CN113644272B - Cerium-bismuth composite oxide doped lithium ion battery positive electrode material and preparation method thereof - Google Patents
Cerium-bismuth composite oxide doped lithium ion battery positive electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cerium bismuth composite oxide doped lithium ion battery anode material, wherein the cerium bismuth composite oxide is doped in the lithium ion battery anode material, wherein the molar ratio of cerium to bismuth in the cerium bismuth composite oxide is (1.5-9): 1. The preparation method comprises the following steps: (1) Mixing a cerium source and a bismuth source according to a molar ratio, dissolving the mixture in a nitric acid solution, adding a sodium hydroxide solution to perform a solvothermal reaction, and filtering and drying the mixture after the reaction is finished to obtain a cerium bismuth composite oxide; (2) Mixing the cerium bismuth composite oxide obtained in the step (1), a positive electrode material precursor and lithium salt according to the stoichiometric ratio of chemical elements, and placing the mixture in an oxygen atmosphere furnace for sintering; (3) And (3) washing and drying the sintered product obtained in the step (2), and then carrying out secondary sintering to obtain the cerium-bismuth composite oxide doped lithium ion battery anode material. According to the invention, the ternary positive electrode material of the lithium ion battery is doped with the cerium bismuth composite oxide, so that the rate characteristic and the cycle performance of the positive electrode material can be improved.
Description
Technical Field
The invention belongs to the field of lithium ion anode materials, and particularly relates to a cerium bismuth composite oxide doped lithium ion battery anode material and a preparation method thereof.
Background
The lithium ion battery can be used in the fields of 3C products, electric tools, new energy automobiles and the like, and the demand of the lithium ion battery is rapidly increased along with the rapid development of the new energy automobiles in recent years. In order to meet the market demands for batteries with high energy density, low cost and high cost performance, high nickel cathode materials are pushed to the front of research.
The main ideas for improving the energy density of materials in the market at present are divided into two main categories, the first category is to improve the service voltage, mainly aiming at lithium cobaltate products, and the other category is to improve the content of Ni elements in the materials. At present, due to the scarcity and high price of Co resources, more market researches turn to high Ni materials, so that the use of Co can be reduced, and the cost can also be reduced. The increase of the Ni content usually generates a phenomenon of high residual lithium, which affects the coating process of material preparation, and usually water washing is needed to remove the residual lithium on the surface, and the water washing damages the surface structure of the positive active material, increases the specific surface area, and has poor cycle performance, so the material is usually modified by doping or coating. The coating usually needs to adopt a second sintering, the temperature of the second sintering is basically lower than that of the first sintering, so that some elements are difficult to effectively coat the surface of the material at a lower temperature in the coating process and achieve the required effect, on the other hand, if the additive components used in the material modification process are non-conductive components, the ionic or electronic conductivity of the material can be influenced in the use process, and further the rate characteristic of the material is directly influenced.
In addition, the high nickel cathode material is accompanied with Li in the process of charging and discharging + The crystal structure of the de-intercalation process is changed, the de-intercalation process is changed from a layered structure to a spinel phase and a nickel oxide phase, oxygen is released simultaneously, the released oxygen further reacts with the electrolyte to form an over-thick SEI film on the surface of the electrode material, the electrolyte is consumed in the process, the migration of lithium ions is also hindered, and the cyclicity of the battery is influencedAccordingly, preventing oxygen diffusion into the electrolyte during cycling can help improve the cycle life of the material. Therefore, how to improve the rate capability and cycle performance of the material simultaneously in the process of modifying the high nickel material becomes a problem to be solved urgently today.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and provides a cerium-bismuth composite oxide doped lithium ion battery positive electrode material and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the cerium bismuth composite oxide-doped lithium ion battery positive electrode material is characterized in that the cerium bismuth composite oxide is doped in the lithium ion battery positive electrode material, wherein the molar ratio of cerium to bismuth in the cerium bismuth composite oxide is (1.5-9): 1.
Preferably, the positive electrode material of the lithium ion battery is in a sphere-like secondary particle structure formed by primary particles, and the particle size D50 of the secondary particles is 2-25 μm.
Preferably, the molecular formula of the positive electrode material of the lithium ion battery is Li a Ni b Co c M d (Ce x Bi 1-x ) e O 2 Wherein M is at least one of Mn, al, zr, P, ti and Mg, and the values of a, b, c, d and e meet the following requirements: a is more than or equal to 0.9 and less than or equal to 1.2, b is more than or equal to 0.7 and less than or equal to 1, c is more than 0 and less than or equal to 0.2, d is more than 0 and less than or equal to 0.1, e is more than or equal to 0.0001 and less than or equal to 0.01, and x is more than 0 and less than 1.
As a general inventive concept, the present invention also provides a preparation method of the above-mentioned cerium bismuth composite oxide doped lithium ion battery positive electrode material, comprising the following steps:
(1) Mixing a cerium source and a bismuth source according to a molar ratio, dissolving the mixture in a nitric acid solution, adding a sodium hydroxide solution to perform a solvothermal reaction, and filtering and drying the mixture after the reaction is finished to obtain a cerium bismuth composite oxide;
(2) Mixing the cerium bismuth composite oxide obtained in the step (1), a positive electrode material precursor and lithium salt according to the stoichiometric ratio of chemical elements, and placing the mixture in an oxygen atmosphere furnace for sintering;
(3) And (3) washing and drying the sintered product obtained in the step (2), and sintering for the second time to obtain the cerium-bismuth composite oxide doped lithium ion battery anode material.
In the preparation method, preferably, in the step (1), the solvothermal reaction temperature is 80-150 ℃ and the reaction time is 15-30h.
In the preparation method, preferably, in the step (1), the concentration of the nitric acid solution is 3-5mol/L, the concentration of the sodium hydroxide solution is 6-10mol/L, and the volume ratio of the sodium hydroxide solution to the nitric acid solution is 5-10.
Preferably, in the step (2), the sintering is to sinter the mixture at 300-550 ℃ for 2-6h, then heat the mixture to 600-850 ℃ and preserve the heat for 2-30h, wherein the heating rate is 3-30 ℃/min.
In the preparation method, preferably, in the step (3), the temperature of the second sintering is 300-700 ℃, and the sintering time is 3-30h.
In the above preparation method, preferably, in step (1), the cerium source is one or more selected from cerium nitrate, cerium phosphate and cerium hydroxide; the bismuth source is selected from one or more of bismuth nitrate, bismuth carbonate and bismuth hydroxide;
in the step (2), the lithium source is one or more selected from lithium hydroxide, lithium carbonate, lithium sulfate and lithium nitrate.
In the above preparation method, preferably, in the step (3), the solvent to be washed is ethanol, methanol or deionized water.
In the above preparation method, preferably, in the step (2), the precursor of the positive electrode material is a hydroxide of nickel cobalt M.
Compared with the prior art, the invention has the advantages that:
(1) According to the invention, the ternary positive electrode material of the lithium ion battery is doped with the cerium bismuth composite oxide, and because the ionic radius of trivalent bismuth is similar to that of tetravalent cerium, the addition of bismuth enables the cerium bismuth composite oxide to have a stable fluorite structure, and can increase oxygen holes of the material, further improve the electronic conductivity and ionic conductivity of the material, and the rate characteristic of the material can be improved by doping the cerium bismuth composite oxide with the lithium ion positive electrode material.
(2) The cerium bismuth composite oxide doped lithium ion battery ternary positive electrode material has the effect of promoting the formation of oxygen vacancies, and oxygen in the crystal lattice of the ternary positive electrode material can be embedded into the oxygen vacancies after being removed, so that the further diffusion of the oxygen vacancies into electrolyte is prevented, the side reaction between oxygen atoms and the electrolyte is reduced, and the cycle performance of the positive electrode material is favorably improved.
(3) In the preparation method, the residual Li remained on the surface of the material is removed by washing, so that the problem of gelation possibly caused by high residual Li in the material coating process is solved, and the influence of secondary sintering, repairing and water washing on the material is avoided.
Drawings
Fig. 1 is a scanning electron microscope image of the positive electrode material of the cerium-bismuth composite oxide-doped lithium ion battery in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the positive electrode material of the cerium-bismuth composite oxide-doped lithium ion battery in example 2 of the present invention.
Fig. 3 is a charge-discharge curve diagram of the positive electrode material of the lithium ion battery doped with the cerium-bismuth composite oxide in example 1 of the present invention.
Fig. 4 is a graph showing the cycle retention rates of the cerium bismuth composite oxide doped lithium ion battery positive electrode material at 25 ℃ and 45 ℃ in example 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
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 specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the molecular formula of the cerium bismuth composite oxide doped lithium ion battery anode material is Li 1.02 Ni 0.88 Co 0.1 Al 0.02 (Ce 0.6 Bi 0.4 ) 0.001 O 2 The lithium ion battery anode material is of a sphere-like secondary particle structure formed by primary particles, and the particle size D50 of the secondary particles is 11.5 mu m.
The preparation method of the cerium bismuth composite oxide doped lithium ion battery anode material of the embodiment comprises the following specific steps:
(1) 4.32mmol of Ce (NO) was taken 3 ) 3 ·6H 2 O and 2.88mmol of Bi (NO) 3 ) 3 ·5H 2 Mixing O, dissolving in 5mL HNO with concentration of 3.5mol/L 3 Adding 35mL of NaOH solution with the concentration of 7mol/L into the solution, then placing the solution into a Teflon reaction kettle for solvothermal reaction, reacting for 16 hours at 100 ℃, filtering, washing with deionized water, and drying to obtain Ce 0.6 Bi 0.4 O 2 ；
(2) Controlling the molar ratio of the total mole of Ni, co and Al to the mole of Li element to be 1:1.03, the total mole of Ni, co and Al and Ce 0.6 Bi 0.4 O 2 In a molar ratio of 1:0.001, adding Ni 0.88 Co 0.1 Al 0.02 (OH) 2 Precursor, lithium hydroxide and Ce 0.6 Bi 0.4 O 2 Mixing, sintering in an oxygen atmosphere furnace at 400 deg.C for 3h, heating to 730 deg.C at a rate of 5 deg.C/min, sintering for 8h, and cooling to obtain matrix material Li with D50=11.5 μm 1.02 Ni 0.88 Co 0.1 Al 0.02 (Ce 0.6 Bi 0.4 O 2 ) 0.001 O 2 ；
(3) Washing the base material prepared in the step (2) with deionized water for 30min, filtering, stirring by using an electric stirrer during washing, drying a filter cake in a vacuum drying oven at the drying temperature of 180 ℃ for 6h, and then grinding and sieving;
(4) And (4) sintering the sample obtained in the step (3) for the second time in an oxygen atmosphere furnace, wherein the temperature of the second sintering is 500 ℃, and the sintering time is 5 hours, so as to obtain the cerium-bismuth composite oxide doped lithium ion battery anode material, and an SEM electron microscope image of the cerium-bismuth composite oxide doped lithium ion battery anode material is shown in figure 1.
The positive electrode material doped with the cerium bismuth composite oxide prepared in the embodiment is made into a button cell taking a metal lithium sheet as a negative electrode for evaluation test, 0.2C charging is carried out under the conditions of normal temperature and 3.0-4.3V of voltage interval, then 0.1C and 1C rate discharging are respectively carried out, and the charging and discharging curve is shown in fig. 3; the results of the cycle retention tests for 50-week 1C charge and 1C discharge at 25 ℃ and for 50-week 0.5C charge and 0.5C discharge at 45 ℃ at 25 ℃ are shown in FIG. 4.
Example 2:
the molecular formula of the cerium bismuth composite oxide doped lithium ion battery anode material is Li 1.02 Ni 0.88 Co 0.1 Al 0.02 (Ce 0.7 Bi 0.3 ) 0.001 O 2 The lithium ion battery anode material is of a sphere-like secondary particle structure formed by primary particles, and the particle size D50 of the secondary particles is 11 microns.
The preparation method of the cerium-bismuth composite oxide doped lithium ion battery positive electrode material comprises the following specific steps:
(1) 3.6mmol of Ce (NO) was taken 3 ) 3 ·6H 2 O and 1.54 mmoleBi (NO) 3 ) 3 ·5H 2 O, according to a molar ratio of 7:3, mixing and dissolving in 5mL of HNO with the concentration of 3.5mol/L 3 Adding 35mL of NaOH solution with the concentration of 7mol/L into the solution, then placing the solution into a Teflon reaction kettle for solvothermal reaction, reacting for 16 hours at 100 ℃, filtering, washing with deionized water, and drying to obtain Ce 0.7 Bi 0.3 O 2 ；
(2) Controlling the molar ratio of the total mole of Ni, co and Al to the mole of Li element to be 1:1.03 total mole of Ni, co, al and Ce 0.7 Bi 0.3 O 2 The molar ratio of substances is 1:0.001, adding Ni 0.88 Co 0.1 Al 0.02 (OH) 2 Precursor, lithium hydroxide and Ce 0.7 Bi 0.3 O 2 Mixing, sintering in an oxygen atmosphere furnace at 400 deg.C for 3h, heating to 730 deg.C at a rate of 5 deg.C/min for 8h to obtain matrix material Li with D50=11.0 μm 1.02 Ni 0.88 Co 0.1 Al 0.02 (Ce 0.7 Bi 0.3 ) 0.001 O 2 ；
(3) Washing the base material prepared in the step (2) with deionized water for 30min, filtering, stirring by using an electric stirrer during washing, drying a filter cake in a vacuum drying box at the drying temperature of 180 ℃ for 6h, and then grinding and sieving;
(4) And (4) carrying out secondary sintering on the sample obtained in the step (3) in an oxygen atmosphere furnace, wherein the temperature of the secondary sintering is 500 ℃, and the sintering time is 5 hours, so as to obtain the cerium-bismuth composite oxide doped lithium ion battery anode material, and an electron microscope image of the cerium-bismuth composite oxide doped lithium ion battery anode material is shown in fig. 2.
Example 3:
the molecular formula of the cerium bismuth composite oxide doped lithium ion battery anode material is Li 1.02 Ni 0.88 Co 0.07 Mn 0.05 (Ce 0.6 Bi 0.4 ) 0.0008 O 2 The anode material of the lithium ion battery is of a sphere-like secondary particle structure formed by primary particles, and the particle size D50 of the secondary particles is 10.2 mu m.
The preparation method of the cerium-bismuth composite oxide doped lithium ion battery positive electrode material comprises the following specific steps:
(1) 4.32mmol of Ce (NO) was taken 3 ) 3 ·6H 2 O and 2.88mmol of Bi (NO) 3 ) 3 ·5H 2 Mixing O, dissolving in 5mL HNO with concentration of 3.5mol/L 3 Adding 35mL of NaOH solution with the concentration of 7mol/L into the solution, then placing the solution into a Teflon reaction kettle for solvothermal reaction, filtering the solution after reacting for 13h at the temperature of 100 ℃, washing the solution by deionized water, and drying the solution to obtain Ce 0.6 Bi 0.4 O 2 ；
(2) According to the total molar sum of Ni, co and MnThe molar ratio of Li element is 1:1.02 total mol of Ni, co, mn and Ce 0.6 Bi 0.4 O 2 In a molar ratio of 1:0.0008, mixing Ni 0.88 Co 0.07 Mn 0.05 (OH) 2 Precursor, lithium hydroxide and Ce 0.6 Bi 0.4 O 2 Mixing, sintering in an oxygen atmosphere furnace at 400 deg.C for 3h, heating to 730 deg.C at a rate of 5 deg.C/min for 8h to obtain matrix material Li with D50=10.2 μm 1.02 Ni 0.88 Co 0.07 Mn 0.05 (Ce 0.6 Bi 0.4 O 2 ) 0.0008 O 2 ；
(3) Washing the base material prepared in the step (2) with deionized water for 20min, filtering, stirring by using an electric stirrer during washing, drying a filter cake in a vacuum drying box at the drying temperature of 180 ℃ for 6h, and then grinding and sieving;
(4) And (4) carrying out secondary sintering on the sample obtained in the step (3) in an oxygen atmosphere furnace, wherein the temperature of the secondary sintering is 550 ℃, and the sintering time is 5 hours, so as to obtain the cerium bismuth composite oxide doped lithium ion battery anode material.
Example 4:
the molecular formula of the cerium bismuth composite oxide doped lithium ion battery anode material is Li 1.02 Ni 0.88 Co 0.07 Mn 0.04 Al 0.01 (Ce 0.7 Bi 0.3 ) 0.0008 O 2 The lithium ion battery anode material is of a sphere-like secondary particle structure formed by primary particles, and the particle size D50 of the secondary particles is 10.6 mu m.
The preparation method of the cerium bismuth composite oxide doped lithium ion battery anode material of the embodiment comprises the following specific steps:
(1) 3.6mmol of Ce (NO) was taken 3 ) 3 ·6H 2 O and 1.54mmol of Bi (NO) 3 ) 3 ·5H 2 Mixing O, dissolving in 5mL HNO with concentration of 3.5mol/L 3 Adding 30mL of 7mol/L NaOH solution into the solution, then placing the solution into a Teflon reaction kettle for solvothermal reaction, reacting for 13 hours at 100 ℃, filtering and removingWashing with ionized water and drying to obtain Ce 0.7 Bi 0.3 O 2 ；
(2) According to the molar ratio of the total mole of Ni, co, mn and Al to the mole of Li element of 1:1.02 total mol of Ni, co, mn, al and Ce 0.7 Bi 0.3 O 2 The molar ratio of substances is 1:0.0008, adding Ni 0.88 Co 0.07 Mn 0.04 Al 0.01 (OH) 2 Precursor, lithium hydroxide, alumina, ce 0.7 Bi 0.3 O 2 Mixing, sintering in an oxygen atmosphere furnace at 400 deg.C for 3h, heating to 730 deg.C at a rate of 5 deg.C/min for 8h to obtain Li as matrix material with particle diameter D50=10.6 μm 1.02 Ni 0.88 Co 0.7 Mn 0.4 Al 0.01 (Ce 0.7 Bi 0.3 ) 0.0008 O 2 ；
(3) Washing the base material prepared in the step (2) with deionized water for 30min, filtering, stirring by using an electric stirrer during washing, drying a filter cake in a vacuum drying oven at the drying temperature of 180 ℃ for 5h, and then grinding and sieving;
(4) And (4) carrying out secondary sintering on the sample obtained in the step (3) in an oxygen atmosphere furnace, wherein the temperature of the secondary sintering is 550 ℃, and the sintering time is 5 hours, so as to obtain the cerium bismuth composite oxide doped lithium ion battery anode material.
Example 5:
the molecular formula of the cerium bismuth composite oxide doped lithium ion battery anode material is Li 1.02 Ni 0.88 Co 0.07 Mn 0.045 Zr 0.005 (Ce 0.8 Bi 0.2 ) 0.001 O 2 The lithium ion battery anode material is of a sphere-like secondary particle structure formed by primary particles, and the particle size D50 of the secondary particles is 11.0 mu m.
The preparation method of the cerium bismuth composite oxide doped lithium ion battery anode material of the embodiment comprises the following specific steps:
(1) 3.6mmol of Ce (NO) was taken 3 ) 3 ·6H 2 O and 0.9mmol of Bi (NO) 3 ) 3 ·5H 2 O, dissolved in 5mL of HNO with a concentration of 3.5mol/L 3 Adding 30mL of 7mol/L NaOH solution into the solution, then placing the solution into a Teflon reaction kettle for solvothermal reaction, filtering the solution after reacting for 13 hours at 100 ℃, washing the solution with deionized water, and drying the solution to obtain Ce 0.7 Bi 0.3 O 2 ；
(2) According to the molar ratio of the total mol of Ni, co, mn and Zr to the Li element of 1:1.02 total moles of Ni, co, mn, zr with Ce 0.8 Bi 0.2 O 2 In a molar ratio of 1:0.001, adding Ni 0.88 Co 0.07 Mn 0.045 Zr 0.005 (OH) 2 Lithium hydroxide and aluminum oxide, ce 0.8 Bi 0.2 O 2 Mixing, sintering in an oxygen atmosphere furnace at 400 deg.C for 3h, heating to 730 deg.C at a rate of 5 deg.C/min for 8h to obtain matrix material Li with particle diameter D50=11.0 μm 1.02 Ni 0.88 Co 0.07 Mn 0.045 Zr 0.005 (Ce 0.8 Bi 0.2 ) 0.001 O 2 ；
(3) Washing the base material prepared in the step (2) with deionized water for 30min, filtering, stirring by using an electric stirrer during washing, drying a filter cake in a vacuum drying box at the drying temperature of 180 ℃ for 5h, and then grinding and sieving;
(4) And (4) carrying out secondary sintering on the sample obtained in the step (3) in an oxygen atmosphere furnace, wherein the temperature of the secondary sintering is 550 ℃, and the sintering time is 5h, so as to obtain the cerium-bismuth composite oxide doped lithium ion battery anode material.
Comparative example 1:
the comparative example is different from example 1 in that a cerium bismuth composite oxide is not synthesized in the preparation process, namely step (1) is omitted, and Ni is directly added in step (2) 0.88 Co 0.1 Al 0.02 (OH) 2 The hydroxide precursor and lithium hydroxide were mixed and sintered under the conditions otherwise consistent with those in example 1, to finally prepare Li with D50=11.0 μm 1.02 Ni 0.88 Co 0.1 Al 0.02 O 2 And (3) sampling.
Comparative example 2:
compared with example 3, the difference is that the preparation process does not comprise a cerium bismuth composite oxide substance, namely step (1) is omitted, and Ni is directly added in step (2) 0.88 Co 0.07 Mn 0.05 (OH) 2 The hydroxide precursor was mixed with lithium hydroxide and sintered under conditions otherwise consistent with those in example 3 to finally prepare Li with D50=10.5 μm 1.02 Ni 0.88 Co 0.07 Mn 0.05 O 2 And (3) sampling.
Comparative example 3:
this comparative example is different from example 3 in that the molar ratio in step (1) in the production process is 1:1 Ce (NO) 3 ) 3 ·6H 2 O and Bi (NO) 3 ) 3 ·5H 2 Preparation of Ce by mixing with O 0.5 Bi 0.5 O 2 With Ni in step (2) 0.88 Co 0.07 Mn 0.05 (OH) 2 The hydroxide precursor and lithium hydroxide were mixed and sintered under the conditions otherwise consistent with those in example 3, to finally prepare Li having a D50 of 10.5. Mu.m 1.02 Ni 0.88 Co 0.07 Mn 0.05 (Ce 0.5 Bi 0.5 ) 0.0008 O 2 And (3) sampling.
Comparative example 4:
this comparative example is different from example 3 in that Ce is added in step b of the preparation process 0.7 Bi 0.3 O 2 Replacement with cerium oxide, otherwise identical to example 3, finally produced Li with a D50 of 10.5 μm 1.02 Ni 0.88 Co 0.7 Mn 0.5 Ce 0.000 8 O 2 And (3) sampling.
Comparative example 5:
the comparative example was prepared with a molar ratio of 3:1 CeO 2 And Bi 2 O 3 Compared with example 3, the difference is that no cerium bismuth composite oxide is synthesized in the preparation process, namely step (1) is omitted, and CeO is directly added 2 、Bi 2 O 3 And Ni 0.88 Co 0.1 Al 0.02 (OH) 2 The hydroxide precursor and the lithium hydroxide are mixed intoThe line sintering process comprises the following specific preparation processes:
(1) According to the molar ratio of the total mole of Ni, co and Mn to the mole of Li element of 1:1.02, the total mole ratio of Ni, co and Mn to the total mole ratio of Ce and Bi is 1:0.0008, mixing Ni 0.88 Co 0.07 Mn 0.05 (OH) 2 Precursor, lithium hydroxide and the molar ratio of 3:1 CeO 2 And Bi 2 O 3 Mixing, placing in an oxygen atmosphere furnace for sintering after mixing, firstly sintering at 400 ℃ for 3h, and then heating to 730 ℃ at the heating rate of 5 ℃/min for sintering for 8h to obtain a base material;
(2) Washing the base material prepared in the step (1) with deionized water for 20min, filtering, stirring by using an electric stirrer during washing, drying a filter cake in a vacuum drying oven at the drying temperature of 180 ℃ for 6h, and then grinding and sieving;
(3) Carrying out secondary sintering on the sample obtained in the step (2) in an oxygen atmosphere furnace, wherein the temperature of the secondary sintering is 550 ℃, and the sintering time is 5h, so as to obtain CeO with the D50 of 10.8 mu m 2 And Bi 2 O 3 The co-doped lithium ion battery anode material.
The high-nickel NCA positive electrode materials finally obtained in examples 1 to 5 and comparative examples 1 to 4 were made into button cells using a metal lithium sheet as a negative electrode for evaluation tests, 0.2C charging was performed under the conditions of normal temperature and a voltage interval of 3.0 to 4.3V, then 0.1C and 1C rate discharging was performed respectively, 1C charging and 1C discharging at 25 ℃ for 50-cycle retention rate tests, and 0.5C charging and 0.5C discharging at 45 ℃ for 50-cycle retention rate tests, and the physicochemical index tests and the power-on results are shown in table 1 below.
TABLE 1 comparison of Performance of example and comparative cathode materials
As can be seen from table 1, in examples 1 to 5, when the cerium bismuth composite oxide with a proper proportion is added in the one-firing process, compared with comparative examples 1 to 2, the positive electrode material of the present invention has higher 0.1C discharge capacity and 1C discharge capacity, and simultaneously has better cycle effects at 25 ℃ and 45 ℃, which indicates that the capacity, rate and cycle retention rate of the cerium bismuth composite oxide material doped with a proper proportion in the positive electrode material are higher. As can be seen from comparison between example 3 and comparative example 3, when the molar ratio of cerium to bismuth in the cerium bismuth composite oxide is less than 1.5, both the cycle performance and rate characteristics of the positive electrode material are affected, and the performance effect is not as good as in example 3. Compared with the embodiment 3, the cerium oxide doped composite material has the advantages that the capacity, multiplying power and cycle performance of the material are not as good as the effect of doping by adding the cerium bismuth composite oxide. The positive electrode material of the cerium-bismuth composite oxide doped lithium ion battery has excellent capacity, rate capability and cycle performance.
Claims (5)
1. The preparation method of the cerium bismuth composite oxide doped lithium ion battery anode material is characterized in that the cerium bismuth composite oxide is doped in the lithium ion battery anode material, wherein the molar ratio of cerium to bismuth in the cerium bismuth composite oxide is (1.5-9): 1, and the molecular formula of the lithium ion battery anode material is Li a Ni b Co c M d (Ce x Bi 1-x ) e O 2 M is at least one of Mn, al, zr, P, ti and Mg, and the values of a, b, c, d and e meet the following requirements: a is more than or equal to 0.9 and less than or equal to 1.2, b is more than or equal to 0.7 and less than or equal to 1, c is more than 0 and less than or equal to 0.2, d is more than 0 and less than or equal to 0.1, e is more than or equal to 0.0001 and less than or equal to 0.01, and x is more than 0 and less than or equal to 1; the preparation method comprises the following steps:
(1) Mixing a cerium source and a bismuth source according to a molar ratio, dissolving the mixture in a nitric acid solution, adding a sodium hydroxide solution to carry out a solvothermal reaction, and filtering and drying the mixture after the reaction is finished to obtain a cerium bismuth composite oxide; wherein the solvothermal reaction temperature is 80-150 ℃, and the reaction time is 15-30h;
(2) Mixing the cerium bismuth composite oxide obtained in the step (1), a positive electrode material hydroxide precursor and lithium salt according to the stoichiometric ratio of chemical elements, and placing the mixture in an oxygen atmosphere furnace for sintering; wherein, the sintering refers to sintering at 300-550 ℃ for 2-6h, then heating to 600-850 ℃ and sintering at a heat preservation time for 2-30h, wherein the heating rate is 3-30 ℃/min;
(3) And (3) washing and drying the sintered product obtained in the step (2), and then performing secondary sintering to obtain the cerium-bismuth composite oxide doped lithium ion battery anode material, wherein the temperature of the secondary sintering is 300-700 ℃, and the sintering time is 3-30h.
2. The method according to claim 1, wherein in the step (1), the concentration of the nitric acid solution is 3 to 5mol/L, the concentration of the sodium hydroxide solution is 6 to 10mol/L, and the volume ratio of the sodium hydroxide solution to the nitric acid solution is 5 to 10.
3. The method according to claim 1 or 2, wherein in the step (1), the cerium source is one or more selected from cerium nitrate, cerium phosphate and cerium hydroxide; the bismuth source is selected from one or more of bismuth nitrate, bismuth carbonate and bismuth hydroxide;
in the step (2), the lithium source is selected from one or more of lithium hydroxide, lithium carbonate, lithium sulfate and lithium nitrate.
4. The method according to any one of claims 1 or 2, wherein in the step (3), the solvent to be washed is ethanol, methanol or deionized water.
5. The method according to claim 1, wherein the positive electrode material for lithium ion batteries has a spheroidal secondary particle structure composed of primary particles, and the secondary particles have a particle diameter D50 of 2 to 25 μm.
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| CN115411257A (en) * | 2022-09-29 | 2022-11-29 | 广东邦普循环科技有限公司 | Surface double-layer coated lithium-rich manganese-based positive electrode material and preparation method and application thereof |
| CN116371397A (en) * | 2023-01-05 | 2023-07-04 | 华南理工大学 | Ce doped Bi 0 /Bi 2 O 3 /Bi 2 O 2.75 Nanosheet photocatalyst and preparation and application thereof |
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