nickel-cobalt-manganese ternary positive electrode material to obtain a homogeneous mixture; and (3) calcining the homogeneous mixture in sections at 450-550 ℃, then calcining at 680-780 ℃, and cooling along with the furnace to obtain the nickel-cobalt-manganese-tantalum composite quaternary cathode material. CN114122380A discloses a preparation method of a zirconium-doped cerium fluoride coated nickel-cobalt-manganese ternary cathode material, in which a nickel-cobalt-manganese hydroxide precursor, a lithium source, and a zirconium source are ball-milled, mixed, and sintered to obtain a zirconium-doped nickel-cobalt-manganese ternary cathode material. Both of the above two patents promote the doping mixing effect of the element through pulverization treatment, however, the physical mixing mode hardly makes the material element reach the mixing of molecular level, the element mixing is uneven and can influence the stability of performance, and the mixing mode has increased the operating procedure, increased the cost.
In addition, surface modification is also an effective strategy for maintaining the stability of a surface structure, and CN104362330A discloses a lithium nickel cobalt manganese oxide material with a surface coated with a boron-lithium composite oxide, which is to coat a layer of boron-lithium composite oxide on the surface of a lithium nickel cobalt manganese oxide positive electrode material. The preparation method of the material comprises the steps of adding the prepared nickel cobalt lithium manganate into a mixed alcohol solution of a lithium source and a boron source, performing ultrasonic treatment to uniformly disperse the nickel cobalt lithium manganate into the solution, adding a dispersing agent, fully soaking the material into the solution, and performing heat treatment after solvent evaporation to obtain the material. The surface coating layer can keep the layered structure of the NCM surface and ensure the structural stability of the NCM material.
Therefore, there is a need for a method for preparing NCM material suitable for industrial production, which comprises doping the NCM material with cations at molecular level and forming a coating layer on the surface of the NCM material to improve the structural stability of the NCM material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a high-voltage nickel-cobalt-manganese hydroxide, a preparation method thereof, a positive electrode material and a lithium ion battery. The preparation method of the invention carries out Ta doping in the preparation stage of the nickel-cobalt-manganese hydroxide matrix, thus realizing the mixing at the molecular level; and (3) performing a coating reaction by using an alkaline environment in a doping stage, and constructing a coating layer on the surface of the Ta-doped nickel-cobalt-manganese hydroxide matrix. The preparation method of the invention can enhance the structural stability of the material.
The high voltage in the high voltage nickel cobalt manganese hydroxide refers to that the anode material prepared from the nickel cobalt manganese hydroxide has high charge cut-off voltage which is more than or equal to 4.5V.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a nickel-cobalt-manganese hydroxide, comprising:
(1) Adding a metal solution A containing Ni, co and Mn, a metal solution B containing Ta and an alkaline solution into the base solution in a concurrent flow manner, and carrying out a coprecipitation reaction to obtain a Ta-doped nickel-cobalt-manganese hydroxide matrix dispersion solution;
(2) Adding alcohols into the Ta doped nickel-cobalt-manganese hydroxide matrix dispersion liquid obtained in the step (1), adding silicates, and reacting to obtain the nickel-cobalt-manganese hydroxide.
The invention provides a preparation method of nickel-cobalt-manganese hydroxide, on one hand, ta is doped in a nickel-cobalt-manganese hydroxide matrix, and Ta doping is mainly lithium-site doping, so that disorder degree of lithium/nickel can be inhibited, a supporting column effect is exerted, and the structure of a material is stabilized. And Ta doping is carried out in the preparation process of the matrix, so that the molecular level mixing can be realized, and the reliability of the material is improved. On the other hand, the alkaline environment in the doping stage is utilized to carry out the coating reaction, and a coating layer is constructed on the surface of the Ta-doped nickel-cobalt-manganese hydroxide matrix, so that the structural stability of the material is enhanced. The preparation method provided by the invention can effectively improve the structural stability of the material, and can effectively adjust and monitor the doping and coating processes. In addition, the doping and coating processes can be carried out in the same reaction vessel, so that the method has no complicated process, saves the cost and is beneficial to industrial production.
As a preferable technical solution of the present invention, the alkaline solution includes a sodium hydroxide solution and an ammonia solution.
The phase of sodium hydroxide is not particularly limited in the present invention, and may be, for example, liquid caustic soda. The sodium hydroxide solution can be prepared by using liquid alkali.
Preferably, the flow ratio of the metal solution A, the metal solution B, the sodium hydroxide solution and the ammonia solution is 10 (0.16-3) to (3.2-4.5) to (0.3-0.7), wherein the selection range of the metal solution B is 0.16-3, such as 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 1; the sodium hydroxide solution can be selected from the range of 3.2 to 4.5, for example, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, or 4.5; the ammonia solution can be selected from the range of 0.3 to 0.7, for example, 0.3, 0.4, 0.5, 0.6 or 0.7, but is not limited to the values recited, and other values not recited in the numerical range are also applicable.
Preferably, the metal solution a includes a Ni-containing compound, a Co-containing compound, and a Mn-containing compound.
Preferably, the Ni-containing compound includes NiSO 4 、Ni(NO 3 ) 2 And NiCl 2 At least one of (1).
Preferably, the Co-containing compound comprises CoSO 4 、Co(NO 3 ) 2 And CoCl 2 At least one of (1).
Preferably, the Mn-containing compound includes MnSO 4 、Mn(NO 3 ) 2 And MnCl 2 At least one of (a).
Preferably, the total concentration of Ni, co and Mn in the metal solution A is 1.6 to 2.4mol/L, and may be, for example, 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, 2.0mol/L, 2.1mol/L, 2.2mol/L, 2.3mol/L or 2.4mol/L, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, in the metal solution a, the molar ratio of Ni, co and Mn is Ni: co: mn = x: y: z, where x + y + z =1, 0.6-x-na 1, for example, x may be 0.65, 0.7, 0.75, 0.8, 0.85, 0.9 or 0.95, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preference is given toThe metal solution B comprises NaTaO 3 And/or NaTaO 5 。
Preferably, the concentration of Ta in the metal solution B is 0.04 to 0.1mol/L, and may be, for example, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, or 0.1mol/L, but is not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
Preferably, the ratio of the total molar amount of Ni, co and Mn in the metal solution a to the molar amount of Ta in the metal solution B is (200 to 999) 1, which may be, for example, 200.
In the invention, the ratio of the total molar weight of Ni, co and Mn in the metal solution A to the molar weight of Ta in the metal solution B has a preferable range, if the ratio is lower than 200; if the ratio is higher than 999.
Preferably, the concentration of the sodium hydroxide solution is 9 to 12mol/L, for example, 9mol/L, 9.5mol/L, 10mol/L, 10.5mol/L, 11mol/L, 11.5mol/L or 12mol/L, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the concentration of the ammonia solution is 7 to 10mol/L, for example, 7mol/L, 7.5mol/L, 8mol/L, 8.5mol/L, 9mol/L, 9.5mol/L or 10mol/L, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the base solution comprises water, ammonia and sodium hydroxide.
The phase of the sodium hydroxide used to prepare the base solution is not particularly limited, and may be, for example, a liquid caustic soda.
As a preferred embodiment of the present invention, the alcohol includes at least one of methanol, ethanol, propanol and butanol.
Preferably, the silicate comprises tetraethyl orthosilicate.
Preferably, the ratio of the total molar amount of Ni, co and Mn in the Ta doped nickel cobalt manganese hydroxide matrix dispersion to the molar amount of Si in the silicate is 100 (0.5 to 1), and may be, for example, 100.
In the invention, the ratio of the total molar weight of Ni, co and Mn in the dispersion liquid to the molar weight of Si in tetraethyl orthosilicate is in a preferred range, if the ratio is lower than 100; if the ratio is higher than 100.
In a preferred embodiment of the present invention, the pH during the coprecipitation reaction in step (1) is controlled to be in the range of 10 to 13, for example, 10, 10.5, 11, 11.5, 12, 12.5 or 13, but is not limited to the values listed above, and other values not listed above within the range of values are also applicable.
Preferably, during the coprecipitation reaction in step (1), the temperature is controlled to be in the range of 40 to 70 ℃, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the coprecipitation reaction in step (1) is carried out under stirring at 250-420 rpm, such as 250rpm, 280rpm, 300rpm, 320rpm, 350rpm, 380rpm, 400rpm or 420rpm, but not limited to the values listed, and other values not listed in the range of values are also applicable.
As a preferred embodiment of the present invention, in the step (2) of the reaction process, the temperature is controlled in the range of 40 to 70 ℃, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, but not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the reaction of step (2) is carried out under stirring at a speed of 250 to 420rpm, for example 250rpm, 280rpm, 300rpm, 320rpm, 350rpm, 380rpm, 400rpm or 420rpm, but not limited to the recited values, and other values not recited within the range of values are also applicable.
As a preferred technical scheme of the present invention, the preparation method specifically comprises the following steps:
preparing a metal solution A with the total concentration of Ni, co and Mn of 1.6-2.4 mol/L, wherein the molar ratio of Ni to Co to Mn = x to y to z, wherein x + y + z =1, and 0.6-x-cloth-1;
preparing a metal solution B with the concentration of Ta of 0.04-0.1 mol/L;
preparing a sodium hydroxide solution with the concentration of 9-12 mol/L;
preparing ammonia solution with the concentration of 7-10 mol/L;
(II) preparing a base solution in a reaction container, and adding a metal solution A, a metal solution B, a sodium hydroxide solution and an ammonia solution in parallel at a flow ratio of 10 (0.16-3) to (3.2-4.5) to (0.3-0.7) to perform coprecipitation reaction to obtain a Ta-doped nickel-cobalt-manganese hydroxide dispersion solution;
(III) adding alcohols into the Ta-doped nickel-cobalt-manganese hydroxide matrix dispersion liquid, adding silicates, and reacting to obtain the nickel-cobalt-manganese hydroxide.
In a second aspect, the invention provides a nickel-cobalt-manganese hydroxide, which is prepared by the preparation method of the first aspect.
Preferably, the nickel-cobalt-manganese hydroxide comprises a Ta-doped nickel-cobalt-manganese hydroxide substrate and a silicon-oxygen coating layer coated on the surface of the Ta-doped nickel-cobalt-manganese hydroxide substrate.
In a preferred embodiment of the present invention, the amount of doped Ta in the Ta-doped Ni-Co-Mn hydroxide matrix is 2000 to 10000ppm, preferably 2000 to 5000ppm, for example 2000ppm, 2500ppm, 3000ppm, 3500ppm, 4000ppm, 4500ppm, 5000ppm, 5500ppm, 6000ppm, 6500ppm, 7000ppm, 7500ppm, 8000ppm, 8500ppm, 9000ppm, 9500ppm or 10000ppm, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
The thickness of the silicon oxide coating is preferably 2 to 14nm, and may be, for example, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm or 14nm, but is not limited to the values listed above, and other values not listed above within the range of values are also applicable.
In a third aspect, the invention provides a cathode material, wherein the cathode material is obtained by mixing and sintering the nickel-cobalt-manganese hydroxide and the lithium source.
Preferably, the positive electrode material comprises a nickel cobalt lithium manganate substrate and a lithiated silicon oxygen coating layer coated on the surface of the nickel cobalt lithium manganate substrate.
In the present invention, lithiated silica means a compound containing Li, si and O. The lithiated silicon oxide coating layer can separate the electrolyte from the nickel cobalt lithium manganate matrix, so that the layered structure of the surface of the nickel cobalt lithium manganate is kept, and the structure of the nickel cobalt lithium manganate is stable. In addition, the lithiated silicon-oxygen coating layer has good capability of conducting lithium ions, and does not influence the transmission of the lithium ions. Therefore, the prepared cathode material can have both high capacity and high cycle stability.
Preferably, the lithium source comprises lithium hydroxide and/or lithium carbonate.
Preferably, the molar ratio of the lithium source to the nickel-cobalt-manganese hydroxide transition metal is (1-1.08): 1, and may be, for example, 1.
Preferably, the sintering temperature is 700 to 900 ℃, for example 700 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the sintering time is 5 to 15 hours, for example, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or 15 hours, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
In a fourth aspect, the present invention provides a lithium ion battery, wherein a positive electrode of the lithium ion battery includes the positive electrode material of the third aspect.
The numerical ranges set forth herein include not only the points recited above, but also any points between the numerical ranges not recited above, and are not exhaustive of the particular points included in the ranges for reasons of brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of nickel-cobalt-manganese hydroxide, on one hand, ta is doped in a nickel-cobalt-manganese hydroxide matrix, and Ta doping belongs to lithium-position doping, so that the disorder degree of lithium/nickel can be inhibited, the pillar effect is exerted, and the structure of a material is stabilized. And Ta doping is carried out in the preparation process of the matrix, so that the molecular level mixing can be realized, and the reliability of the material is improved. On the other hand, the alkaline environment in the doping stage is utilized to carry out the coating reaction, and a coating layer is constructed on the surface of the Ta-doped nickel-cobalt-manganese hydroxide matrix, so that the structural stability of the material is enhanced. The preparation method provided by the invention can effectively improve the structural stability of the material, and can effectively adjust and monitor the doping and cladding processes. In addition, the doping and coating processes can be carried out in the same reaction vessel, so that the method has no complicated process, saves the cost and is beneficial to industrial production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a preparation method of nickel-cobalt-manganese hydroxide, which specifically comprises the following steps:
(1) By using NiSO 4 、CoSO 4 And Mn (NO) 3 ) 2 Preparing a metal solution A, wherein the total concentration of Ni, co and Mn is 2.4mol/L, and the molar ratio of Ni, co and Mn is 0.65; preparing a metal solution B with the concentration of Ta of 0.04 mol/L; preparing a sodium hydroxide solution with the concentration of 9 mol/L; preparing an ammonia solution with the concentration of 7 mol/L;
(2) Injecting a proper amount of water, ammonia and liquid alkali into a reaction container, fully stirring and mixing to prepare a base solution, wherein the pH value of the base solution is 10-11, then adding a metal solution A, a metal solution B, a sodium hydroxide solution and an ammonia solution into the reaction container in parallel flow at the flow rates of 10L/h, 3L/h, 3.2L/h and 0.3L/h respectively, wherein the ratio of the total molar amount of Ni, co and Mn in the added metal solution A to the molar amount of Ta in the metal solution B is 200, carrying out coprecipitation reaction under the conditions of pH value of 10.3-10.5 and temperature of 40 ℃, carrying out the coprecipitation reaction under stirring, wherein the stirring speed is 250rpm, and obtaining a Ta-doped manganese-nickel cobalt hydroxide dispersion solution after the reaction;
(3) Under the conditions that the temperature is 40 ℃ and the stirring speed is 250rpm, adding ethanol into the Ta-doped nickel-cobalt-manganese hydroxide matrix dispersion liquid, then adding tetraethyl orthosilicate, controlling the ratio of the total molar weight of Ni, co, mn and Ta in the dispersion liquid to the molar weight of Si in the tetraethyl orthosilicate to be 100.5, and drying after reaction to obtain the nickel-cobalt-manganese hydroxide.
The nickel-cobalt-manganese hydroxide prepared by the embodiment comprises a Ta-doped nickel-cobalt-manganese hydroxide substrate and a silicon-oxygen coating layer coated on the surface of the substrate, wherein the doping amount of Ta in the Ta-doped nickel-cobalt-manganese hydroxide substrate is 10000ppm, and the thickness of the silicon-oxygen coating layer is 2nm.
The embodiment also provides a positive electrode material, and the preparation method of the positive electrode material comprises the following steps:
and mixing the nickel-cobalt-manganese hydroxide with lithium hydroxide, and sintering at 850 ℃ for 8h to obtain the cathode material.
Example 2
The embodiment provides a preparation method of nickel-cobalt-manganese hydroxide, which specifically comprises the following steps:
(1) By using NiSO 4 、CoSO 4 And Mn (NO) 3 ) 2 Preparing a metal solution A, wherein the total concentration of Ni, co and Mn is 2.4mol/L, and the molar ratio of Ni, co and Mn is 0.8; preparing a metal solution B with the concentration of Ta of 0.06 mol/L; preparing a sodium hydroxide solution with the concentration of 11 mol/L; preparing an ammonia solution with the concentration of 10mol/L;
(2) Injecting a proper amount of water, ammonia and liquid caustic soda into a reaction container, fully stirring and mixing to prepare a base solution, wherein the pH value of the base solution is 11-12, then adding a metal solution A, a metal solution B, a sodium hydroxide solution and an ammonia solution into the reaction container in parallel flow at the flow rates of 10L/h, 0.45L/h, 4.36L/h and 0.4L/h respectively, wherein the ratio of the total molar weight of Ni, co and Mn in the added metal solution A to the molar weight of Ta in the metal solution B is 889, carrying out coprecipitation reaction under the conditions of pH value of 11.2-11.5 and temperature of 47 ℃, carrying out the coprecipitation reaction under stirring, wherein the stirring speed is 292rpm, and obtaining a Ta-doped nickel-cobalt-manganese hydroxide dispersion solution after the reaction;
(3) Under the conditions that the temperature is 47 ℃ and the stirring speed is 292rpm, adding ethanol into the Ta-doped nickel-cobalt-manganese hydroxide matrix dispersion liquid, then adding tetraethyl orthosilicate, controlling the ratio of the total molar weight of Ni, co, mn and Ta in the dispersion liquid to the molar weight of Si in the tetraethyl orthosilicate to be 100.5, and drying after reaction to obtain the nickel-cobalt-manganese hydroxide.
The nickel-cobalt-manganese hydroxide prepared by the embodiment comprises a Ta-doped nickel-cobalt-manganese hydroxide substrate and a silicon-oxygen coating layer coated on the surface of the substrate, wherein the doping amount of Ta in the Ta-doped nickel-cobalt-manganese hydroxide substrate is 2100, and the thickness of the silicon-oxygen coating layer is 2nm.
The embodiment also provides a positive electrode material, and the preparation method of the positive electrode material comprises the following steps:
and mixing the nickel-cobalt-manganese hydroxide with lithium hydroxide, and sintering at 750 ℃ for 8h to obtain the cathode material.
Example 3
The embodiment provides a preparation method of nickel-cobalt-manganese hydroxide, which specifically comprises the following steps:
(1) By using NiSO 4 、CoCl 2 And Mn (NO) 3 ) 2 Preparing a metal solution A, wherein the total concentration of Ni, co and Mn is 2.3mol/L, and the molar ratio of Ni, co and Mn is 0.8; preparing a metal solution B with the concentration of Ta of 0.06 mol/L; preparing a sodium hydroxide solution with the concentration of 10.5 mol/L; preparing ammonia solution with the concentration of 8.5 mol/L;
(2) Injecting a proper amount of water, ammonia and liquid alkali into a reaction container, fully stirring and mixing to prepare a base solution, wherein the pH value of the base solution is 11-12, then adding a metal solution A, a metal solution B, a sodium hydroxide solution and an ammonia solution into the reaction container in parallel at the flow rates of 10L/h, 0.8L/h, 3.85L/h and 0.5L/h respectively, wherein the ratio of the total molar weight of Ni, co and Mn in the added metal solution A to the molar weight of Ta in the metal solution B is 479;
(3) Under the conditions that the temperature is 55 ℃ and the stirring speed is 335rpm, adding ethanol into the Ta-doped nickel-cobalt-manganese hydroxide matrix dispersion liquid, then adding tetraethyl orthosilicate, controlling the ratio of the total molar weight of Ni, co, mn and Ta in the dispersion liquid to the molar weight of Si in the tetraethyl orthosilicate to be 100.75, and drying after reaction to obtain the nickel-cobalt-manganese hydroxide.
The nickel-cobalt-manganese hydroxide prepared in this example includes a Ta-doped nickel-cobalt-manganese hydroxide substrate and a silicon-oxygen coating layer coated on the surface of the substrate, the doping amount of Ta in the Ta-doped nickel-cobalt-manganese hydroxide substrate is 4100ppm, and the thickness of the silicon-oxygen coating layer is 8nm.
The embodiment also provides a positive electrode material, and the preparation method of the positive electrode material comprises the following steps:
and mixing the nickel-cobalt-manganese hydroxide with lithium hydroxide, and sintering at 750 ℃ for 8h to obtain the cathode material.
Example 4
The embodiment provides a preparation method of nickel-cobalt-manganese hydroxide, which specifically comprises the following steps:
(1) Using NiCl 2 、CoSO 4 And MnCl 2 Preparing a metal solution A, wherein the total concentration of Ni, co and Mn is 1.85mol/L, and the molar ratio of Ni, co and Mn is 0.9; preparing a metal solution B with the concentration of Ta of 0.07 mol/L; preparing a sodium hydroxide solution with the concentration of 11 mol/L; preparing ammonia solution with the concentration of 9 mol/L;
(2) Injecting a proper amount of water, ammonia and liquid alkali into a reaction container, fully stirring and mixing to prepare a base solution, wherein the pH value of the base solution is 12-13, then adding a metal solution A, a metal solution B, a sodium hydroxide solution and an ammonia solution into the reaction container in parallel flow at the flow rates of 10L/h, 0.8L/h, 4.2L/h and 0.4L/h respectively, wherein the ratio of the total molar weight of Ni, co and Mn in the added metal solution A to the molar weight of Ta in the metal solution B is 330, carrying out coprecipitation reaction under the conditions of pH value of 12.3-12.5 and temperature of 62 ℃, carrying out the coprecipitation reaction under stirring, wherein the stirring speed is 377rpm, and obtaining a Ta-doped nickel cobalt manganese hydroxide dispersion solution after the reaction;
(3) Under the conditions that the temperature is 62 ℃ and the stirring speed is 377rpm, adding ethanol into the Ta-doped nickel-cobalt-manganese hydroxide matrix dispersion liquid, then adding tetraethyl orthosilicate, controlling the ratio of the total molar weight of Ni, co, mn and Ta in the dispersion liquid to the molar weight of Si in the tetraethyl orthosilicate to be 100.83, and drying after reaction to obtain the nickel-cobalt-manganese hydroxide.
The nickel-cobalt-manganese hydroxide prepared by the embodiment comprises a Ta-doped nickel-cobalt-manganese hydroxide substrate and a silicon-oxygen coating layer coated on the surface of the substrate, wherein the doping amount of Ta in the Ta-doped nickel-cobalt-manganese hydroxide substrate is 5900ppm, and the thickness of the silicon-oxygen coating layer is 10nm.
The embodiment also provides a positive electrode material, and the preparation method of the positive electrode material comprises the following steps:
and mixing the nickel-cobalt-manganese hydroxide, the lithium hydroxide and the lithium carbonate, and sintering at 700 ℃ for 7h to obtain the cathode material.
Example 5
The embodiment provides a preparation method of nickel-cobalt-manganese hydroxide, which specifically comprises the following steps:
(1) Using Ni (NO) 3 ) 2 、Co(NO 3 ) 2 And Mn (NO) 3 ) 2 Preparing a metal solution A, wherein the total concentration of Ni, co and Mn is 1.6mol/L, and the molar ratio of Ni, co and Mn is 0.95; preparing a metal solution B with the concentration of Ta of 0.1mol/L; preparing a sodium hydroxide solution with the concentration of 12mol/L; preparing an ammonia solution with the concentration of 10mol/L;
(2) Injecting a proper amount of water, ammonia and liquid alkali into a reaction container, fully stirring and mixing to prepare a base solution, wherein the pH value of the base solution is 12-13, then adding a metal solution A, a metal solution B, a sodium hydroxide solution and an ammonia solution into the reaction container in parallel flow at the flow rates of 10L/h, 0.17L/h, 4.5L/h and 0.7L/h respectively, wherein the ratio of the total molar weight of Ni, co and Mn in the added metal solution A to the molar weight of Ta in the metal solution B is 941 1, carrying out coprecipitation reaction under the conditions that the pH value is 12.7-13.0 and the temperature is 70 ℃, carrying out the coprecipitation reaction under stirring, wherein the stirring speed is 420rpm, and obtaining Ta-doped nickel cobalt manganese hydroxide dispersion liquid after the reaction;
(3) Under the conditions that the temperature is 70 ℃ and the stirring speed is 420rpm, adding ethanol into the Ta-doped nickel-cobalt-manganese hydroxide matrix dispersion liquid, then adding tetraethyl orthosilicate, controlling the ratio of the total molar weight of Ni, co, mn and Ta in the dispersion liquid to the molar weight of Si in the tetraethyl orthosilicate to be 100, and drying after reaction to obtain the nickel-cobalt-manganese hydroxide.
The nickel-cobalt-manganese hydroxide prepared by the embodiment comprises a Ta-doped nickel-cobalt-manganese hydroxide substrate and a silicon-oxygen coating layer coated on the surface of the substrate, wherein the doping amount of Ta in the Ta-doped nickel-cobalt-manganese hydroxide substrate is 2100ppm, and the thickness of the silicon-oxygen coating layer is 14nm.
The embodiment also provides a positive electrode material, and the preparation method of the positive electrode material comprises the following steps:
and mixing the nickel-cobalt-manganese hydroxide with lithium hydroxide, and sintering at 700 ℃ for 6h to obtain the cathode material.
Example 6
The embodiment provides a preparation method of nickel-cobalt-manganese hydroxide, which specifically comprises the following steps:
(1) Using Ni (NO) 3 ) 2 、Co(NO 3 ) 2 And Mn (NO) 3 ) 2 Preparing a metal solution A, wherein the total concentration of Ni, co and Mn is 1.9mol/L, and the molar ratio of Ni, co and Mn is 0.8; preparing a metal solution B with the concentration of Ta of 0.08 mol/L; preparing a sodium hydroxide solution with the concentration of 11 mol/L; preparing ammonia solution with the concentration of 9 mol/L;
(2) Injecting a proper amount of water, ammonia and liquid alkali into a reaction container, fully stirring and mixing to prepare a base solution, wherein the pH value of the base solution is 11-12, then adding a metal solution A, a metal solution B, a sodium hydroxide solution and an ammonia solution into the reaction container in parallel flow at the flow rates of 10L/h, 0.8L/h, 3.45L/h and 0.6L/h respectively, wherein the ratio of the total molar weight of Ni, co and Mn in the added metal solution A to the molar weight of Ta in the metal solution B is 297;
(3) Under the conditions that the temperature is 70 ℃ and the stirring speed is 420rpm, adding ethanol into the Ta doped nickel-cobalt-manganese hydroxide matrix dispersion liquid, then adding tetraethyl orthosilicate, controlling the ratio of the total molar weight of Ni, co, mn and Ta in the dispersion liquid to the molar weight of Si in the tetraethyl orthosilicate to be 0.5, and drying after reaction to obtain the nickel-cobalt-manganese hydroxide.
The nickel-cobalt-manganese hydroxide prepared by the embodiment comprises a Ta-doped nickel-cobalt-manganese hydroxide substrate and a silicon-oxygen coating layer coated on the surface of the substrate, wherein the doping amount of Ta in the Ta-doped nickel-cobalt-manganese hydroxide substrate is 6600ppm, and the thickness of the silicon-oxygen coating layer is 2nm.
The embodiment also provides a positive electrode material, and the preparation method of the positive electrode material comprises the following steps:
and mixing the nickel-cobalt-manganese hydroxide with lithium hydroxide, and sintering at 750 ℃ for 8h to obtain the cathode material.
Example 7
This example provides a method for preparing nickel cobalt manganese hydroxide, which is different from example 3 in that, in step (2), the ratio of the total molar amount of Ni, co and Mn in the metal solution a to the molar amount of Ta in the metal solution B is adjusted to 190, and the other operation steps are exactly the same as the process parameters in example 3.
The embodiment also provides a cathode material, and the preparation method of the cathode material is completely the same as that of the embodiment 3.
Example 8
This example provides a method for preparing nickel cobalt manganese hydroxide, which is different from example 3 in that in step (2), the ratio of the total molar amount of Ni, co and Mn in the metal solution a to the molar amount of Ta in the metal solution B is adjusted to 1009 1, and the other operation steps are exactly the same as the process parameters and example 3.
The embodiment also provides a cathode material, and the preparation method of the cathode material is completely the same as that of the embodiment 3.
Example 9
This example provides a method for preparing nickel cobalt manganese hydroxide, which is different from example 3 in that, in step (3), the ratio of the total molar amount of Ni, co, mn and Ta in the dispersion to the molar amount of Si in tetraethyl orthosilicate is adjusted to 100.4, and the other operation steps are exactly the same as the process parameters and example 3.
The embodiment also provides a positive electrode material, and the preparation method of the positive electrode material is completely the same as that of the embodiment 3.
Example 10
This example provides a method for preparing nickel cobalt manganese hydroxide, which is different from example 3 in that, in step (3), the ratio of the total molar amount of Ni, co, mn and Ta in the dispersion to the molar amount of Si in tetraethyl orthosilicate is adjusted to 100.1, and the other operation steps are exactly the same as the process parameters and example 3.
The embodiment also provides a cathode material, and the preparation method of the cathode material is completely the same as that of the embodiment 3.
Comparative example 1
The comparative example provides a preparation method of nickel-cobalt-manganese hydroxide, which specifically comprises the following steps:
(1) Using Ni (NO) 3 ) 2 、Co(NO 3 ) 2 And Mn (NO) 3 ) 2 Preparing a metal solution A, wherein the total concentration of Ni, co and Mn is 1.9mol/L, and the molar ratio of Ni, co and Mn is 0.8; preparing a sodium hydroxide solution with the concentration of 11 mol/L; preparing ammonia solution with the concentration of 9 mol/L;
(2) Injecting a proper amount of water, ammonia and liquid caustic soda into a reaction container, fully stirring and mixing to prepare a base solution, wherein the pH value of the base solution is 11-12, then adding a metal solution A, a sodium hydroxide solution and an ammonia solution into the reaction container in parallel flow at the flow rates of 10L/h, 3.45L/h and 0.6L/h respectively, carrying out coprecipitation reaction under the conditions that the pH value is 11.3-11.5 and the temperature is 70 ℃, carrying out the coprecipitation reaction under stirring, wherein the stirring speed is 420rpm, and obtaining a nickel-cobalt-manganese hydroxide dispersion solution after the reaction;
(3) Under the conditions that the temperature is 70 ℃ and the stirring speed is 420rpm, adding ethanol into the nickel-cobalt-manganese hydroxide matrix dispersion liquid, then adding tetraethyl orthosilicate, controlling the ratio of the total molar weight of Ni, co and Mn in the dispersion liquid to the molar weight of Si in the tetraethyl orthosilicate to be 0.5, and drying after reaction to obtain the nickel-cobalt-manganese hydroxide.
The comparative example also provides a positive electrode material, and the preparation method of the positive electrode material comprises the following steps:
and mixing the nickel-cobalt-manganese hydroxide with lithium hydroxide, and sintering at 750 ℃ for 8h to obtain the cathode material.
Comparative example 2
This comparative example provides a preparation method of a nickel cobalt manganese hydroxide, which is different from example 6 in that the Ta-doped nickel cobalt manganese hydroxide dispersion was directly centrifuged, washed and dried without performing step (3) to obtain a nickel cobalt manganese hydroxide.
The comparative example also provides a positive electrode material, and the preparation method of the positive electrode material comprises the following steps:
and mixing the nickel-cobalt-manganese hydroxide with lithium hydroxide, and sintering at 750 ℃ for 8h to obtain the cathode material.
Comparative example 3
The comparative example provides a preparation method of nickel-cobalt-manganese hydroxide, which specifically comprises the following steps:
(1) Using Ni (NO) 3 ) 2 、Co(NO 3 ) 2 And Mn (NO) 3 ) 2 Preparing a metal solution A, wherein the total concentration of Ni, co and Mn is 1.9mol/L, and the molar ratio of Ni, co and Mn is 0.8; preparing a sodium hydroxide solution with the concentration of 11 mol/L; preparing an ammonia solution with the concentration of 9 mol/L;
(2) Injecting a proper amount of water, ammonia and liquid alkali into a reaction container, fully stirring and mixing to prepare a base solution, wherein the pH value of the base solution is 11-12, then adding a metal solution A, a sodium hydroxide solution and an ammonia solution into the reaction container in parallel flow at the flow rates of 10L/h, 3.45L/h and 0.6L/h respectively, carrying out coprecipitation reaction under the conditions of pH value of 11.3-11.5 and temperature of 70 ℃, carrying out the coprecipitation reaction under stirring at the stirring speed of 420rpm, obtaining a nickel-cobalt-manganese hydroxide dispersion solution after the reaction, centrifuging the nickel-cobalt-manganese hydroxide dispersion solution, washing and drying to obtain the nickel-cobalt-manganese hydroxide.
The comparative example also provides a positive electrode material, and the preparation method of the positive electrode material comprises the following steps:
and mixing the nickel-cobalt-manganese hydroxide with lithium hydroxide, and sintering at 750 ℃ for 8h to obtain the cathode material.
Comparative example 4
The comparative example provides a preparation method of nickel-cobalt-manganese hydroxide, which specifically comprises the following steps:
(1) Using Ni (NO) 3 ) 2 、Co(NO 3 ) 2 And Mn (NO) 3 ) 2 Preparing a metal solution A, wherein the total concentration of Ni, co and Mn is 1.9mol/L, and the molar ratio of Ni, co and Mn is 0.8; preparing a metal solution B with the concentration of Ta of 0.08 mol/L; preparing a sodium hydroxide solution with the concentration of 11 mol/L; preparing ammonia solution with the concentration of 9 mol/L;
(2) Injecting a proper amount of water, ammonia and liquid alkali into a reaction container, fully stirring and mixing to prepare a base solution, wherein the pH value of the base solution is 11-12, then adding a metal solution A, a metal solution B, a sodium hydroxide solution and an ammonia solution into the reaction container in parallel at the flow rates of 10L/h, 0.8L/h, 3.45L/h and 0.6L/h respectively, wherein the ratio of the total molar weight of Ni, co and Mn in the added metal solution A to the molar weight of Ta in the metal solution B is 297 1, carrying out coprecipitation reaction under the conditions of pH value of 11.3-11.5 and temperature of 70 ℃, carrying out the coprecipitation reaction under stirring, wherein the stirring speed is 420rpm, obtaining a Ta-doped nickel-cobalt-manganese hydroxide dispersion liquid after the reaction, and carrying out the steps of centrifuging, washing and drying to obtain the Ta-doped nickel-cobalt-manganese hydroxide.
(3) Under the conditions that the temperature is 70 ℃ and the stirring speed is 420rpm, fully and uniformly stirring Ta-doped nickel-cobalt-manganese hydroxide in an ethanol solution, adding a proper amount of ammonia solution with the concentration of 9mol/L, then adding tetraethyl orthosilicate, controlling the ratio of the total molar weight of Ni, co, mn and Ta in the dispersion liquid to the molar weight of Si in the tetraethyl orthosilicate to be 0.5, and drying after reaction to obtain the nickel-cobalt-manganese hydroxide.
The comparative example also provides a positive electrode material, and the preparation method of the positive electrode material comprises the following steps:
and mixing the nickel-cobalt-manganese hydroxide with lithium hydroxide, and sintering at 750 ℃ for 8h to obtain the cathode material.
And (3) performance testing:
the positive electrode materials provided in examples 1 to 10 and comparative examples 1 to 4 were combined with other parts to prepare lithium ion batteries by the following methods: 80wt% of the positive electrode material, 10wt% of Super-P and 10wt% of polyvinylidene fluoride (PVDF) were thoroughly dispersed in N-methylpyrrolidone (NMP) solution to prepare an electrode slurry, and then further prepared into an electrode. The prepared electrode was used as a positive electrode, lithium metal was used as a negative electrode, and 1M LiPF 6 With a mixture of EC, DMC and EMC (EC: DMC: EMC = 1.
And (3) testing conditions: at 3.0-4.5V (vs Li/Li) + ) In between, the test is performed within the voltage window.
The test results are shown in table 1.
TABLE 1
From the results of example 3, example 7 and example 8, it can be seen that if the ratio of the total molar amount of Ni, co and Mn in the metal solution a to the molar amount of Ta in the metal solution B is too low, the Ta doping content in the nickel-cobalt-manganese hydroxide matrix is too high, and since Ta doping is mainly lithium-site doping, too much Ta causes the ion conductivity of the material to deteriorate, and the prepared cathode material exhibits a lower capacity; if the ratio is too high, the doping content of Ta in the nickel-cobalt-manganese hydroxide matrix is too low, and the structural stability of the material cannot be effectively improved due to too little Ta, so that the structural stability of the material is poor, and the prepared cathode material has a low capacity retention rate.
From the results of examples 3, 9, and 10, it is understood that a ratio of the total molar amount of Ni, co, mn, and Ta in the dispersion to the molar amount of Si in tetraethyl orthosilicate is too low, resulting in an excessively thick coating layer, inhibiting performance of the positive electrode material, and having a low specific capacity; and too high ratio can lead to too thin coating layer, and the thin coating layer can not effectively inhibit boundary reaction, thereby reducing the electrochemical stability of the material.
From the results of example 6 and comparative examples 1 to 3, it can be seen that if the nickel-cobalt-manganese hydroxide matrix is not doped with Ta and only the surface of the matrix is coated, or only the nickel-cobalt-manganese hydroxide matrix is doped with Ta and not coated, the prepared positive electrode material shows poorer cycle stability; the nickel-cobalt-manganese hydroxide prepared without doping or coating has poorer structural stability, and the prepared anode material has poorer cycle stability. The method provided by the invention not only dopes Ta but also coats, so that the obtained nickel-cobalt-manganese hydroxide has more excellent structural stability and reliability, and the prepared cathode material has high discharge capacity and excellent cycle stability. The method for doping and coating Ta can improve the structural stability of the material and the performance of the material.
From the results of example 6 and comparative example 4, it is known that after the Ta doped nickel cobalt manganese hydroxide dispersion is prepared, compared with the method of drying and then performing wet coating, the alkaline environment of the Ta doped nickel cobalt manganese hydroxide dispersion is directly used for performing wet coating, and the obtained positive electrode material has excellent performance.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of nickel-cobalt-manganese hydroxide is characterized by comprising the following steps:
(1) Adding a metal solution A containing Ni, co and Mn, a metal solution B containing Ta and an alkaline solution into the base solution in a concurrent flow manner, and carrying out a coprecipitation reaction to obtain a Ta-doped nickel-cobalt-manganese hydroxide matrix dispersion solution;
(2) Adding alcohols into the Ta doped nickel-cobalt-manganese hydroxide matrix dispersion liquid obtained in the step (1), adding silicates, and reacting to obtain the nickel-cobalt-manganese hydroxide.
2. The production method according to claim 1, wherein the alkaline solution includes a sodium hydroxide solution and an ammonia solution;
preferably, the flow ratio of the metal solution A, the metal solution B, the sodium hydroxide solution and the ammonia solution is 10 (0.16-3): 3.2-4.5): 0.3-0.7;
preferably, the metal solution a includes a Ni-containing compound, a Co-containing compound, and a Mn-containing compound;
preferably, the Ni-containing compound includes NiSO 4 、Ni(NO 3 ) 2 And NiCl 2 At least one of;
preferably, the Co-containing compound comprises CoSO 4 、Co(NO 3 ) 2 And CoCl 2 At least one of (a);
preferably, the Mn-containing compound includes MnSO 4 、Mn(NO 3 ) 2 And MnCl 2 At least one of (a);
preferably, the total concentration of Ni, co and Mn in the metal solution A is 1.6-2.4 mol/L;
preferably, the molar ratio of Ni, co and Mn in the metal solution A is Ni: co: mn = x: y: z, wherein x + y + z =1, 0.6-n-1;
preferably, the metal solution B comprises NaTaO 3 And/or NaTaO 5 ；
Preferably, the concentration of Ta in the metal solution B is 0.04-0.1 mol/L;
preferably, the ratio of the total molar amount of Ni, co and Mn in the metal solution A to the molar amount of Ta in the metal solution B is (200-999): 1;
preferably, the concentration of the sodium hydroxide solution is 9-12 mol/L;
preferably, the concentration of the ammonia solution is 7-10 mol/L;
preferably, the base solution comprises water, ammonia and sodium hydroxide.
3. The production method according to claim 1 or 2, wherein the alcohol comprises at least one of methanol, ethanol, propanol and butanol;
preferably, the silicate comprises tetraethyl orthosilicate;
preferably, the ratio of the total molar amount of Ni, co and Mn in the Ta-doped nickel-cobalt-manganese hydroxide matrix dispersion liquid to the molar amount of Si in the silicate ester is 100 (0.5-1).
4. The production method according to any one of claims 1 to 3, wherein during the coprecipitation reaction in step (1), the pH is controlled to be in the range of 10 to 13;
preferably, in the coprecipitation reaction process in the step (1), the temperature is controlled within the range of 40-70 ℃;
preferably, the coprecipitation reaction in step (1) is carried out under stirring, and the stirring speed is 250-420 rpm.
5. The production method according to any one of claims 1 to 4, wherein during the reaction in the step (2), the temperature is controlled in the range of 40 to 70 ℃;
preferably, the reaction in the step (2) is carried out under stirring, and the stirring speed is 250-420 rpm.
6. The preparation method according to any one of claims 1 to 5, comprising in particular the steps of:
preparing a metal solution A with the total concentration of Ni, co and Mn of 1.6-2.4 mol/L, wherein the molar ratio of Ni to Co to Mn = x to y to z, wherein x + y + z =1, and 0.6-x-cloth-1;
preparing a metal solution B with the concentration of Ta of 0.04-0.1 mol/L;
preparing a sodium hydroxide solution with the concentration of 9-12 mol/L;
preparing ammonia solution with the concentration of 7-10 mol/L;
(II) preparing a base solution in a reaction container, and adding a metal solution A, a metal solution B, a sodium hydroxide solution and an ammonia solution in parallel according to a flow ratio of (0.16-3) to (3.2-4.5) to (0.3-0.7) to perform a coprecipitation reaction to obtain a Ta-doped nickel-cobalt-manganese hydroxide dispersion solution;
(III) adding alcohols into the Ta-doped nickel-cobalt-manganese hydroxide matrix dispersion liquid, adding silicates, and reacting to obtain the nickel-cobalt-manganese hydroxide.
7. A nickel cobalt manganese hydroxide, wherein the nickel cobalt manganese hydroxide is prepared by the preparation method of claims 1 to 6;
preferably, the nickel-cobalt-manganese hydroxide comprises a Ta-doped nickel-cobalt-manganese hydroxide substrate and a silicon-oxygen coating layer coated on the surface of the Ta-doped nickel-cobalt-manganese hydroxide substrate.
8. A nickel cobalt manganese hydroxide according to claim 7 characterised in that the amount of Ta doped in the Ta doped nickel cobalt manganese hydroxide matrix is from 2000 to 10000ppm, preferably from 2000 to 5000ppm;
preferably, the thickness of the silicon oxide coating layer is 2-14 nm.
9. A positive electrode material obtained by mixing and sintering the nickel-cobalt-manganese hydroxide according to claim 7 or 8 with a lithium source;
preferably, the positive electrode material comprises a nickel cobalt lithium manganate substrate and a lithiated silicon oxygen coating layer coated on the surface of the nickel cobalt lithium manganate substrate;
preferably, the sintering temperature is 700-900 ℃;
preferably, the sintering time is 5-15 h.
10. A lithium ion battery comprising the positive electrode material according to claim 9 in a positive electrode.
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| CN202211444495.8A CN115745023A (en) | 2022-11-18 | 2022-11-18 | High-voltage nickel-cobalt-manganese hydroxide, preparation method thereof, positive electrode material and lithium ion battery |
| PCT/CN2022/140460 WO2024103481A1 (en) | 2022-11-18 | 2022-12-20 | High-voltage nickel-cobalt-manganese hydroxide and preparation method therefor, positive electrode material, and lithium-ion battery |
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| CN105680018A (en) * | 2016-03-08 | 2016-06-15 | 北京理工大学 | Ternary positive electrode material and preparation method therefor and lithium ion battery |
| CN109103446A (en) * | 2018-08-08 | 2018-12-28 | 欣旺达电子股份有限公司 | Silica coats nickelic presoma, modified high-nickel material and preparation method thereof |
| CN112072082A (en) * | 2020-07-27 | 2020-12-11 | 西安交通大学 | Precursor of nickel-cobalt-manganese hydroxide of silicon dioxide coated lithium ion battery anode material and preparation method thereof |
| CN112635735A (en) * | 2020-12-21 | 2021-04-09 | 惠州亿纬锂能股份有限公司 | Nickel-cobalt lithium manganate precursor with coating structure, preparation method and application thereof |
| CN112794370A (en) * | 2020-12-18 | 2021-05-14 | 北京当升材料科技股份有限公司 | Doped positive electrode material precursor, preparation method and application thereof, doped positive electrode material, preparation method and application thereof |
| CN113582249A (en) * | 2021-07-26 | 2021-11-02 | 广东佳纳能源科技有限公司 | Ternary precursor doped with metal elements, and preparation method and application thereof |
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- 2022-11-18 CN CN202211444495.8A patent/CN115745023A/en active Pending
- 2022-12-20 WO PCT/CN2022/140460 patent/WO2024103481A1/en unknown
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| CN105680018A (en) * | 2016-03-08 | 2016-06-15 | 北京理工大学 | Ternary positive electrode material and preparation method therefor and lithium ion battery |
| CN109103446A (en) * | 2018-08-08 | 2018-12-28 | 欣旺达电子股份有限公司 | Silica coats nickelic presoma, modified high-nickel material and preparation method thereof |
| CN112072082A (en) * | 2020-07-27 | 2020-12-11 | 西安交通大学 | Precursor of nickel-cobalt-manganese hydroxide of silicon dioxide coated lithium ion battery anode material and preparation method thereof |
| CN112794370A (en) * | 2020-12-18 | 2021-05-14 | 北京当升材料科技股份有限公司 | Doped positive electrode material precursor, preparation method and application thereof, doped positive electrode material, preparation method and application thereof |
| CN112635735A (en) * | 2020-12-21 | 2021-04-09 | 惠州亿纬锂能股份有限公司 | Nickel-cobalt lithium manganate precursor with coating structure, preparation method and application thereof |
| CN113582249A (en) * | 2021-07-26 | 2021-11-02 | 广东佳纳能源科技有限公司 | Ternary precursor doped with metal elements, and preparation method and application thereof |
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