CN112670506B - Nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by fast ion conductor and preparation method thereof - Google Patents
Nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by fast ion conductor and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by a fast ion conductor and a preparation method thereof, wherein the preparation method comprises the following steps: s1, taking lithium salt and tantalum salt for pulverization treatment, and then mixing with a precursor of the nickel-cobalt-manganese ternary positive electrode material to obtain a homogeneous mixture; s2, performing sectional calcination on the homogeneous mixture, firstly calcining at the temperature of 450-550 ℃, then calcining at the temperature of 680-780 ℃, and cooling along with the furnace to obtain the catalyst. The surface of the nickel-cobalt-manganese-tantalum composite quaternary positive electrode material prepared by the invention is coated with LiTaO with a certain thickness3The preparation method can help the high nickel material to realize rapid lithium ion de-intercalation in the charging and discharging processes, and keep the structure stable, so that the high nickel material shows good rate performance and cycling stability, and the defects of the traditional ion doping and solid phase mixed coating method are overcome.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by a fast ionic conductor and a preparation method thereof.
Background
In recent years, with the continuous development of clean energy, lithium ion batteries have been gradually used in the field of electric vehicles as novel secondary energy devices, but the existing lithium ion batteries still cannot meet the requirement of long endurance mileage of electric vehicles. As an important device for limiting the energy density of lithium ion batteries, the development of high-performance cathode materials is still crucial. Among the numerous positive electrode materials, the high nickel type positive electrode material LiTMO2(0.5<Ni<1, TM ═ Ni, Co, Mn, Ti, etc.) has received much attention because of its advantages such as high energy density, low cost, and environmental friendliness.
However, although the high-nickel type cathode material can provide a considerable specific discharge capacity, the material still has serious problems at present, for example, as the content of nickel increases, the cycling stability and rate capability of the material become worse, and the cycle life and power density of the corresponding lithium ion battery decrease. Therefore, it is important to improve the cycle stability and rate capability of the high nickel type cathode material.
At present, the most common methods for improving the performance of the high-nickel type cathode material comprise surface coating, ion doping and special structure design, but each of the methods has certain defects: 1) the surface coating process needs post-treatment, which increases the operation cost; 2) the ion doping can cause the surface of the high-nickel type anode material to form a impure phase, and the specific discharge capacity of the material is influenced; 3) the special structure needs to precisely regulate and control synthesis parameters, and influences the consistency and yield of final products. Therefore, it is very important to develop a high-performance and easily-prepared high-nickel type cathode material.
Chinese patent CN110993903A discloses a tantalum modified high nickel positive electrode material, and a preparation method and application thereof, and the technical scheme thereof is substantially (embodiment 1): putting LiOH into a mortar, adding ethanol for wet grinding, and then adding a precursor of a high-nickel anode material and Ta2O5Grinding until alcohol is evaporated to dryness to obtain solid powder; performing segmented calcination on the solid powder in an oxygen atmosphere, calcining for 5H at 500 ℃, then heating to 720 ℃ and calcining for 15H, wherein the heating rate is 2 ℃/min, the cooling rate is 5 ℃/min, and thus obtaining the Ta-modified high-nickel cathode material, wherein LiOH & H & lt/EN & gt2The molar ratio of O to the high-nickel precursor powder is 1.02:1, and the impurity content of Ta is 0.1-2%. The patent technology is characterized in that a precursor of a high-nickel anode material is mixed with Ta2O5And mixing with lithium hydroxide, calcining at high temperature, and doping Ta into the surface layer structure of the high-nickel material to realize Ta doping, wherein the Ta doping can stabilize the structure of the high-nickel anode material and widen a lithium ion channel, so that the electrochemical performance of the material is improved, and particularly, the cycle performance of the material can be improved.
By analyzing the technical principle of the patent technology, the following can be obtained: the patent technology is that tantalum pentoxide, a high-nickel precursor and LiOH are mixed according to a certain molar ratio and then directly sintered at high temperature, and Ta at high temperature is utilized2O5Into the high nickel precursor surface, causing the precursor material to undergo a lithiation process (i.e., from Ni)xCo1-x(OH)2To LiNixCo1-xO2A process for converting a hydroxide precursor to a finished oxide containing lithium) there is not only the incorporation of lithium but also the incorporation of tantalum. After the lithiation process is finished, certain lattice doping of tantalum elements exists on the surface of the finished product material, and surface doping is achieved. However, because of the high decomposition temperature of tantalum pentoxide, only a small amount of tantalum salt can enter the surface of the material, and if the addition amount of tantalum salt is too large, part of electrochemically inactive tantalum pentoxide can adhere to the surface of the material, thereby affecting the electrochemical performance. Meanwhile, the technology of the patent belongs to the surface doping technology, and the technology still exists to be highThe surface of the nickel anode material forms a mixed phase, which influences the discharge specific capacity of the material.
Disclosure of Invention
The invention aims to: aiming at the existing problems, the invention provides a nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by a fast ion conductor and a preparation method thereof, wherein the ratio of lithium salt to tantalum salt is far higher than the normal ratio, then the preparation processes of pulverization, low-temperature melting and the like are combined, a tantalum compound is added in the lithiation process as a tantalum source, and by utilizing the ion diffusion in the high-temperature sintering process and the mutual reaction between the lithium source and the tantalum salt, Ta element can be uniformly distributed in the high-nickel material body, and the Ta element staying on the surface of the high-nickel positive electrode material can consolidate and regenerate fast ion conductor lithium tantalate and be coated on the surface of the material as a coating layer, so that the fast lithium ion deintercalation of the high-nickel material can be realized in the charging and discharging processes, the multiplying power performance of the material can be improved, the interlayer spacing of the material can be widened by matching with tantalum doping, the material structure can be stabilized, and the multiplying power performance can be improved, the material shows good rate performance and cycling stability, and overcomes the defects of the traditional ion doping and solid phase mixed coating method.
The technical scheme adopted by the invention is as follows: a preparation method of a nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by a fast ion conductor is characterized by comprising the following steps of:
s1, taking lithium salt and tantalum salt for pulverization treatment, and then mixing a precursor of the nickel-cobalt-manganese ternary positive electrode material, wherein the ratio of Li: the molar ratio of (Ni + Co + Mn + Ta) is 1.1-1.3: 1, obtaining a homogeneous mixture;
s2, performing sectional calcination on the homogeneous mixture, firstly calcining at 550 ℃ of 450-. The calcination atmosphere is air or oxygen, and preferably oxygen.
In the tantalum modified high nickel cathode material and the preparation method thereof mentioned in the background art, the mentioned molar ratio comprises two parts:
(1) the ratio of the high nickel precursor to the lithium salt, which is a molar ratio, is mainly aimed at ensuring that the precursor material has a sufficient but not excessive lithium source during the lithiation process, thereby obtaining a material with better performance, i.e. a precursor in the patent technology: LiOH ═ 1-1.1: 1, which is a conventional practice, theoretically the ratio should be 1:1 (i.e. Ni)xCo1-x(OH)2To LiNixCo1-xO2In the ideal case, the molar ratio between precursor and lithium is 1: 1) the redundant lithium salt is used for compensating the volatilization and loss of lithium in the high-temperature sintering process;
(2) the ratio of high nickel precursor and tantalum salt, i.e. the precursors claimed in the patent: ta2O5The value of the ratio is 0.2-3% by mass, and the value represents that the method of the inventor aims to explore the influence of different amounts of tantalum salt doping on the performance of the material and reflects that the patent aims to obtain a tantalum-doped high-nickel material.
The above two ratios can be converted by the following method: taking 1mol of NixCo1-x(OH)2Material, corresponding to the molar weight of lithium salt being 1-1.1 mol; and the molar weight of the tantalum salt is 1M (Ni)xCo1-x(OH)2)*(0.002-0.03)/M(Ta2O5). Where M represents the relative molecular mass of the substance in the subscript brackets, since the relative molecular masses of nickel and cobalt are very close (M (ni) ═ 58.69, M (co) ═ 58.93), and this patent is directed to high nickel type materials and the example is NC91, ni (oh) can be taken2As NixCo1-x(OH)2Relative molecular mass of the material, namely 92.69, and Ta2O5Has a relative molecular mass of 441.89, so the molar mass of the tantalum salt is 1 × 92.69 (0.002-0.03)/441.89 ═ 4.2 × 10-4-6.3x10-3And (mol). Therefore, the molar ratio of the three components is 1-1.1: 1: 4.2X10-4-6.3x10-3。
In the invention, the molar ratio adopted by the invention is as follows: li: (Ni + Co + Mn + Ta) 1.1 to 1.3: 1, the ratio of lithium salt and tantalum salt is much higher than that of the prior art, which results in substantial difference between the invention idea and the technical principle of the patent technology, and the technical principle of the invention is as follows: according to the method, the lithium salt and the tantalum salt are subjected to powdering operation and low-temperature melting operation, so that the lithium salt and the tantalum salt can be fully mixed and then sintered at high temperature, the lithium salt and the tantalum salt can be synchronously decomposed by high-temperature sintering, and the Ta element doping of the precursor material can be simultaneously realized in the lithiation process. Furthermore, excessive lithium ions and tantalum ions can react again in the cooling process to generate lithium tantalate which is uniformly attached to the surface of the material, the property of the newly generated lithium tantalate is different from that of the tantalum salt added in the early stage, the particle size is smaller, and the newly generated lithium tantalate can be closely attached to the surface of the lithium nickel cobalt manganese tantalum quaternary material to play a role in physical isolation and fast ion conductor.
Therefore, the lithium salt and the tantalum salt are fully mixed through the pulverization operation and the low-temperature melting, then the decomposition of the lithium salt and the tantalum salt is synchronously realized through the high-temperature sintering, further, the doping of the Ta element is simultaneously realized in the lithiation process of the precursor material, a large amount of excessive lithium ions and tantalum ions react again in the cooling process to generate lithium tantalate which is uniformly attached to the surface of the material, and the electrode material is protected from being corroded by electrolyte, which cannot be realized by the traditional solid-phase coating and ion doping method. The preparation method provided by the invention can help the high-nickel material realize rapid lithium ion deintercalation in the charging and discharging processes, improve the rate capability of the material, and combine with the effects of tantalum doping, widening the interlayer spacing of the material, stabilizing the material structure and improving the rate capability, so that the high-nickel material shows good rate capability and cycling stability, and the defects of the traditional ion doping and solid phase mixed coating method are overcome.
The nickel-cobalt-manganese ternary positive electrode material precursor is prepared by a hydroxide coprecipitation method, the shape of the nickel-cobalt-manganese ternary positive electrode material precursor is spherical, the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary positive electrode material precursor is x: y: z, wherein x is more than 0.5 and less than 1, y is more than 0 and less than 0.5, z is more than 0 and less than 0.5, and x + y + z is 1.
Further, the lithium salt is LiOH or Li2CO3And LiNO3Preferably LiOH.
Further, the tantalum salt is Ta2O5、TaB、LiTaO3And NaTaO3Preferably LiTaO, preferably3。
Preferably, the precursor composition of the nickel-cobalt-manganese ternary cathode material is Ni0.80Co0.10Mn0.10(OH)2。
Preferably, Li: the molar ratio (Ni + Co + Mn + Ta) was 1.2: 1.
preferably, the first-stage calcination temperature is 500-550 ℃, the calcination time is 240-260min, the second-stage calcination temperature is 750-780 ℃, and the calcination time is 600-660 min.
The invention also comprises a nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by the fast ion conductor, wherein the nickel-cobalt-manganese-tantalum composite quaternary positive electrode material is prepared by the preparation method, and the chemical composition of the nickel-cobalt-manganese-tantalum composite quaternary positive electrode material is Li (Ni)xCoyMnzTah)O2Wherein 0.5<x<1，0<y<0.5，0<z<0.5，0<h<0.5, x + y + z + h is 1, and the surface of the alloy is coated with LiTaO with a certain thickness3The positive electrode material has uniform particle size distribution, high discharge specific capacity and excellent cycle performance and multiplying power performance.
The invention also comprises a lithium ion battery which is prepared by adopting the nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by the fast ion conductor.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. according to the invention, the three are fully mixed through pulverization operation and low-temperature melting, then the decomposition of lithium salt and tantalum salt is synchronously realized through high-temperature sintering, tantalum ions and lithium ions can automatically diffuse into a layered structure to form a nickel-cobalt-manganese-tantalum quaternary positive electrode material, so that the doping of Ta element is simultaneously realized in the lithiation process of a precursor material, and a large amount of excessive lithium ions and tantalum ions are re-reacted under the action of certain oxygen partial pressure in the cooling process to generate lithium tantalate which is uniformly attached to the surface of the material to protect the electrode material from being corroded by electrolyte, which cannot be realized by the traditional solid-phase coating and ion doping method;
2. the surface of the nickel-cobalt-manganese-tantalum composite quaternary positive electrode material prepared by the invention is coated with LiTaO with a certain thickness3The positive electrode material has uniform particle size distribution, high discharge specific capacity and excellent cycle performance and multiplying power performance;
3. the preparation method provided by the invention can help the high-nickel material realize rapid lithium ion deintercalation in the charging and discharging processes, improve the rate capability of the material, and combine with the effects of tantalum doping, widening the interlayer spacing of the material, stabilizing the material structure and improving the rate capability, so that the high-nickel material shows good rate capability and cycling stability, and the defects of the traditional ion doping and solid phase mixed coating method are overcome.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the final product prepared in example 1;
FIG. 2 is a Transmission Electron Microscope (TEM) image of the final product prepared in example 1;
FIG. 3 is an SEM photograph of the final product prepared in example 2;
FIG. 4 is a TEM image of the final product prepared in example 2;
FIG. 5 is a 1C rate cycle plot at 2.75-4.3V for the assembled cells of examples 1 and 2;
fig. 6 is a graph of different rate capacities at 2.75-4.3V for the assembled batteries of examples 1 and 2.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Additionally, the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the following examples, the material characterization analysis methods used were as follows:
scanning Electron Microscope (SEM) testing: scanning electron microscope, instrument model: FEI Quanta, the netherlands.
Transmission Electron Microscope (TEM) testing: transmission electron microscope, instrument type: JEOL JEM-2100, Japan.
Inductively coupled plasma atomic emission spectroscopy (ICP-AES) test: inductively coupled plasma spectrometer (ICP emission spectrometer), instrument model: agilent ICPOES730, Agilent usa.
Assembly and testing of CR2025 button cells: a nickel-cobalt-manganese-tantalum quaternary positive electrode material (a final product prepared in an example), acetylene black and polyvinylidene fluoride (PVDF) dissolved in N-methylpyrrolidone (NMP) are prepared into slurry according to the mass ratio of the positive electrode material to the acetylene black to the PVDF of 8:1:1 and coated on an aluminum foil, after drying, the aluminum foil loaded with an active substance is cut into small round pieces with the diameter of 11mm by a cutting machine and used as a positive electrode, a metal lithium piece is used as a negative electrode, U.S. Celgard2500 is used as a diaphragm, a 1M carbonic ester solution is used as an electrolyte (wherein, a solvent is a mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1:1, and a solute is LiPF6), and the small round piece is assembled into a CR2025 button cell in an argon glove box.
The assembled CR2025 button cell is subjected to constant-current charge and discharge tests under different current densities by adopting a CT2001A LAND cell tester, wherein the current density of 1C is defined to be 200mA/g, the charge and discharge voltage interval is 2.75V-4.3V, and the test temperature is 25 ℃.
Example 1
A preparation method of a nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by a fast ion conductor comprises the following steps:
s1, weighing NiSO according to the molar ratio of Ni to Co to Mn of 8 to 14·6H2O、CoSO4·7H2O and MnSO4·H2Preparing a mixed metal salt solution with the total concentration of transition metal ions being 2mol/L by using 100mL of deionized water, and preparing a mixed alkali solution with the concentration of NaOH being 2mol/L by using 200mL of deionized water and NaOH and ammonia water according to the molar ratio of 1: 2;
s2, adding 50mL of deionized water into a continuous stirred tank reactor to serve as reaction base liquid, dropwise adding ammonia water to adjust the pH of the reaction base liquid to be about 11, introducing argon gas to serve as protective gas, setting the stirring speed to be 600r/min, setting the reaction temperature to be 55 ℃, and simultaneously injecting a metal salt solution and alkali liquor;
s3, after the reaction is finished, filtering the obtained precipitate, washing and carrying out vacuum drying to obtain the precursor of the nickel-cobalt-manganese ternary positive electrode material, wherein the molecular formula is Ni0.8Co0.1Mn0.1(OH)2；
S4, weighing 1g of Ni of nickel-cobalt-manganese ternary positive electrode material precursor0.8Co0.1Mn0.1(OH)2According to Li: (Ni + Co + Mn): ta 1.2: 1: weighing LiOH and LiTaO at a ratio of 0.013Mixing LiOH and LiTaO3Placing the mixture into a mortar for forcefully grinding for 5min, then adding a nickel-cobalt-manganese ternary positive electrode material precursor, stirring the three substances to uniformly mix, adding absolute ethyl alcohol or deionized water serving as a dispersing agent to enhance the mixing effect, and performing vacuum drying for 2h at the temperature of 60 ℃ after the mixing is finished;
s5, placing the dried mixed material into a tube furnace, calcining the mixed material in an oxygen atmosphere at 550 ℃ for 300min, then calcining the mixed material at 750 ℃ for 600min, and cooling the calcined material to obtain the nickel-cobalt-manganese-tantalum quaternary anode material with the surface coated by lithium tantalate, wherein the obtained material is marked as LTO-1.
The ICP-AES test result shows that the element component is Li1.052Ni0.788Co0.100Mn0.101Ta0.011O2.16The material is not a pure-phase nickel-cobalt-manganese-tantalum quaternary positive electrode material.
The SEM result of the final product prepared in S5 is shown in fig. 1, and it can be seen from the figure that the final product is spherical secondary particles in which the primary particles are closely composed, and no significant impurity phase exists on the surface.
The TEM result of the final product is shown in FIG. 2, and it can be seen that a uniform nano-scale coating layer exists outside the final product, which proves that the surface of the material is successfully coated with lithium tantalate.
The results of the charge-discharge cycle curves of the assembled battery at 2.75-4.3V, 0.2C rate are shown in FIG. 5, and the analysis results are shown in Table 1.
The results of the charge-discharge cycle curves of the assembled battery of the final product at 2.75-4.3V and different multiplying factors are shown in FIG. 6, and the analysis results are shown in Table 2.
Example 2
A preparation method of a nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by a fast ion conductor comprises the following steps:
s1, weighing NiSO according to the molar ratio of Ni to Co to Mn of 80 to 104·6H2O、CoSO4·7H2O and MnSO4·H2Preparing a mixed metal salt solution with the total concentration of transition metal ions being 2mol/L by using 100mL of deionized water, and preparing a mixed alkali solution with the concentration of NaOH being 2mol/L by using 200mL of deionized water and NaOH and ammonia water according to the molar ratio of 1: 2;
s2, adding 50mL of deionized water into the continuous stirred tank reactor to serve as reaction base liquid, dropwise adding ammonia water to adjust the pH of the reaction base liquid to be about 11, introducing argon gas to serve as protective gas, setting the stirring speed to be 650r/min, setting the reaction temperature to be 55 ℃, and simultaneously injecting a metal salt solution and alkali liquor;
s3, after the reaction is finished, filtering the obtained precipitate, washing and carrying out vacuum drying to obtain the precursor of the nickel-cobalt-manganese ternary positive electrode material, wherein the molecular formula is Ni0.80Co0.10Mn0.10(OH)2；
S4, weighing 1g of Ni of nickel-cobalt-manganese ternary positive electrode material precursor0.80Co0.10Mn0.10(OH)2According to Li: (Ni + Co + Mn): ta 1.1: 1: weighing LiOH and LiTaO at a ratio of 0.023Mixing LiOH and LiTaO3Placing the mixture into a mortar for forcefully grinding for 5min, then adding a nickel-cobalt-manganese ternary positive electrode material precursor, stirring the three substances to uniformly mix, adding absolute ethyl alcohol or deionized water serving as a dispersing agent to enhance the mixing effect, and performing vacuum drying for 2h at the temperature of 60 ℃ after the mixing is finished;
and S5, placing the dried mixed material into a tube furnace, calcining the mixed material in an oxygen atmosphere at 500 ℃ for 300min, calcining the calcined material at 780 ℃ for 600min, and cooling the calcined material to obtain the nickel-cobalt-manganese-tantalum quaternary anode material with the surface coated by lithium tantalate, wherein the obtained material is marked as LTO-2.
The ICP-AES test result shows that the element component is Li1.012Ni0.778Co0.110Mn0.101Ta0.021O2.13The material is not a pure-phase nickel-cobalt-manganese-tantalum quaternary positive electrode material.
The SEM result of the final product prepared in S5 is shown in fig. 3, from which it can be seen that the final product is spherical secondary particles having a compact composition of primary particles, and no significant impurity phase exists on the surface.
The TEM result of the final product is shown in FIG. 4, and it can be seen that a uniform nano-scale coating layer exists outside the final product, which proves that the surface of the material is successfully coated with lithium tantalate.
The results of the charge-discharge cycle curves of the assembled battery at 2.75-4.3V, 1C rate are shown in FIG. 5, and the analysis results are shown in Table 1.
The results of the charge-discharge cycle curves of the assembled battery of the final product at 2.75-4.3V and different multiplying factors are shown in FIG. 6, and the analysis results are shown in Table 2.
TABLE 1 test results of charge-discharge cycle performance
Fig. 5 is a graph of the 1C rate cycle at 2.75-4.3V for the assembled batteries of examples 1 and 2, with the cycle number on the abscissa, specific discharge capacity on the ordinate, and electrochemical performance results for the different materials shown in table 1. As the nickel content of the final product of the embodiment is reduced along with the increase of the addition amount of the tantalum salt, the first-cycle specific discharge capacity of the material is reduced to a certain extent through graphical analysis, but due to the existence of the lithium tantalate coating layer, the first-cycle coulombic efficiency of the material and the capacity retention rate after 100 cycles are improved.
Fig. 6 is a graph of the assembled batteries of examples 1 and 2 tested at different rates of 2.75-4.3V, the abscissa is cycle number, the ordinate is specific discharge capacity, and the electrochemical performance results of different materials are shown in table 2. After comparison, the discharge specific capacities of the lithium tantalate coated nickel-cobalt-manganese-tantalum quaternary positive electrode material under low rate and high rate are similar, so that the material is proved to have ideal large-current charge-discharge and small-current charge-discharge performance, and the power density of the electric automobile is improved. The comprehensive electrochemical performance comparison can be concluded that the nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by the lithium tantalate prepared by the method has high cycle stability and excellent rate performance.
Table 2 test results of charge-discharge cycle performance under different multiplying power
The test results of the embodiment show that the material is a nickel-cobalt-manganese-tantalum quaternary positive electrode material with the surface coated with lithium tantalate, the thickness of the coating layer on the surface of the material can be obviously changed by changing the addition amount of the tantalum salt in the preparation process, and meanwhile, the final product material shows good cycle stability and rate capability, and can be used as a promising positive electrode material of a lithium ion battery for an electric vehicle. The raw materials used in the method disclosed by the invention are low in cost, non-toxic and environment-friendly, secondary sintering operation is not required in the preparation process, the whole process flow is simple, efficient and environment-friendly, the experimental conditions are wide, the reliability is high, and the method has a good industrial application prospect.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A preparation method of a nickel-cobalt-manganese-tantalum composite quaternary positive electrode material coated by a fast ion conductor is characterized by comprising the following steps of:
s1, taking lithium salt and tantalum salt for pulverization treatment, and then mixing a precursor of the nickel-cobalt-manganese ternary positive electrode material, wherein the ratio of Li: (Ni + Co + Mn): molar ratio of Ta 1.2: 1: 0.01 or 1.1: 1: 0.02, obtaining a homogeneous mixture;
s2, performing sectional calcination on the homogeneous mixture, firstly calcining at 550 ℃ of 450-.
2. The method for preparing the fast ionic conductor coated nickel-cobalt-manganese-tantalum composite quaternary positive electrode material as claimed in claim 1, wherein the nickel-cobalt-manganese ternary positive electrode material precursor is prepared by a hydroxide coprecipitation method, the shape of the nickel-cobalt-manganese ternary positive electrode material precursor is spherical, and the molar ratio of nickel, cobalt and manganese in the nickel-cobalt-manganese ternary positive electrode material precursor is x: y: z, wherein x is more than 0.5 and less than 1, y is more than 0 and less than 0.5, z is more than 0.5, and x + y + z = 1.
3. The method of claim 2, wherein the lithium salt is LiOH or Li2CO3And LiNO3One or more of (a).
4. The method of claim 3, wherein the tantalum salt is Ta2O5、TaB、LiTaO3And NaTaO3One or more of (a).
5. The method for preparing the fast ionic conductor coated nickel-cobalt-manganese-tantalum composite quaternary positive electrode material as claimed in claim 3, wherein the precursor composition of the nickel-cobalt-manganese ternary positive electrode material is Ni0.80Co0.10Mn0.10(OH)2。
6. The method of claim 3, wherein the lithium salt is LiOH and the tantalum salt is LiTaO3。
7. The method as claimed in claim 1, wherein the first-stage calcination temperature is 500-550 ℃, the calcination time is 240-260min, the second-stage calcination temperature is 750-780 ℃, and the calcination time is 600-660 min.
8. A fast ion conductor coated nickel-cobalt-manganese-tantalum composite quaternary positive electrode material, which is prepared by the preparation method of any one of claims 1 to 7, and has a chemical composition of Li (Ni)xCoyMnzTah)O2Wherein 0.5<x<1，0<y<0.5，0<z<0.5，0<h<0.5, x + y + z + h =1, the surface of which is coated with a certain thickness of LiTaO3And (4) coating the fast ions.
9. A lithium ion battery, characterized in that, the lithium ion battery is prepared by the positive electrode material of claim 8.
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| CN113851623A (en) * | 2021-09-14 | 2021-12-28 | 蜂巢能源科技有限公司 | High-nickel multi-element positive electrode material, preparation method thereof and lithium ion battery |
| CN114566641B (en) * | 2022-02-28 | 2024-02-23 | 蜂巢能源科技股份有限公司 | Positive electrode material and preparation method and application thereof |
| CN114725354A (en) * | 2022-04-29 | 2022-07-08 | 远景动力技术(江苏)有限公司 | Positive electrode material and application thereof |
| CN114784265B (en) * | 2022-05-19 | 2023-11-21 | 巴斯夫杉杉电池材料有限公司 | Modified high-nickel monocrystal nickel cobalt lithium manganate positive electrode material, preparation method thereof and lithium ion battery |
| CN115036475A (en) * | 2022-05-31 | 2022-09-09 | 四川大学 | High-nickel layered cathode material with radial texture morphology and preparation method thereof |
| CN114864947A (en) * | 2022-06-21 | 2022-08-05 | 远东电池江苏有限公司 | Lithium supplementing method for coated high-nickel ternary cathode material |
| CN114914434A (en) * | 2022-06-30 | 2022-08-16 | 广州博粤新材料科技有限公司 | Positive electrode material containing lithium supplement agent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8877388B1 (en) * | 2010-01-20 | 2014-11-04 | Sandia Corporation | Solid-state lithium battery |
| JP2017162801A (en) * | 2016-03-08 | 2017-09-14 | 住友金属鉱山株式会社 | Positive electrode for nonaqueous electrolyte secondary battery, positive electrode active material used therefor, and secondary battery using the same |
| CN109671922A (en) * | 2018-11-07 | 2019-04-23 | 中国科学院过程工程研究所 | A kind of system and method for fast-ionic conductor coated lithium ion battery positive electrode |
| CN110800141A (en) * | 2017-09-12 | 2020-02-14 | 住友精化株式会社 | Electrode mixture for nonaqueous electrolyte secondary battery |
| CN110970604A (en) * | 2018-09-30 | 2020-04-07 | 深圳市贝特瑞纳米科技有限公司 | Coated ternary cathode material, and preparation method and application thereof |
| CN110993903A (en) * | 2019-11-13 | 2020-04-10 | 北京理工大学 | Tantalum modified high-nickel cathode material and preparation method and application thereof |
| CN111740096A (en) * | 2020-05-28 | 2020-10-02 | 北京理工大学 | High-nickel cathode material with rock salt phase thin layer on primary particle surface layer and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6258486B1 (en) * | 1999-07-15 | 2001-07-10 | Mitsubishi Chemical Corporation | Electrochemical cell having a surface modified electrode and associated fabrication process |
| KR101562237B1 (en) * | 2007-09-04 | 2015-10-21 | 미쓰비시 가가꾸 가부시키가이샤 | Lithium transition metal-type compound powder |
| EP3121880B1 (en) * | 2014-03-18 | 2018-09-19 | Kabushiki Kaisha Toshiba | Active material for batteries, non-aqueous electrolyte battery, and battery pack |
-
2020
- 2020-12-22 CN CN202011525373.2A patent/CN112670506B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8877388B1 (en) * | 2010-01-20 | 2014-11-04 | Sandia Corporation | Solid-state lithium battery |
| JP2017162801A (en) * | 2016-03-08 | 2017-09-14 | 住友金属鉱山株式会社 | Positive electrode for nonaqueous electrolyte secondary battery, positive electrode active material used therefor, and secondary battery using the same |
| CN110800141A (en) * | 2017-09-12 | 2020-02-14 | 住友精化株式会社 | Electrode mixture for nonaqueous electrolyte secondary battery |
| CN110970604A (en) * | 2018-09-30 | 2020-04-07 | 深圳市贝特瑞纳米科技有限公司 | Coated ternary cathode material, and preparation method and application thereof |
| CN109671922A (en) * | 2018-11-07 | 2019-04-23 | 中国科学院过程工程研究所 | A kind of system and method for fast-ionic conductor coated lithium ion battery positive electrode |
| CN110993903A (en) * | 2019-11-13 | 2020-04-10 | 北京理工大学 | Tantalum modified high-nickel cathode material and preparation method and application thereof |
| CN111740096A (en) * | 2020-05-28 | 2020-10-02 | 北京理工大学 | High-nickel cathode material with rock salt phase thin layer on primary particle surface layer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Local Electric-Field-Driven Fast Li Diffusion Kinetics at the Piezoelectric LiTaO3 Modified Li-Rich Cathode–Electrolyte Interphase;Mengting Si等;《Advanced Science》;20191217;第1902538(1-9)页 * |
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