CN115385393A - Zirconium-doped nickel-cobalt-manganese hydroxide and preparation method and application thereof - Google Patents
Zirconium-doped nickel-cobalt-manganese hydroxide and preparation method and application thereof Download PDFInfo
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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 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 43
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 35
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000975 co-precipitation Methods 0.000 claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011572 manganese Substances 0.000 claims abstract description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 20
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 14
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 13
- 239000010406 cathode material Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 18
- 239000010405 anode material Substances 0.000 abstract description 7
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
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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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention provides a zirconium-doped nickel-cobalt-manganese hydroxide, and a preparation method and application thereof. The preparation method comprises the following steps: and adding the mixed salt solution of the zirconium-doped nickel-cobalt-manganese, the precipitator solution and the complexing agent solution in a parallel flow manner, and carrying out a coprecipitation reaction to obtain the zirconium-doped nickel-cobalt-manganese hydroxide. According to the invention, a mode of co-feeding the main element of nickel, cobalt and manganese and the doping element zirconium is adopted, so that redundant working procedures are reduced, the cost is reduced, the content of the zirconium element in the nickel, cobalt and manganese can be effectively stabilized, the original mature coprecipitation working procedure can be adopted, the process improvement is reduced, the cost is reduced, the nickel, cobalt and manganese hydroxide precursor with uniformly distributed zirconium is obtained, and the electrochemical performance of the zirconium-doped nickel, cobalt and manganese anode material is further improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a zirconium-doped nickel-cobalt-manganese hydroxide, and a preparation method and application thereof.
Background
In recent years, research and industrialization of ternary material power batteries have been greatly advanced, and it is widely believed that NCM power batteries will become the mainstream choice of future electric vehicles. Generally, the ternary power battery mainly adopts 333, 442 and 523 series with relatively low nickel content based on safety and cyclicity considerations, but as the requirement of EV on energy density is higher and higher, the high nickel ternary material is also more and more valued.
High nickel ternary materials have higher energy density, but it is well known that the higher the nickel content in the ternary material, the poorer the stability and safety of the material. In order to improve the problem, one of the means is to modify the material by doping, and dope some metal ions in the crystal lattice of the ternary material, so that the mixed arrangement of cations of Li/Ni can be inhibited, the first irreversible capacity can be reduced, and the metal ion doping can enable the layered structure to be more complete, thereby being beneficial to improving the multiplying power, improving the stability of the ternary material structure and improving the cycle performance.
Since the doping is usually not uniform during the sintering process, the sintering temperature may be increased or the sintering process may be increased in order to ensure the doping amount and improve the doping uniformity, which has the disadvantages of poor uniformity, high energy consumption and more processes.
CN111682198A discloses a stepped gradient doped ternary cathode material and a preparation method thereof. The preparation method comprises the following steps: fully mixing a ternary material precursor, a first lithium source and a doping agent a, and sintering at 750-950 ℃ for 2-8 h to obtain a lithiation product; and fully mixing the lithiation product, a second lithium source and the dopant b, and sintering at 750-950 ℃ for 2-8 h to obtain the stepped gradient doped ternary positive electrode material.
CN109742336A discloses a surface layer coated lithium tungstate and W-doped ternary cathode material and a preparation method thereof. The preparation of the precursor in the method adopts the existing industrialized coprecipitation method by hydroxide, and the method is simple and convenient, low in production cost and mild in process conditions. The preparation of the ternary cathode material with the surface layer coated with the lithium tungstate and the W-doped ternary cathode material is realized by adopting a one-step method, namely, a tungsten source is added in the process of mixing a precursor and a lithium salt, and then high-temperature calcination is carried out, so that the ternary cathode material is obtained, and the preparation method is simple.
The above documents are doped during the sintering process, and this stage usually results in non-uniform doping.
In contrast, in recent years, researchers gradually act element doping on a precursor, so that the doping uniformity is improved, the sintering process is reduced, and the electrochemical performance of the cathode material is improved.
Therefore, how to reduce the preparation processes in the precursor doping process, reduce the cost, and stabilize the content of the doping element, thereby improving the electrochemical performance of the finally obtained cathode material is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a zirconium-doped nickel-cobalt-manganese hydroxide, and a preparation method and application thereof. According to the invention, a mode of co-feeding the main element of nickel, cobalt and manganese and the doping element zirconium is adopted, so that redundant working procedures are reduced, the cost is reduced, the content of the zirconium element in the nickel, cobalt and manganese can be effectively stabilized, the original mature coprecipitation working procedure can be adopted, the process improvement is reduced, the cost is reduced, the nickel, cobalt and manganese hydroxide precursor with uniformly distributed zirconium is obtained, and the electrochemical performance of the zirconium-doped nickel, cobalt and manganese anode material is further improved.
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 zirconium-doped nickel-cobalt-manganese hydroxide, comprising the steps of:
and adding the mixed salt solution of the zirconium-doped nickel-cobalt-manganese, the precipitator solution and the complexing agent solution in a parallel flow manner, and carrying out a coprecipitation reaction to obtain the zirconium-doped nickel-cobalt-manganese hydroxide.
The preparation method provided by the invention is suitable for precursor materials with various nickel contents, such as low nickel, medium nickel or high nickel.
According to the invention, a mode of co-feeding the main element of nickel, cobalt and manganese and the doping element zirconium is adopted, so that redundant working procedures are reduced, the cost is reduced, the content of the zirconium element in the nickel, cobalt and manganese can be effectively stabilized, the original mature coprecipitation working procedure can be adopted, the process improvement is reduced, the cost is reduced, the nickel, cobalt and manganese hydroxide precursor with uniformly distributed zirconium is obtained, and the electrochemical performance of the zirconium-doped nickel, cobalt and manganese anode material is further improved.
In the invention, if the doping element zirconium and the main element of nickel, cobalt and manganese are separately fed, the preparation of a plurality of raw materials can occur, the working procedure redundancy of a feeding pipeline is increased when the coprecipitation is carried out, the doping content of zirconium is continuously monitored in the reaction process, the feeding flow of the zirconium raw material is timely adjusted, and the like.
Preferably, the molar concentration of the mixed salt solution of zirconium-doped nickel cobalt manganese is 1.5-2 mol/L, such as 1.5mol/L, 1.55mol/L, 1.6mol/L, 1.65mol/L, 1.7mol/L, 1.75mol/L, 1.8mol/L, 1.85mol/L, 1.9mol/L, 1.95mol/L or 2mol/L, and the like.
Preferably, the molar concentration of zirconium in the mixed salt solution of zirconium-doped nickel cobalt manganese is 2 to 8mmol/L, such as 2mmol/L, 2.5mmol/L, 3mmol/L, 3.5mmol/L, 4mmol/L, 4.5mmol/L, 5mmol/L, 5.5mmol/L, 6mmol/L, 6.5mmol/L, 7mmol/L, 7.5mmol/L or 8mmol/L, etc.
In the invention, the molar concentration of zirconium in the mixed salt solution of zirconium-doped nickel, cobalt and manganese is too low, the performance of the doped material is not obviously improved, and if the molar concentration is too high, the material cannot play a role in stabilizing the structure in the process of cyclic charge and discharge in the anode material, but the specific discharge capacity of the material is reduced.
Preferably, the precipitant solution comprises a potassium hydroxide solution and/or a sodium hydroxide solution.
Preferably, the complexing agent solution comprises ammonia.
Preferably, the reaction temperature of the coprecipitation reaction is 50 to 60 ℃, for example, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃, or 60 ℃.
Preferably, the pH of the co-precipitation reaction is 10 to 12, such as 10, 10.3, 10.5, 10.8, 11, 11.3, 11.5, 11.8 or 12, and the like.
Preferably, the stirring rate of the coprecipitation reaction is 200 to 400rpm, such as 200rpm, 230rpm, 250rpm, 280rpm, 300rpm, 330rpm, 350rpm, 380rpm, 400rpm, or the like.
Preferably, the coprecipitation reaction is followed by centrifugation, washing and drying in that order.
Preferably, the method of washing comprises washing with water and lye alternately.
Preferably, the drying temperature is 160-210 ℃, such as 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃ or 210 ℃.
In the invention, the drying temperature is too low, which can cause the specific surface area of the precursor to be too small and influence the sintering of the anode material; too high drying temperature can lead to serious oxidation of the precursor, cause unqualified product quality percentage and influence on the sintering of the anode material.
As a preferred technical scheme, the preparation method comprises the following steps:
adding a zirconium-doped nickel-cobalt-manganese mixed salt solution, a potassium hydroxide solution and ammonia water in a concurrent flow manner, carrying out a coprecipitation reaction at a stirring speed of 200-400 rpm and a reaction temperature of 50-60 ℃ in an environment with a pH value of 10-12, centrifuging, alternately washing water and alkali liquor, and drying at 160-210 ℃ to obtain a zirconium-doped nickel-cobalt-manganese hydroxide;
wherein the molar concentration of the mixed salt solution of the zirconium-doped nickel, cobalt and manganese is 1.5-2 mol/L, and the molar concentration of zirconium in the mixed salt solution of the zirconium-doped nickel, cobalt and manganese is 2-8 mmol/L.
In a second aspect, the present invention provides a zirconium-doped nickel cobalt manganese hydroxide, wherein the zirconium-doped nickel cobalt manganese hydroxide is prepared by the preparation method of the zirconium-doped nickel cobalt manganese hydroxide according to the first aspect.
In a third aspect, the invention provides a zirconium-doped nickel-cobalt-manganese positive electrode material, which is obtained by mixing and sintering the zirconium-doped nickel-cobalt-manganese hydroxide according to the second aspect with a lithium source.
In a fourth aspect, the present invention further provides a lithium ion battery, which includes the zirconium-doped nickel-cobalt-manganese positive electrode material according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a mode of co-feeding the main element of nickel, cobalt and manganese and the doping element zirconium is adopted, so that redundant working procedures are reduced, the cost is reduced, the content of the zirconium element in the nickel, cobalt and manganese can be effectively stabilized, the original mature coprecipitation working procedure can be adopted, the process improvement is reduced, the cost is reduced, a nickel, cobalt and manganese hydroxide precursor with uniformly distributed zirconium is obtained, and the electrochemical performance of the zirconium-doped nickel, cobalt and manganese cathode material is further improved.
Drawings
Figure 1 is an XRD pattern of zirconium doped nickel cobalt manganese hydroxide provided in example 1.
Fig. 2 is an SEM image of zirconium doped nickel cobalt manganese hydroxide provided in example 2.
Fig. 3 is an SEM image of zirconium doped nickel cobalt manganese hydroxide provided in example 3.
Fig. 4 is a distribution diagram of the elements of zirconium in the zirconium doped nickel cobalt manganese hydroxide provided in example 3.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This embodiment provides a preparation method of a zirconium-doped nickel-cobalt-manganese hydroxide, where the preparation method includes:
step 1: preparing ternary solution (sulfate) with the molar ratio of Ni to Co to Mn = 0.5;
step 2: respectively controlling the flow rates of the zirconium-doped ternary solution (sulfate), the sodium hydroxide solution and the ammonia water solution to be 32L/h, injecting the zirconium-doped ternary solution (sulfate), the sodium hydroxide solution and the ammonia water solution into a stirrer at 10.1L/h and 2.4L/h, and carrying out coprecipitation reaction at the stirring speed of 380rpm and the temperature of 52 ℃ and with the pH = 11.2-11.4;
and step 3: the slurry after the coprecipitation reaction is thrown into a centrifuge and is washed by hot water and liquid caustic soda;
and 4, step 4: and drying filter residues obtained by centrifugal washing in an oven at 200 ℃ to finally obtain the zirconium-doped nickel-cobalt-manganese hydroxide precursor.
Fig. 1 shows an XRD pattern of the zirconium-doped nickel cobalt manganese hydroxide provided in example 1, and it can be seen from fig. 1 that no peak of oxide appears under the existing reaction process and drying conditions.
Example 2
This embodiment provides a preparation method of a zirconium-doped nickel-cobalt-manganese hydroxide, where the preparation method includes:
step 1: preparing 2mol/L ternary solution (sulfate) with the molar ratio of Ni to Co to Mn = 0.7;
step 2: respectively controlling the flow rates of the zirconium-doped ternary solution (sulfate), the sodium hydroxide solution and the ammonia water solution to be 32L/h,6.3L/h and 0.65L/h, injecting the zirconium-doped ternary solution (sulfate), the sodium hydroxide solution and the ammonia water solution into a stirrer, and carrying out coprecipitation reaction at the stirring speed of 260rpm, the temperature of 58 ℃ and the pH = 10.2-10.4;
and step 3: the slurry after the coprecipitation reaction is thrown into a centrifuge and is washed by hot water and liquid caustic soda;
and 4, step 4: and drying filter residues obtained by centrifugal washing in an oven at 180 ℃ to finally obtain the zirconium-doped nickel-cobalt-manganese hydroxide precursor.
Example 3
This embodiment provides a preparation method of a zirconium-doped nickel-cobalt-manganese hydroxide, where the preparation method includes:
step 1: preparing 1.5mol/L ternary liquid (nitrate) with the molar ratio of Ni to Co to Mn = 0.7;
step 2: respectively controlling the flow rates of the doped zirconium ternary solution (sulfate), the sodium hydroxide solution and the ammonia water solution to be 32L/h, injecting the mixed zirconium ternary solution (sulfate), the sodium hydroxide solution and the ammonia water solution into a stirrer at 10.1L/h and 2.4L/h, and carrying out coprecipitation reaction at the stirring speed of 340rpm, the temperature of 58 ℃ and the pH of = 11.0-11.2;
and 3, step 3: the slurry after the coprecipitation reaction is thrown into a centrifuge and is washed by hot water and liquid caustic soda;
and 4, step 4: and drying filter residues obtained by centrifugal washing in an oven at 160 ℃ to finally obtain the zirconium-doped nickel-cobalt-manganese hydroxide precursor.
Fig. 2 shows an SEM image of the zirconium-doped nickel cobalt manganese hydroxide provided in example 2, fig. 3 shows an SEM image of the zirconium-doped nickel cobalt manganese hydroxide provided in example 3, and it can be seen from fig. 2 and fig. 3 that when the reaction pH is lower, the primary crystal form of the zirconium-doped nickel cobalt manganese hydroxide is coarse, and when the reaction pH is higher, the crystal form thereof can be refined.
Fig. 4 shows the distribution diagram of the elements of zirconium in the zirconium-doped nickel cobalt manganese hydroxide provided in example 3, and it can be seen from fig. 4 that the use of the co-mixed feeding method reduces the complicated processes, and the distribution of zirconium in the nickel cobalt manganese hydroxide is relatively uniform.
Example 4
The difference between the present example and example 1 is that the molar concentration of zirconium in the ternary liquid in step 1 of the present example is 1.5mmol/L.
The remaining preparation methods and parameters were in accordance with example 1.
Example 5
The difference between the present example and example 1 is that the molar concentration of zirconium in the ternary liquid in step 1 of the present example is 9mmol/L.
The remaining preparation methods and parameters were in accordance with example 1.
Example 6
This example differs from example 1 in that the drying temperature in step 4 of this example is 150 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The difference between this example and example 1 is that in step 1 of this example, the Zr element needs to be separately prepared into a 33.53mmol/L solution, and a separate feeding pipe is added for feeding, and the feeding is performed at a ternary liquid feeding rate 6.4 times of the Zr solution feeding rate.
The remaining preparation methods and parameters were in accordance with example 1.
It is understood from the comparison between example 1 and examples 4 and 5 that the mixed salt solution has too low molar concentration of zirconium, and thus the effect of stabilizing the structure of the positive electrode material is not significant, while if the molar concentration of zirconium is too high, the cycle stability of the positive electrode material is reduced, and the positive effect is not achieved.
As can be seen from comparison between example 1 and example 6, the BET of the precursor is too low due to too low temperature during the drying process, which affects the preparation of the positive electrode material.
As can be seen from the comparison between example 1 and comparative example 1, in comparative example 1, the feeding is performed separately, the feeding pipe is added, so that the number of operation steps is increased, and the separate feeding manner is influenced by the preparation result or the operation of the process such as the feeding pump, so that the doping ratio of Zr in the ternary precursor does not reach the target ratio, and thus a series of detection and adjustment are performed, which affects the whole production time.
In conclusion, the method adopts a mode of feeding the main element of nickel, cobalt and manganese and the doping element zirconium together, reduces redundant working procedures and cost, can effectively stabilize the content of the zirconium element in the nickel, cobalt and manganese, can adopt the original mature coprecipitation working procedure, reduces process transformation and cost, obtains the precursor of nickel, cobalt and manganese hydroxide with uniformly distributed zirconium, and further improves the electrochemical performance of the zirconium-doped nickel, cobalt and manganese anode material.
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 zirconium-doped nickel-cobalt-manganese hydroxide is characterized by comprising the following steps:
and adding a zirconium-doped nickel-cobalt-manganese mixed salt solution, a precipitator solution and a complexing agent solution in a parallel flow manner, and performing a coprecipitation reaction to obtain the zirconium-doped nickel-cobalt-manganese hydroxide.
2. The method of claim 1 wherein the mixed salt solution of zirconium-doped nickel cobalt manganese has a molar concentration of 1.5 to 2mol/L.
3. The method of claim 1 or 2, wherein the molar concentration of zirconium in the mixed salt solution of zirconium-doped nickel cobalt manganese is 2 to 8mmol/L.
4. The method of any one of claims 1 to 3 wherein the precipitant solution comprises a potassium hydroxide solution and/or a sodium hydroxide solution;
preferably, the complexing agent solution comprises ammonia.
5. The method of any one of claims 1 to 4, wherein the reaction temperature of the coprecipitation reaction is 50 to 60 ℃;
preferably, the pH value of the coprecipitation reaction is 10-12;
preferably, the stirring rate of the coprecipitation reaction is 200 to 400rpm.
6. The method of any one of claims 1 to 5, wherein the coprecipitation reaction is followed by centrifugation, washing and drying;
preferably, the method of washing comprises washing with water and lye alternately;
preferably, the temperature of the drying is 160 to 210 ℃.
7. The method of preparing zirconium doped nickel cobalt manganese hydroxide according to any one of claims 1 to 6, characterized in that it comprises the following steps:
adding a zirconium-doped nickel-cobalt-manganese mixed salt solution, a potassium hydroxide solution and ammonia water in a concurrent flow manner, carrying out a coprecipitation reaction at a stirring speed of 200-400 rpm and a reaction temperature of 50-60 ℃ in an environment with a pH value of 10-12, centrifuging, alternately washing water and alkali liquor, and drying at 160-210 ℃ to obtain the zirconium-doped nickel-cobalt-manganese hydroxide;
wherein the molar concentration of the mixed salt solution of the zirconium-doped nickel, cobalt and manganese is 1.5-2 mol/L, and the molar concentration of zirconium in the mixed salt solution of the zirconium-doped nickel, cobalt and manganese is 2-8 mmol/L.
8. A zirconium doped nickel cobalt manganese hydroxide prepared by the method of any one of claims 1 to 7.
9. A zirconium-doped nickel-cobalt-manganese cathode material, wherein the zirconium-doped nickel-cobalt-manganese cathode material is obtained by mixing and sintering the zirconium-doped nickel-cobalt-manganese hydroxide according to claim 8 with a lithium source.
10. A lithium ion battery comprising the zirconium-doped nickel cobalt manganese cathode material of claim 9.
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