CN115259239A - Zirconium ion in-situ doped high-nickel ternary precursor, preparation method and application thereof - Google Patents

Zirconium ion in-situ doped high-nickel ternary precursor, preparation method and application thereof Download PDF

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CN115259239A
CN115259239A CN202210721807.9A CN202210721807A CN115259239A CN 115259239 A CN115259239 A CN 115259239A CN 202210721807 A CN202210721807 A CN 202210721807A CN 115259239 A CN115259239 A CN 115259239A
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nickel
zirconium
cobalt
salt
manganese
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伍儒锋
尹俊
秦波
乜雅婧
高志强
李金龙
李森
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Guangdong Jinsheng New Energy Co ltd
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Abstract

The invention discloses a zirconium ion in-situ doped high-nickel ternary precursor, a preparation method and application thereof; belongs to the field of lithium ion battery anode materials; the molar ratio of the amount of the zirconium element doped in the ternary precursor to the total amount of the nickel, cobalt and manganese elements is (0.001-0.005): 1; the preparation method comprises the following steps: 1) Dispersing zirconium salt and nickel-cobalt-manganese transition metal salt in deionized water, and uniformly stirring; 2) Adding an ammonia water solution and a sodium hydroxide solution into the solution obtained in the step 1) during stirring, adjusting the pH of the solution to 11.5, continuing to heat the solution to 40-60 ℃, and then continuing to stir the solution until the reaction is finished; centrifuging, washing and drying by using ethanol and deionized water to obtain a zirconium ion in-situ doped hydroxide precursor; the invention aims to provide a zirconium ion in-situ doped high-nickel ternary precursor with scientific compatibility and good stability, a preparation method and application thereof; the method is used for preparing the high-nickel ternary cathode material.

Description

Zirconium ion in-situ doped high-nickel ternary precursor, preparation method and application thereof
Technical Field
The invention relates to a ternary precursor for a lithium ion battery anode material, in particular to a zirconium ion in-situ doped high-nickel ternary precursor. The invention also relates to a preparation method and application of the ternary precursor.
Background
With the rapid development of the electric vehicle, consumer electronics and power grid industries, there is a need for research and reporting on novel rechargeable energy storage devices with high energy density, high power density and long life. Among the various energy storage devices, lithium ion batteries are considered to be one of the most promising energy storage devices due to their higher energy density. At present, the energy density of the lithium ion battery is mainly limited by the specific discharge capacity and the working potential of the anode material, and in the actual industrial production, the cost of the anode material accounts for more than 30% of the total production cost of the battery. Layered ternary nickel-rich cathode material LiNixCoyMn1-x-yO2The method has the advantages of high energy density, good safety, low production cost and the like, and a great deal of research is carried out.
However, the poor structural stability of the positive electrode material during cycling greatly limits further commercial applications of this material. Moreover, during the heat treatment process, a large amount of lithium ions remained on the surface of the cathode material can cause serious lithium-nickel mixing and formation of an inert layer, and further influence the de-intercalation process of the lithium ions during the charging and discharging processes.
In order to reduce the problem of lithium-nickel mixed-row in the ternary cathode material and further improve the structural stability, bulk phase doping is one of the main methods adopted at present. The principle of bulk phase doping is that metal ions with a radius slightly larger than that of lithium ions are introduced to occupy partial lithium positions, so that the nickel ions do not occupy the lithium positions in the charging and discharging process, and simultaneously, the unit cell parameters and the layer spacing of the anode material are further enlarged, and the structural stability of the material and the diffusion rate of the lithium ions are improved. However, most of the currently used bulk phase doping is to mix a fired cathode material with a doping metal salt and then perform secondary sintering, which not only causes uneven distribution of doping elements, but also causes the cathode material to be affected by water and oxygen during doping process by a complicated process, so as to generate more inorganic inert layers on the surface of the material.
Disclosure of Invention
The first purpose of the present invention is to provide a zirconium ion in-situ doped high-nickel ternary precursor with scientific compatibility and good stability, which is in view of the above disadvantages of the prior art.
The second purpose of the invention is to provide a method for preparing the zirconium ion in-situ doped high-nickel ternary precursor.
The third purpose of the invention is to provide the application of the zirconium ion in-situ doped high-nickel ternary precursor.
The technical scheme of the invention aiming at the first purpose is realized as follows: the zirconium ion in-situ doped high-nickel ternary precursor has the molar ratio of the doped zirconium element to the total amount of nickel, cobalt and manganese elements of 0.001-0.005): 1.
The technical scheme of the invention aiming at the second purpose is realized as follows: a preparation method of the zirconium ion in-situ doped high-nickel ternary precursor comprises the following steps:
1) Dispersing zirconium salt and nickel-cobalt-manganese transition metal salt in deionized water, and continuously stirring for 3-5 h under the condition that the stirring speed is 300-700 r/min; wherein the total concentration of metal ions is 2mol/L; the nickel-cobalt-manganese transition metal salt is manganese salt, nickel salt, cobalt salt and lithium salt;
2) Under the condition that the stirring speed is 300-700 r/min, adding an ammonia water solution and a sodium hydroxide solution into the solution obtained in the step 1), adjusting the pH value of the solution to 11.5, continuing to heat the solution to 40-60 ℃, and then continuing to stir the solution until the reaction is finished; centrifuging, washing and drying by using ethanol and deionized water to obtain a zirconium ion in-situ doped hydroxide precursor; wherein the molar mass of the ammonia water solution is 4mol/L, and the concentration of the sodium hydroxide solution is 3mol/L.
In the above preparation method, the zirconium salt is one or more of zirconium sulfate, zirconium carbonate, zirconium chloride and zirconium acetate.
In the preparation method, the manganese salt is one or more than two of manganese sulfate, manganese chloride, manganese acetate or manganese nitrate.
In the above preparation method, the nickel salt is one or more of nickel sulfate, nickel chloride, nickel acetate or nickel nitrate.
In the above preparation method, the cobalt salt is one or more of cobalt sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
In the above preparation method, the lithium salt is one or more of lithium nitrate, lithium acetate, lithium carbonate, and lithium hydroxide.
In the above preparation method, in the steps 1) to 2), the atmosphere condition at the stirring position is one or more of nitrogen and argon.
By adopting the method, doping modification can be completed in the preparation process of the precursor, so that zirconium ions are distributed in the ternary cathode material more uniformly, the structure of the cathode material is more stable, and the cycle stability of the cathode material is effectively improved. Meanwhile, the in-situ doping method has simple process, is easy to control and is more suitable for industrial large-scale production.
The technical scheme of the invention aiming at the third purpose is realized as follows: the zirconium ion in-situ doped high-nickel ternary precursor is applied to a high-nickel ternary cathode material.
The application comprises the following steps: fully mixing the zirconium ion in-situ doped high-nickel ternary precursor of claim 1 with a lithium source, then putting the mixture into a tubular furnace, heating to 700-760 ℃ in an oxygen atmosphere, and calcining for 10-18 h to obtain a ternary high-nickel positive electrode material; wherein, the ratio of the total molar weight of nickel, cobalt and manganese to the molar weight of lithium is 1.02-1.06.
After the method is adopted, compared with the prior art, the method has the advantages that:
1) The in-situ doped high-nickel ternary cathode material prepared by the invention has the advantages of good structural stability, high specific capacity, long cycle life and the like.
2) The preparation method of the in-situ doped high-nickel ternary cathode material is simple to operate, environment-friendly in process, good in controllability and reproducibility and suitable for large-scale production.
Drawings
The invention will be described in further detail with reference to examples of embodiments shown in the drawings, which should not be construed as limiting the invention in any way.
Fig. 1 is a scanning electron microscope image of an in-situ doped high-nickel ternary cathode material precursor prepared in example 1 of the present invention.
Fig. 2 is an element line scan distribution diagram of the in-situ doped high-nickel ternary cathode material precursor prepared in example 1 of the present invention.
FIG. 3 is a scanning electron microscope image of an in-situ doped high-nickel ternary cathode material prepared in example 1 of the present invention.
Fig. 4 is an elemental line scan distribution diagram of an in-situ doped high-nickel ternary cathode material prepared in example 1 of the present invention.
Fig. 5 is an XRD curve of the in-situ doped high-nickel ternary positive electrode material precursor prepared in example 2 of the present invention.
Fig. 6 is an XRD profile of the in-situ doped high-nickel ternary positive electrode material prepared in example 2 of the present invention.
Fig. 7 is a transmission electron microscope image of the in-situ doped high-nickel ternary cathode material prepared in example 2 of the present invention.
Fig. 8 is a charge-discharge curve diagram of lithium ion Chi Shoujuan made from the in-situ doped high-nickel ternary positive electrode material prepared in embodiment 2 of the present invention.
Fig. 9 is a cycle performance diagram of a lithium ion battery made of the in-situ doped high-nickel ternary cathode material prepared in example 2 according to the present invention at a low current density.
Fig. 10 is a cycle performance diagram of a lithium ion battery made of the in-situ doped high-nickel ternary cathode material prepared in embodiment 3 of the present invention under a large current density.
Detailed Description
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
The zirconium ion in-situ doped high-nickel ternary precursor has the molar ratio of the doped zirconium element to the total amount of nickel, cobalt and manganese elements of 0.001-0.005: 1.
The preparation method comprises the following steps:
1) Dispersing zirconium salt and nickel-cobalt-manganese transition metal salt in deionized water, and continuously stirring for 3-5 h under the condition that the stirring speed is 300-700 r/min; wherein the total concentration of metal ions is 2mol/L.
2) Under the condition that the stirring speed is 300-700 r/min, adding an ammonia water solution and a sodium hydroxide solution into the solution obtained in the step 1), adjusting the pH of the solution to 11.5, continuously heating to 40-60 ℃, and then continuously stirring until the reaction is finished; centrifuging, washing and drying by using ethanol and deionized water to obtain a zirconium ion in-situ doped hydroxide precursor; wherein the molar mass of the ammonia water solution is 4mol/L, and the concentration of the sodium hydroxide solution is 3mol/L.
Preferably, the zirconium salt is one or more of zirconium sulfate, zirconium chloride or zirconium acetate.
The manganese salt is one or more than two of manganese sulfate, manganese chloride, manganese acetate or manganese nitrate.
The nickel salt is one or more than two of nickel sulfate, nickel chloride, nickel acetate or nickel nitrate.
The cobalt salt is one or more than two of cobalt sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
The lithium salt is one or more than two of lithium nitrate, lithium acetate, lithium carbonate or lithium hydroxide.
Further preferably, in the steps 1) to 2), the atmosphere condition at the stirring position is one or more of nitrogen and argon. The manganese salt is one or more than two of manganese nitrate, manganese acetate, manganese chloride or manganese sulfate.
The zirconium ion in-situ doped high-nickel ternary precursor is applied to a high-nickel ternary cathode material. The method specifically comprises the following steps: fully mixing the zirconium ion in-situ doped high-nickel ternary precursor of claim 1 with a lithium source, then putting the mixture into a tubular furnace, heating to 700-760 ℃ in an oxygen atmosphere, and calcining for 10-18 h to obtain a ternary high-nickel positive electrode material; wherein, the ratio of the total molar weight of nickel, cobalt and manganese to the molar weight of lithium is 1.02-1.06.
Zirconium salt is directly dispersed in a nickel-cobalt-manganese raw material salt solution, and then zirconium ions and nickel-cobalt-manganese ions are jointly and uniformly precipitated under an alkaline condition to obtain the zirconium-doped nickel-cobalt-manganese ternary precursor material.
Zirconium ions are doped in a nickel-cobalt-manganese precursor in situ in the coprecipitation process, so that the zirconium ions are more uniformly distributed in the precursor material, and the subsequent ternary cathode material obtained by the existence of the zirconium ions has a more stable structure and more excellent cycle stability. The method is simple and efficient, uses materials and is environment-friendly and suitable for large-scale industrial application.
Example 1
(1) Weighing MnSO according to a molar ratio Zr to M (Ni + Mn + Co) =0.0034·H2O、NiSO4·6H2O and CoSO4·7H2O、Zr(SO4)2·4H2Dispersing O in deionized water under the nitrogen atmosphere, adding 4mol/L ammonia water solution and 3mol/L NaOH solution after completely dispersing, adjusting the pH to 11.5, heating to 60 ℃, and fully stirring for 4 hours under the condition of 500r/min until the reaction is finished. Respectively suction-filtering and washing with ethanol and deionized water for 2 times, filtering and washing with deionized waterDrying in a vacuum oven at 100 ℃ for 12h to obtain the zirconium ion in-situ doped high-nickel ternary positive electrode precursor material Ni0.92Co0.039Mn0.038Zr0.003(OH)2. Weighing 2g of Ni according to the mass ratio of 10.92Co0.039Mn0.038Zr0.003(OH)2Precursor and 0.9944g of analytically pure LiOH. H2And fully grinding the mixture in a mortar to obtain mixture powder.
(2) Putting the powder obtained in the step 1 into a tubular furnace for heat treatment, heating to 720 ℃ at a speed of 2 ℃/min in an oxygen atmosphere, preserving heat for 18h, and cooling along with the furnace to obtain a high-nickel ternary cathode material LiNi with fine granularity0.92Co0.039Mn0.038Zr0.003O2。
Fig. 1 is a scanning electron microscope image of the in-situ doped high-nickel ternary positive electrode precursor material in the embodiment, and as shown in the figure, the prepared precursor material grows uniformly and is spherical particles with the particle size of about 15-20 μm. FIG. 2 is the element line scanning distribution diagram of the cross section, and as shown in the figure, mn, ni, co, zr and O elements are uniformly distributed. Fig. 3 is the in-situ doped high-nickel ternary cathode material in the present embodiment, and it is seen from the figure that the obtained layered oxide is a secondary particle formed by sintering and agglomerating primary particles, and the perfect spherical morphology is retained. Fig. 4 is a line-scanning distribution diagram of elements in the cross section, and it can be seen that the distribution of each element in the sintered positive electrode material is still uniform.
Example 2
(1) Weighing MnCl according to a molar ratio Zr to M (Ni + Mn + Co) =0.0012·6H2O、NiCl2·6H2O and CoCl2·6H2O、ZrCl4Dispersing in deionized water under air atmosphere, adding 5mol/L ammonia water solution and 2mol/L NaOH solution after completely dispersing, adjusting pH to 11.5, heating to 40 ℃, and fully stirring for 5h under the condition of 300r/min until the reaction is completed. Washing and centrifuging for 2 times by using ethanol and deionized water respectively, and drying in a vacuum oven at 100 ℃ for 10h to obtain the zirconium ion in-situ doped high-nickel ternary positive electrode precursor material Ni0.92Co0.039Mn0.038Zr0.001(OH)2. Weighing 2g of Ni according to the mass ratio of 10.92Co0.039Mn0.038Zr0.001(OH)2Precursor and 0.9569g of analytically pure LiOH. H2And fully grinding the mixture in a mortar to obtain mixture powder.
(2) Putting the powder obtained in the step 1 into a crucible for heat treatment, heating to 720 ℃ at a speed of 2 ℃/min in an oxygen atmosphere, preserving heat for 18h, and cooling along with the furnace to obtain a high-nickel ternary cathode material LiNi with fine granularity0.92Co0.039Mn0.038Zr0.001O2。
The in-situ doped high-nickel ternary precursor material of the present embodiment and the cathode material prepared by sintering are subjected to X-ray diffraction tests, and XRD curves thereof are shown in fig. 5 and 6, respectively. The analysis shows that the main phase of the precursor material is Ni (OH)2(14-0117), the splitting of each diffraction peak is good and sharp, which indicates that the obtained precursor material has good crystallinity. As shown in FIG. 6, zrO appeared in the in-situ doped positive electrode material2Indicates that the doped form of Zr ions is a metal oxide, and I thereof(003)/I(104)The value is larger, which indicates that the layered structure of the doped material is more stable. As shown in fig. 7, which is a transmission electron microscope image of the in-situ doped high-nickel ternary cathode material prepared in this embodiment, it is seen from the image that the obtained ternary cathode material has better crystallinity, and no redundant inert layer is on the surface; meanwhile, the (101) interplanar spacing is 0.255nm, which is slightly larger than the theoretical value (0.245 nm), thus indicating Zr2+The introduction of the lithium ion battery enlarges the interlayer spacing of the cathode material, and can promote the extraction of lithium ions in the charge and discharge process.
The in-situ doped high-nickel ternary precursor material of the embodiment is prepared into a lithium ion battery to perform electrochemical performance test, and the first charge-discharge curve of the lithium ion battery is shown in fig. 8. From the figure, it can be seen that the first coulombic efficiency of the doped high-nickel ternary cathode material at 0.5C is high (88.0%) and the first irreversible capacity is low (27.72 mAh/g). Fig. 9 shows the cycle performance of the cathode material, and as shown in the figure, after 60 cycles at 1C, the first discharge specific capacity of the material is 170.30mAh/g, the capacity retention rate is 93.6%, the cycle stability of the material is good, which indicates that the introduction of zirconium ions improves the structural stability of the material.
Example 3
(1) Weighing MnCl according to a molar ratio Zr to M (Ni + Mn + Co) =0.0052·6H2O、NiSO4·6H2O and CoSO4·7H2O、Zr(SO4)2·4H2Dispersing O in deionized water under the nitrogen atmosphere, adding 6mol/L ammonia water solution and 4mol/L NaOH solution after completely dispersing, adjusting the pH to 11.5, heating to 50 ℃, and fully stirring for 3h under the condition of 700r/min until the reaction is completed. Respectively filtering and washing the mixture for 2 times by using ethanol and deionized water, and drying the mixture for 24 hours in a vacuum oven at the temperature of 90 ℃ to obtain the zirconium ion in-situ doped high-nickel ternary positive electrode precursor material Ni0.92Co0.039Mn0.038Zr0.005(OH)2. Weighing 2g of Ni according to the mass ratio of 10.92Co0.039Mn0.038Zr0.005(OH)2Precursor and 0.9756g of analytically pure LiOH. H2And fully grinding the mixture in a mortar to obtain mixture powder.
(2) Putting the powder obtained in the step 1 into a tubular furnace for heat treatment, heating to 700 ℃ at a speed of 2 ℃/min in an oxygen atmosphere, preserving heat for 10 hours, and cooling along with the furnace to obtain a high-nickel ternary cathode material LiNi with fine granularity0.92Co0.039Mn0.038Zr0.005O2。
The in-situ doped high-nickel ternary cathode material of the embodiment is prepared into a lithium ion battery for performance test, the cycle performance under high current density (2C) is shown in fig. 10, the cycle performance under 2C is 100 circles, the first discharge specific capacity of the material is 139.30mAh/g, the capacity retention rate is 96.3%, the cycle stability of the material is good, and the introduction of zirconium ions improves the structural stability of the material.
The above-mentioned embodiments are only for convenience of description, and are not intended to limit the present invention in any way, and those skilled in the art will understand that the technical features of the present invention can be modified or changed by other equivalent embodiments without departing from the scope of the present invention.

Claims (10)

1. The zirconium ion in-situ doped high-nickel ternary precursor is characterized in that the molar ratio of the doped zirconium element to the total amount of nickel, cobalt and manganese elements is (0.001-0.005): 1.
2. The preparation method of the zirconium ion in-situ doped high-nickel ternary precursor according to claim 1, characterized by comprising the following steps:
1) Dispersing zirconium salt and nickel-cobalt-manganese transition metal salt in deionized water, and continuously stirring for 3-5 h under the condition that the stirring speed is 300-700 r/min; wherein the total concentration of metal ions is 1-3 mol/L; the nickel-cobalt-manganese transition metal salt is manganese salt, nickel salt, cobalt salt and lithium salt;
2) Under the condition that the stirring speed is 300-700 r/min, adding an ammonia water solution and a sodium hydroxide solution into the solution obtained in the step 1), adjusting the pH value of the solution to 11.5, continuing to heat the solution to 40-60 ℃, and then continuing to stir the solution until the reaction is finished; washing and drying by using ethanol and deionized water to obtain a hydroxide precursor in-situ doped with zirconium ions; wherein the molar mass of the ammonia water solution is 4-6 mol/L, and the concentration of the sodium hydroxide solution is 2-4 mol/L.
3. The method of claim 2, wherein: the zirconium salt is one or more of zirconium sulfate, zirconium carbonate, zirconium chloride or zirconium acetate.
4. The method of claim 2, wherein: the manganese salt is one or more than two of manganese sulfate, manganese chloride, manganese acetate or manganese nitrate.
5. The method of claim 2, wherein: the nickel salt is one or more of nickel sulfate, nickel chloride, nickel acetate or nickel nitrate.
6. The method of claim 2, wherein: the cobalt salt is one or more than two of cobalt sulfate, cobalt chloride, cobalt acetate or cobalt nitrate.
7. The method of claim 2, wherein: the lithium salt is one or more than two of lithium nitrate, lithium acetate, lithium carbonate or lithium hydroxide.
8. The method of claim 2, wherein: in the steps 1) to 2), the atmosphere condition of the stirring part is one or more of nitrogen and argon.
9. The use of the zirconium ion in-situ doped high-nickel ternary precursor of claim 1 in a high-nickel ternary cathode material.
10. Use according to claim 9, characterized in that it comprises the following steps: fully mixing the zirconium ion in-situ doped high-nickel ternary precursor and a lithium source, then putting the mixture into a tubular furnace, heating to 700-760 ℃ at the speed of 2 ℃/min in an oxygen atmosphere, and preserving the temperature for 10-18 h to obtain a ternary high-nickel anode material; wherein, the ratio of the total molar weight of nickel, cobalt and manganese to the molar weight of lithium is 1.02-1.06.
CN202210721807.9A 2022-06-24 2022-06-24 Zirconium ion in-situ doped high-nickel ternary precursor, preparation method and application thereof Pending CN115259239A (en)

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