CN113381004A - Preparation method of vanadium pentoxide in-situ coated NCM111 ternary cathode material - Google Patents

Preparation method of vanadium pentoxide in-situ coated NCM111 ternary cathode material Download PDF

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CN113381004A
CN113381004A CN202110649850.4A CN202110649850A CN113381004A CN 113381004 A CN113381004 A CN 113381004A CN 202110649850 A CN202110649850 A CN 202110649850A CN 113381004 A CN113381004 A CN 113381004A
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ncm111
room temperature
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陈绍军
叶旋
钟燕辉
涂华锦
邱志文
王凌云
丁安莉
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Heyuan Polytechnic
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    • 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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Abstract

The invention discloses a preparation method of a vanadium pentoxide in-situ coated NCM111 ternary cathode material, wherein V is used in the method2O5For NCM111 material (V)2O5Accounting for 1 percent of the mass of the NCM111 material) to be coated, thereby preparing the NCM111 ternary cathode material with uniform particle size, tighter particles, bigger particles, good morphology and excellent electrochemical performance. The cycle performance, rate capability, impedance and charge-discharge test of the coated material are optimized, the coated material has excellent electrochemical performance, the first discharge capacity reaches 201.516mAh/g (under 0.5C rate), the capacity retention rate is high, and the coated material has the optimal cycle stabilityAnd the rate performance, and the excellent electrochemical performance is fully shown.

Description

Preparation method of vanadium pentoxide in-situ coated NCM111 ternary cathode material
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a vanadium pentoxide in-situ coated NCM111 ternary cathode material.
Background
Ternary positive electrode material LiNi of lithium ion battery1/3Co1/3Mn1/3O2Has the characteristics of moderate cost, good cycling stability, high specific capacity and the like. LiNi1/3Co1/3Mn1/3O2The theoretical capacity of the reactor is 278mAh/g, and the actual production capacity is 170-180 mAh/g. The material can simultaneously and effectively overcome the problems of high cost of lithium cobaltate material, low cycle performance of lithium manganate material, small specific capacity of lithium iron phosphate and the like. Many ternary material systems, such as LiNi, with different compositions of Ni, Co, Mn ratios, are now being investigated1/ 3Co1/3Mn1/3O2(type 333) LiNi5Co2Mn3O2(523 type), LiNi4Co4Mn4O2(type 442) LiNi8Co1Mn1O2(811 type) and lithium-rich ternary materials, etc.
The nickel-cobalt-manganese ternary material comprehensively utilizes the advantages of Ni, Co and Mn, overcomes the respective disadvantages, and has more advantages than other anode materials. However, it also has some disadvantages, such as lower rate capability, fast capacity fading, etc. In order to improve the electrochemical performance of the LiNi catalyst, the LiNi catalyst can be controlled by a surfactant-assisted hydrothermal synthesis method1/3Co1/3Mn1/3O2The material has a proper micro-morphology structure, and the structural stability of the material is enhanced, so that the physical performance and the electrochemical performance of the material are improved.
Currently LiNi1/3Co1/3Mn1/3O2The most common preparation techniques mainly include solid phase synthesis, coprecipitation, sol-gel, surfactant-assistedHydrothermal method, etc.
(1) High temperature solid phase process
The principle of the method is that: lithium salt and hydroxide (oxide or acetate) of transition metal are uniformly mixed according to the stoichiometric ratio, and the mixture is sintered at high temperature to obtain a product. The high-temperature solid phase method has the advantages of simple process equipment and condition control, easy industrialization and the like, but because the raw materials are refined and mixed by adopting a mechanical means, the mixing uniformity is limited, impurities are easy to introduce, the stoichiometric ratio is difficult to control, and impure phases are easy to form. In addition, the heat treatment temperature is higher, the time is longer, and the cost is increased.
(2) Coprecipitation method
The coprecipitation method can be classified into a direct coprecipitation method and an indirect coprecipitation method. The direct coprecipitation method is to precipitate lithium salt and nickel, cobalt and manganese salts directly under the action of a precipitator, and then to sinter at high temperature to prepare the corresponding material. The indirect coprecipitation method is to prepare a precursor, then to filter, wash, dry and the like the precursor, to mix the precursor with lithium salt evenly and to sinter the mixture, or to add lithium salt into the prepared precursor solution, to freeze or evaporate and dry the mixture, and to sinter the mixture at high temperature to obtain the material. The coprecipitation method can control the granularity and the appearance of the product by controlling the pH value, the temperature, the concentration, the sintering temperature, the stirring speed and the like of the reaction solution, so that the product components have the advantages of small particle size, uniform granularity, good batch property of mass production and the like.
(3) Sol-gel process
The sol-gel method and the coprecipitation method have similar advantages, the synthesized product has uniform chemical components, high purity, small particles and accurately controllable stoichiometric ratio, but the sol-gel method has complex process and higher cost, and the appearance and the particle size of the product are not easy to control.
(4) Surfactant assisted hydrothermal process
The surfactant-assisted hydrothermal method is characterized in that based on a hydrothermal synthesis method, a surfactant is added for assisting to change the growth directions and microstructures of primary and secondary (secondary) crystal structures of crystal particles. The surfactant is effectively adsorbed in the hydrothermal and crystallization processesOn the surface of the material particles, the soft template is exerted, the further growth and agglomeration of the material particles are prevented, the uniformity of particle growth is improved, and the shape of nano size and uniform distribution is beneficial to Li+The transmission in the material improves the electrochemical performance of the material.
Along with the rapid development of social economy, the demand of human beings on energy is also improved, particularly the rising of the new energy power automobile industry, people are prompted to continuously research and develop a lithium ion battery anode material with better electrochemical performance, and LiNi1/3Co1/ 3Mn1/3O2The ternary material is a novel anode material researched in recent years, has considerable market application prospect, but has the defects of low rate performance, high capacity attenuation, low tap density and the like, and researches show that LiNi is a novel anode material1/3Co1/3Mn1/3O2The electrochemical performance of the electrochemical element has a close relationship with the microstructure of the electrochemical element, so that the research of improving the microstructure of the electrochemical element to make the electrochemical element have better electrochemical performance is always the key point of the research.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of a vanadium pentoxide in-situ coated NCM111 ternary cathode material, and aims to solve the problem of the existing LiNi1/3Co1/3Mn1/3O2The electrochemical performance of (2) is low.
The technical scheme of the invention is as follows:
(1) the molar ratio of Ni to Co to Mn to 1 is calculated and weighed as 1.578g of NiSO4·6H2O、1.687g CoSO4·7H2O、1.014g MnSO4·H2Adding O into 80mL of deionized water, and fully stirring for 1-2 h at room temperature by using a DF-101S type heat collection type constant-temperature magnetic stirrer to obtain a nickel-cobalt-manganese source solution;
(2) 1.908g of anhydrous sodium carbonate and 0.696g of sodium dodecyl benzene sulfonate are weighed and added into 80mL of deionized water, and the mixture is fully stirred for 1-2 hours at room temperature by using a DF-101S type heat collection type constant temperature magnetic stirrer to obtain a carbonate surfactant mixed solution;
(3) dropwise adding the carbonate surfactant mixed solution into the nickel-cobalt-manganese source solution, and fully stirring for 1-2 hours at room temperature to obtain a mixed solution;
(4) transferring the mixed solution into a 200mL polytetrafluoroethylene lining, sealing, putting into a reaction kettle, and preserving heat for 14h under the condition that the set temperature is 170 ℃ (the hydrothermal temperature can be respectively changed into 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, and the hydrothermal time can be respectively changed into 10h, 12h and 14 h);
(5) after the reaction kettle is cooled to room temperature, vacuum filtration is carried out, and then drying is carried out for 12 hours at the temperature of 80 ℃ to obtain Ni1/ 3Co1/3Mn1/3CO3A precursor;
(6) dissolving 1g of ammonium metavanadate solid in 200mL of distilled water, stirring at a constant temperature of 80 ℃ by using a DF-101S type heat collection type constant-temperature magnetic stirrer until the ammonium metavanadate solid is completely dissolved, stopping heating and naturally cooling to room temperature when the aqueous solution is light yellow to obtain V2O5A solution;
(7) 1.25g of Ni are calculated and weighed according to the molar ratio of 1:1.051/3Co1/3Mn1/3CO3Precursor, 0.568g LiOH. H2O, the Ni1/3Co1/3Mn1/3CO3Precursor and LiOH. H2Grinding the O in a clean agate mortar until the O is uniformly mixed to obtain a mixture; adding the mixture into 5mL of V while stirring by using a DF-101S type heat collection type constant-temperature magnetic stirrer2O5Fully stirring the solution for 1-5 h, uniformly stirring, and drying in an oven at 80 ℃;
(8) placing the dried sample into a muffle furnace for secondary sintering (firstly preserving heat at 550 ℃ for 5h, and then preserving heat at 850 ℃ for 18h), wherein the heating rate of the muffle furnace is 5 ℃/min; when the sintering is finished and the temperature of the muffle furnace is cooled to the room temperature, V is obtained2O5Coated LiNi1/3Co1/3Mn1/3O2A ternary positive electrode material.
Has the advantages that: the present invention providesA preparation method of a vanadium pentoxide in-situ coated NCM111 ternary positive electrode material uses V2O5For NCM111 material (V)2O5Accounting for 1 percent of the mass of the NCM111 material) to be coated, thereby preparing the NCM111 ternary cathode material with uniform particle size, tighter particles, bigger particles, good morphology and excellent electrochemical performance. The cycle performance, rate capability, impedance and charge-discharge test of the coated material are optimized, the coated material has excellent electrochemical performance, the first discharge capacity reaches 201.516mAh/g (under 0.5C rate), the capacity retention rate is high, the coated material has the best cycle stability and rate capability, and the excellent electrochemical performance is fully shown.
Drawings
FIG. 1 shows comparative example with addition of SDBS and V2O5XRD contrast pattern of the clad examples.
FIG. 2 shows comparative example with addition of SDBS and V2O5SEM comparison of the coated examples.
FIG. 3 shows comparative example with addition of SDBS and V2O5Comparative cycle chart of the coated examples.
FIG. 4 shows comparative example with addition of SDBS and V2O5CV curve comparison of coating examples.
FIG. 5 shows comparative example with addition of SDBS and V2O5First charge and discharge curves of the coating examples are compared.
FIG. 6 shows comparative example with addition of SDBS and V2O5Magnification comparison of coating examples.
FIG. 7 shows comparative example with addition of SDBS and V2O5EIS curves of the clad examples are compared.
FIG. 8 is V2O5EDS test plots of the coating examples.
FIG. 9 is V2O5Graph of EDS test results for the clad examples.
Detailed Description
The invention provides a preparation method of a vanadium pentoxide in-situ coated NCM111 ternary cathode material, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Examples
The preparation method of the vanadium pentoxide in-situ coated NCM111 ternary cathode material of the embodiment includes the following steps:
(1) the molar ratio of Ni to Co to Mn to 1 is calculated and weighed as 1.578g of NiSO4·6H2O、1.687g CoSO4·7H2O、1.014g MnSO4·H2And adding O into 80mL of deionized water, and fully stirring for 1h by using a DF-101S type heat collection type constant-temperature magnetic stirrer at room temperature to obtain the nickel-cobalt-manganese source solution.
(2) 1.908g of anhydrous sodium carbonate and 0.696g (1mmol) of Sodium Dodecyl Benzene Sulfonate (SDBS) are weighed and added into 80mL of deionized water, and the mixture is fully stirred for 2 hours at room temperature by using a DF-101S type heat collection type constant temperature magnetic stirrer to obtain a carbonate surfactant mixed solution.
(3) Slowly dripping the mixed solution of the carbonate surfactant into the nickel-cobalt-manganese source solution, and fully stirring for 1h at room temperature to obtain a mixed solution.
(4) The mixed solution is transferred into a 200mL polytetrafluoroethylene lining and sealed, and then is put into a stainless steel reaction kettle, and the temperature is kept for 14h under the condition that the set temperature is 170 ℃.
(5) After the reaction kettle is cooled to room temperature, vacuum filtration is carried out, and then drying is carried out for 12 hours at the temperature of 80 ℃, and finally Ni is obtained1/3Co1/3Mn1/3CO3And (3) precursor.
(6) Dissolving 1g of ammonium metavanadate solid in 200mL of distilled water, stirring at a constant temperature of 80 ℃ by using a DF-101S type heat collection type constant-temperature magnetic stirrer until the ammonium metavanadate solid is completely dissolved, stopping heating and naturally cooling to normal temperature when the aqueous solution is light yellow to obtain V2O5And (3) solution.
(7) Calculated according to a molar ratio of 1:1.05 and weighed 1.25g Ni1/3Co1/3Mn1/3CO3Precursor, 0.568g LiOH. H2O, placing them cleanGrinding the mixture in an agate mortar to be uniformly mixed, adding the mixture into 5mL of V while stirring on a DF-101S type heat collection type constant-temperature magnetic stirrer2O5And (3) fully stirring the solution for 1-5 hours, uniformly mixing, and then drying in an oven at 80 ℃.
(8) Placing the dried sample into a muffle furnace for secondary sintering (firstly preserving heat at 550 ℃ for 5h, and then preserving heat at 850 ℃ for 18h), wherein the heating rate is 5 ℃/min; after sintering is finished and the furnace temperature is cooled to room temperature, LiNi can be obtained1/ 3Co1/3Mn1/3O2/V2O5And (3) a ternary cathode material (namely the NCM111 ternary cathode material is coated with vanadium pentoxide in situ).
Comparative example
(1) The molar ratio of Ni to Co to Mn to 1 is calculated and weighed as 1.578g of NiSO4·6H2O、1.687g CoSO4·7H2O、1.014g MnSO4·H2And adding O into 80mL of deionized water, and fully stirring for 1h by using a DF-101S type heat collection type constant-temperature magnetic stirrer at room temperature to obtain the nickel-cobalt-manganese source solution.
(2) 1.908g of anhydrous sodium carbonate and 0.696g (1mmol) of Sodium Dodecyl Benzene Sulfonate (SDBS) are weighed and added into 80mL of deionized water, and the mixture is fully stirred for 2 hours at room temperature by using a DF-101S type heat collection type constant temperature magnetic stirrer to obtain a carbonate surfactant mixed solution.
(3) Slowly dripping the mixed solution of the carbonate surfactant into the nickel-cobalt-manganese source solution, and fully stirring for 2 hours at room temperature to obtain a mixed solution.
(4) The mixed solution was transferred to a 200mL Teflon liner and sealed, and then placed in a stainless steel reactor and held at a set temperature of 170 ℃ for 14h (hydrothermal temperature: 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, hydrothermal time: 10h, 12h, 14h, respectively).
(5) After the reaction kettle is cooled to room temperature, vacuum filtration is carried out, and then drying is carried out for 12 hours at the temperature of 80 ℃, and finally Ni is obtained1/3Co1/3Mn1/3CO3And (3) precursor.
(6) According to the molar ratio of 1:1.05 calculation and weighing 1.25g Ni1/3Co1/3Mn1/3CO3Precursor, 0.568g LiOH. H2O, they were ground in a clean agate mortar until mixed well.
(7) Putting the mixed sample into a muffle furnace for secondary sintering (firstly preserving heat at 550 ℃ for 5h, and then preserving heat at 850 ℃ for 18h), wherein the heating rate is 5 ℃/min; obtaining LiNi of the comparative example added with SDBS after sintering is finished and the furnace temperature is cooled to room temperature1/3Co1/3Mn1/3O2A ternary positive electrode material.
The NCM111 ternary cathode material is coated with vanadium pentoxide in situ and prepared according to the embodiment by using 1% of V2O5The material is coated, the performance of the material is comprehensively improved, incomparable superiority is shown in the cycle performance, the rate performance, the impedance and the charge and discharge test of the coated material, the structure of the material is more compact, the particles are larger and more uniform, and the performance of the material is compared with that of a comparative example prepared by adding SDBS (sodium dodecyl benzene sulfonate) shown in figures 1-7, V2O5The EDS test patterns and EDS test results of the coating examples are shown in fig. 8 to 9.
FIG. 1 shows comparative example with addition of SDBS and V2O5The XRD contrast patterns of the cladding examples are high in diffraction peak intensity of both samples, and the diffraction peaks of the (006/102) and (108/110) are separated to a large extent, so that both samples have good layered structures. The c/a-4.974 (a-2.86003, c-14.22646), I, of the SDBS-added sample can be determined by jade 6.0 and calculation003/I104＝1.092(I003＝3653，I104＝3346)；1％V2O5C/a-4.976, I for sample003/I104＝1.212(I003＝3985，I1043287); comparison of the two, 1% V2O5The sample has a better layered structure, the lithium-nickel mixed-arrangement degree is small, and the electrochemical performance is more excellent.
FIG. 2 shows comparative example with addition of SDBS and V2O5The SEM comparison graph of the coating example shows that the composite material particles coated by 1% vanadium pentoxide are larger, primary particles are more uniform, the particles are more compact, and the grain boundary is more obvious; to dopeAlthough the surface of the material is smooth, the particles are small and uneven, and the structure is not as compact. The results show that 1% V2O5The performance of the coated material is better.
FIG. 3 shows comparative example with addition of SDBS and V2O5According to a cyclic comparison graph of the coating embodiment, the discharge specific capacity of a coated sample is higher, the specific capacities of the coated sample before and after the cycle are 201.516mAh/g and 172.870mAh/g respectively, the specific capacities of the uncoated sample before and after the cycle are 186.148mAh/g and 158.607mAh/g respectively, the capacity retention rates corresponding to the two samples are 86.0% (coating) and 85.20% (blank), and the result shows that the coated sample not only has higher capacity, but also has better capacity retention rate, and the cyclic stability of the material is improved.
FIG. 4 shows comparative example with addition of SDBS and V2O5CV curve comparison of coating examples, with 1% V2O5The coated sample has higher redox peak height, larger area and better symmetry, the difference between the peak potential and the peak current of the oxidation peak and the reduction peak is minimum, the height and the area of the redox peak of the blank sample are smaller, the symmetry is poorer, and the difference between the peak potential and the peak current is larger, which shows that the coated sample has better reversible performance and higher cycle stability.
FIG. 5 shows comparative example with addition of SDBS and V2O5First discharge specific capacity of 181.407mAh/g and 1% V of blank sample (with SDBS)2O5The specific discharge capacity of the coated sample is 194.290mAh/g, and the sample has charge and discharge platforms at about 3.6V and 4.5V. The result shows that the charge and discharge platform of the blank sample is shorter, while the charge and discharge platform of the coated sample is longer and more gentle, the polarization effect is small, the capacity is high, and the electrochemical performance is best.
FIG. 6 shows comparative example with addition of SDBS and V2O5The ratio comparison graph of the coating embodiment shows that the discharge specific capacity of the coated sample is remarkably improved under the same ratio, and the coated sample shows more excellent ratio performance under large ratio. Under different multiplying powers, the first discharge specific capacity of the blank sample is 227.241 mAh-g. 202.655mAh/g, 188.747mAh/g, 165.425mAh/g, 143.298mAh/g, 101.012mAh/g and 87.805mAh/g, the first discharge specific capacity of the coated sample is 207.712mAh/g, 184.954mAh/g, 166.057mAh/g, 138.241mAh/g, 118.081mAh/g, 75.793mAh/g and 54.931mAh/g, compared with the two, the discharge specific capacity of the blank sample is reduced along with the increase of the multiplying power, the discharge specific capacity of the blank sample is only 54.931mAh/g under the multiplying power of 10C, and the discharge specific capacity of the coated sample can also reach 87.805mAh/g, therefore, on the basis of adding SDBS, 1% V is used2O5The coated sample shows more excellent rate capability.
FIG. 7 shows comparative example with addition of SDBS and V2O5EIS curves of the coated examples are compared with each other, and the charge transfer resistances of the blank samples are 299.548 Ω and 201.097 Ω, so that the charge transfer resistances of the coated samples are smaller, and Li+The material is easier to be removed and embedded, the conductivity of the material is improved, and the electrochemical performance of the material is improved.
FIG. 8 is V2O5EDS test chart of the coating example, FIG. 9 is V2O5The EDS test result chart of the coating embodiment shows that the coating of the vanadium pentoxide does not affect the element content, and only a layer of uniform coating film is formed on the surface of the material, so that the material structure is more compact, and the thermal stability, the cycle stability, the rate capability and the like of the material are improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (2)

1. A preparation method of a vanadium pentoxide in-situ coated NCM111 ternary cathode material is characterized by comprising the following steps:
(1) 1.578g of NiSO are calculated and weighed according to the molar ratio of Ni to Co to Mn of 1 to 14·6H2O、1.687g CoSO4·7H2O、1.014g MnSO4·H2O is added to 80mLFully stirring for 1-2 hours in ionized water by using a DF-101S type heat collection type constant-temperature magnetic stirrer at room temperature to obtain a nickel-cobalt-manganese source solution;
(2) 1.908g of anhydrous sodium carbonate and 0.696g of sodium dodecyl benzene sulfonate are weighed and added into 80mL of deionized water, and the mixture is fully stirred for 1-2 hours at room temperature by using a DF-101S type heat collection type constant temperature magnetic stirrer to obtain a carbonate surfactant mixed solution;
(3) dropwise adding the carbonate surfactant mixed solution into the nickel-cobalt-manganese source solution, and fully stirring for 1-2 hours at room temperature to obtain a mixed solution;
(4) transferring the mixed solution into a 200mL polytetrafluoroethylene lining, sealing, putting into a reaction kettle, and preserving heat for 14h under the condition that the set temperature is 170 ℃;
(5) after the reaction kettle is cooled to room temperature, vacuum filtration is carried out, and then drying is carried out for 12 hours at the temperature of 80 ℃ to obtain Ni1/3Co1/ 3Mn1/3CO3A precursor;
(6) dissolving 1g of ammonium metavanadate solid in 200mL of distilled water, stirring at a constant temperature of 80 ℃ by using a DF-101S type heat collection type constant-temperature magnetic stirrer until the ammonium metavanadate solid is completely dissolved, stopping heating and naturally cooling to room temperature when the aqueous solution is light yellow to obtain V2O5A solution;
(7) 1.25g of Ni are calculated and weighed according to the molar ratio of 1:1.051/3Co1/3Mn1/3CO3Precursor, 0.568g LiOH. H2O, the Ni1/3Co1/3Mn1/3CO3Precursor and LiOH. H2Grinding the O in a clean agate mortar until the O is uniformly mixed to obtain a mixture; adding the mixture into 5mL of V while stirring by using a DF-101S type heat collection type constant-temperature magnetic stirrer2O5Fully stirring the solution for 1-5 h, uniformly stirring, and drying in an oven at 80 ℃;
(8) placing the dried sample into a muffle furnace for secondary sintering, wherein the heating rate of the muffle furnace is 5 ℃/min; when the sintering is finished and the temperature of the muffle furnace is cooled to the room temperature, V is obtained2O5Coated LiNi1/3Co1/3Mn1/3O2A ternary positive electrode material.
2. The method for preparing the ternary cathode material of vanadium pentoxide in-situ coated NCM111 according to claim 1, wherein the process conditions of the second-stage sintering are as follows: the temperature is firstly preserved for 5h at 550 ℃ and then preserved for 18h at 850 ℃.
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