CN108054371B - Lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life and preparation method thereof - Google Patents
Lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life and preparation method thereof Download PDFInfo
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Abstract
A lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life and a preparation method thereof belong to the technical field of material synthesis, and the chemical formula of the positive electrode material is L i [ L i ]a(MnxNiyCoz)1−a]O2. The preparation method comprises the following steps: preparing a manganese nickel cobalt carbonate spherical precursor by adopting a coprecipitation method; uniformly mixing and calcining the manganese-nickel-cobalt-carbonate spherical precursor and a lithium source to obtain a spherical lithium-rich manganese-based positive electrode material; and carrying out hydrothermal post-treatment on the spherical lithium-rich manganese-based positive electrode material to obtain the lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life. According to the invention, through the combined action of the crystal nucleation control agent and the complexing agent, the crystallization surface energy of a coprecipitation system is reduced, the tap density of the material is improved, the high discharge capacity is provided by utilizing the multi-metal synergistic action of manganese nickel cobalt, the thickness and the proportion of mixed-arrangement layers of nickel and lithium on the surfaces of secondary particles are reduced by utilizing the hydrothermal solid-liquid interface reaction, the diffusion coefficient of lithium ions is improved, the rate capacity of the material is enhanced, and the cycle stability of the material is improved.
Description
Technical Field
The invention belongs to the technical field of material synthesis, relates to a lithium ion battery positive electrode material and a preparation method thereof, and particularly relates to a lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life and a preparation method thereof.
Background
Lithium ion batteries have found widespread use in the field of portable electronic devices, both in electric vehicles and in energy storageThe high-performance lithium ion positive electrode material has the following elements of higher discharge voltage and capacity, stable and reliable cycle performance, good thermal stability, higher electron/ion conductivity, easy synthesis, low production cost and environmental friendliness2(TM is transition metal ion such as Co, Ni, Mn, etc.), spinel structure L iMn2O4And olivine structure L iFePO4And the like.
The actual capacity of the materials is between 100 and 200 mAh/g, and the development requirements of the positive electrode material for improving reversible specific capacity and reducing cost are difficult to meeta(MnvNixCoy)1−a]O2The positive electrode material can provide an actual reversible specific capacity of 250-300 mAh/g under a charging voltage higher than 4.5V, has the advantages of high energy density, good thermal stability, low raw material cost, environmental friendliness and the like, and is used for developing high energy density>300 Wh/kg), an important candidate positive electrode material for low-cost lithium ion batteries. Research shows that the micron-sized spherical structure is beneficial to improving the volume energy density of the lithium-rich manganese-based material, but the lithium-rich manganese-based anode material obtained by the traditional preparation process has large particle size and longer lithium ion diffusion path, so that the material has poor high-current discharge and high rate performance; the particle structure is not compact, the tap density is low, and the increase of the volume energy density of the material is limited; in addition, metal element segregation is easily generated on the particle surface, so that the nickel-lithium mixed-discharge degree on the surface is high, the generation of a surface heterogeneous phase is easily induced, and the capacity attenuation of the material in the circulation process is accelerated.
Disclosure of Invention
The invention aims to solve the problems of low tap density, poor rate performance and fast capacity attenuation of the existing lithium-rich manganese-based cathode material, and provides a lithium-rich manganese-based cathode material with high tap density, high rate and long service life and a preparation method thereof. According to the method, micron-sized compact spherical particles are constructed, high tap density is provided, high discharge capacity is provided by utilizing the synergistic effect of multiple metals in secondary particles, the thickness of a nickel-lithium mixed arrangement layer on the surface of the secondary particles is reduced and the nickel-lithium mixed arrangement proportion on the surface is reduced by utilizing hydrothermal solid-liquid interface reaction, so that the diffusion coefficient of lithium ions is improved, the multiplying power capacity of a material is enhanced, and the cycle performance of the material is improved. The nucleation and growth of crystal grains are regulated and controlled by a coprecipitation method, the high-tap lithium-rich manganese-based anode material with moderate particle size and compact structure is prepared, the atomic arrangement of the surface of secondary particles is regulated and controlled by adopting hydrothermal post-treatment, the thickness of the nickel-lithium mixed arrangement layer on the surface is reduced, the nickel-lithium mixed arrangement proportion on the surface is reduced, the rate capability of the material is improved, and the cycle life of the material is prolonged.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life has a chemical formula of L i [ L i ]a(MnxNiyCoz)1−a]O2Wherein, 0<a<0.5，x+y+z=1，0≤y<x，0≤z<x, x<1，0≤y≤0.5，0≤z≤0.5。
The preparation method of the lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life comprises the following steps:
the method comprises the following steps: the preparation method of the manganese nickel cobalt carbonate spherical precursor by adopting a coprecipitation method comprises the following specific steps:
(1) according to the formula L i [ L ia(MnxNiyCoz)1−a]O2Weighing soluble manganese salt, nickel salt and cobalt salt with corresponding molar ratios and a certain amount of crystal nucleation control agent, and dissolving the raw materials in deionized water to prepare a solution M with the total concentration of manganese and nickel cobalt being 0.5-5 mol/L and the concentration of the crystal nucleation control agent being 0.05-0.5 mol/L;
(2) preparing a carbonate precipitant and a complexing agent into a solution B with the solubility of the carbonate precipitant being 0.5-5 mol/L and the concentration of the complexing agent being 0.1-0.5 mol/L by using deionized water;
(3) adding the solution B into the solution M under strong stirring, controlling the molar ratio of the mixed metal salt to the crystal nucleation control agent to the carbonate precipitant to the complexing agent to be 1: 0.05-0.2: 1: 0.1-0.5, and reacting for 3-10 hours under the conditions that the stirring speed is 500-1500 rpm and the temperature is 10-25 ℃ to obtain a manganese nickel cobalt carbonate spherical precursor;
step two: uniformly mixing and calcining a manganese nickel cobalt carbonate spherical precursor and a lithium source to obtain a spherical lithium-rich manganese-based anode material, which comprises the following specific steps:
(1) uniformly mixing the manganese-nickel-cobalt carbonate spherical precursor with a lithium source;
(2) heating the mixture from room temperature to 600-900 ℃ at the heating rate of 1-5 ℃/min, and calcining for 6-15 h to obtain the spherical lithium-rich manganese-based positive electrode material;
step three: carrying out hydrothermal post-treatment on the spherical lithium-rich manganese-based positive electrode material, and specifically comprising the following steps:
(1) adding a certain amount of spherical lithium-rich manganese-based positive electrode material into deionized water, controlling the solid-liquid mass ratio to be 1: 1-5, putting mixed solid and liquid into a stainless steel hot kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment at a certain temperature for a certain time;
(2) after the reaction is finished, filtering and collecting the sample, putting the sample into a muffle furnace, and performing reaction at 100-300 DEG CoCAnd drying in the air for 12 h to obtain the lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, through the combined action of the crystal nucleation control agent and the complexing agent, the crystallization surface energy of a coprecipitation system is reduced, the rapid preparation (3-10 h) of the compact spherical lithium-rich manganese-based positive electrode material is realized under the conditions of no need of pH value adjustment and low temperature (10-25 ℃), the particle size of the material is about 3-5 mu m, and the tap density is 2.4-2.8 g/cm3High loading of active material during coating (>8 mg/cm2）。
(2) By utilizing the multi-metal synergy of manganese, nickel and cobaltThe effect of providing high discharge capacity (the capacity can reach 270-310 mAh/g under 0.1C), the hydrothermal solid-liquid interface reaction reduces the thickness of the nickel-lithium mixed discharge layer on the surface of the secondary particles (<3 nm) and reduced surface Ni-Li mixing ratio<2%) to increase the lithium ion diffusion coefficient: (>7.0×10-13cm2And/s), the multiplying power capacity of the material is enhanced (the capacity under 1C can reach 220-260 mAh/g, the capacity under 5C can reach 150-190 mAh/g, the capacity under 10C can reach 110-150 mAh/g), and the cycle performance of the material is improved (the capacity retention rate is more than 85% after 200 cycles under 1C and 400 cycles under 3C).
(3) The invention has simple process and obvious and reliable performance improvement, and is suitable for large-scale production.
Drawings
Fig. 1 is an SEM image of the cathode material prepared by the present invention.
Fig. 2 is an XRD pattern of the cathode material prepared in the present invention.
Fig. 3 is a STEM graph of the secondary particle surface before hydrothermal treatment of the positive electrode material prepared in the present invention.
Fig. 4 is a STEM magnified view of the secondary particle surface before hydrothermal treatment of the positive electrode material prepared in the present invention.
Fig. 5 is a STEM graph of the secondary particle surface after hydrothermal treatment of the positive electrode material prepared in the present invention.
Fig. 6 is a STEM magnified view of the secondary particle surface after hydrothermal treatment of the positive electrode material prepared in the present invention.
FIG. 7 is a graph of the rate performance of the positive electrode material prepared by the invention.
Fig. 8 is a capacity curve diagram of the positive electrode material prepared by the present invention cycling 200 times at 1C.
Fig. 9 is a capacity curve diagram of the positive electrode material prepared by the present invention cycling 400 times at 3C.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
In one embodiment, the lithium-rich manganese-based positive electrode material has a high tap density, a high magnification and a long life, and the chemical formula of the positive electrode material is L i [ L i ]a(MnxNiyCoz)1−a]O2Wherein, 0<a<0.5，x+y+z=1，0≤y<x，0≤z<x, x<1，0≤y≤0.5，0≤z≤0.5。
The second embodiment is as follows: a method for preparing a lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life, which is a combination of coprecipitation, high-temperature sintering and hydrothermal reaction, comprises the following steps:
the method comprises the following steps: the preparation method of the manganese nickel cobalt carbonate spherical precursor by adopting a coprecipitation method comprises the following specific steps:
(1) according to the formula L i [ L ia(MnxNiyCoz)1−a]O2Weighing soluble manganese salt, nickel salt and cobalt salt with corresponding molar ratios and a certain amount of crystal nucleation control agent, and dissolving the raw materials in deionized water to prepare a solution M with the total concentration of manganese and nickel cobalt being 0.5-5 mol/L and the concentration of the crystal nucleation control agent being 0.05-0.5 mol/L;
(2) preparing a carbonate precipitant and a complexing agent into a solution B with the solubility of the carbonate precipitant being 0.5-5 mol/L and the concentration of the complexing agent being 0.1-0.5 mol/L by using deionized water;
(3) adding the solution B into the solution M under strong stirring, controlling the molar ratio of the mixed metal salt to the crystal nucleation control agent to the carbonate precipitant to the complexing agent to be 1: 0.05-0.2: 1: 0.1-0.5, and reacting for 3-10 hours under the conditions that the stirring speed is 500-1500 rpm and the temperature is 10-25 ℃ to obtain a manganese nickel cobalt carbonate spherical precursor;
step two: uniformly mixing and calcining a manganese nickel cobalt carbonate spherical precursor and a lithium source to obtain a spherical lithium-rich manganese-based anode material, which comprises the following specific steps:
(1) uniformly mixing the manganese-nickel-cobalt carbonate spherical precursor with a lithium source;
(2) heating the mixture from room temperature to 600-900 ℃ at the heating rate of 1-5 ℃/min, and calcining for 6-15 h to obtain the spherical lithium-rich manganese-based positive electrode material;
step three: carrying out hydrothermal post-treatment on the spherical lithium-rich manganese-based positive electrode material, and specifically comprising the following steps:
(1) adding a certain amount of spherical lithium-rich manganese-based positive electrode material into deionized water, controlling the solid-liquid mass ratio to be 1: 1-5, putting mixed solid and liquid into a stainless steel hot kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment at a certain temperature for a certain time;
(2) after the reaction is finished, filtering and collecting the sample, putting the sample into a muffle furnace, and performing reaction at 100-300 DEG CoCAnd drying in the air for 12 h to obtain the lithium-rich manganese-based anode material subjected to hydro-thermal treatment, namely the lithium-rich manganese-based anode material with high tap density, high multiplying power and long service life.
The third concrete implementation mode: in the preparation method of the lithium-rich manganese-based positive electrode material with high tap density, high magnification and long life according to the second embodiment, in the first step, the manganese salt is one or a mixture of manganese sulfate, manganese formate, manganese acetate, manganese oxalate, manganese chloride or manganese nitrate; the nickel salt is one or a mixture of nickel sulfate, nickel formate, nickel acetate, nickel oxalate, nickel chloride or nickel nitrate; the cobalt salt is one or a mixture of more of cobalt sulfate, cobalt formate, cobalt acetate, cobalt oxalate, cobalt chloride or cobalt nitrate; the crystal nucleation control agent is one or a mixture of more of triton, polyvinylpyrrolidone, cetyl trimethyl ammonium bromide and polyvinyl alcohol; the carbonate precipitant is one or more of sodium carbonate, sodium bicarbonate and ammonium carbonate; the complexing agent is one or a mixture of more of ammonium bicarbonate, ammonium bisulfate, ammonium sulfate and ammonia water.
The fourth concrete implementation mode: in the second step, the lithium source is one or a mixture of more of lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate, lithium carbonate, and lithium chloride; the mixing mode adopted when the manganese nickel cobalt carbonate spherical precursor is mixed with the lithium source is liquid phase mixing or solid phase mixing, the liquid phase mixed solvent is absolute ethyl alcohol, and the mass ratio of the total solid salt to the solvent is 1: 1.
The fifth concrete implementation mode: in the second specific embodiment, the preparation method of the lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life includes the third step, the hydrothermal treatment temperature is 120-220%oC; the hydrothermal treatment time is 5-10 h.
The sixth specific implementation mode: in the second and third steps, the lithium-rich manganese-based positive electrode material has a compact spherical structure, the particle size is 3-5 μm, and the tap density is 2.4-2.8 g/cm3。
Example 1:
weighing manganese sulfate, nickel sulfate and cobalt sulfate according to a molar ratio of Mn to Ni to Co = 0.54 to 0.13, weighing a certain amount of crystal nucleation control agent (polyvinylpyrrolidone), dissolving the raw materials in deionized water to prepare a solution M with a total concentration of manganese and nickel cobalt of 0.5 mol/L and a concentration of the crystal nucleation control agent of 0.05 mol/L, adding a solution (ammonium bicarbonate) of 0.5 mol/L sodium carbonate precipitant and 0.2 mol/L complexing agent into the solution M by adopting a coprecipitation method, controlling the molar ratio of mixed metal salt, the crystal nucleation control agent, the carbonate precipitant and the complexing agent to be 1:0.1:1:0.2, stirring at 1200 rpm, reacting at 20 ℃ for 5 hours, performing suction filtration after the reaction is finished, repeatedly washing, removing impurities, drying to obtain a manganese nickel cobalt spherical precursor, weighing lithium carbonate and a manganese nickel cobalt spherical precursor according to a molar ratio of 1.2:0.8, uniformly mixing the manganese nickel cobalt spherical precursor with a solid-phase carbonate precursor, placing the manganese nickel cobalt spherical precursor into a muffle furnace in an air atmosphere, heating the mixed metal cobalt spherical precursor to obtain a mixed manganese nickel cobalt spherical precursor, calcining a certain amount of lithium-nickel cobalt material, controlling a temperature of a solid-lithium-enriched stainless steel-based mixed material from a temperature lining of 10 liter stainless steel kettle to a temperature of 10-lithium-oC, carrying out hydrothermal treatment for 6 hours, filtering and collecting a sample after the reaction is finished, and carrying out hydrothermal treatment in a muffle furnace 200oCDrying the mixture in the air for 12 hours,obtaining the lithium-rich manganese-based material subjected to hydro-thermal treatment, namely the lithium-rich manganese-based anode material with high tap density, high multiplying power and long service life, wherein the chemical formula is L i1.2Mn0.54Ni0.13Co0.13O2. As shown in FIG. 1, the spherical lithium-rich manganese-based cathode material prepared in this example has a uniform spherical morphology, which is characterized in that the spherical particle size of the material is about 3 μm, and the tap density is about 2.6 g/cm3. As shown in fig. 2, the XRD curve of the material prepared in this example showed characteristic peaks of superlattice, indicating that the synthesized material is a lithium-rich manganese-based material. As shown in fig. 3 and 4, the atomic scale high resolution scanning transmission electron microscope shows that a nickel-lithium mixed-arranged layer of about 3 nm exists on the surface of the secondary particles of the material before the hydrothermal treatment, and the nickel-lithium mixed-arranged ratio is 3.5%. As shown in FIGS. 5 and 6, the nickel-lithium mixed-layer on the surface after the hydrothermal treatment<0.5 nm, the nickel-lithium mixed discharge ratio is 1.3%, and the lithium ion diffusion coefficient of the lithium-rich manganese-based cathode material with high tap density, high multiplying power and long service life obtained by hydrothermal treatment is 7.9 × 10-13cm2And s. Under 0.1C, the discharge specific capacity of the obtained material at 2-4.8V can reach 301 mAh/g; as shown in the rate performance curve of fig. 7, the discharge specific capacities of the materials prepared in this example at 1, 3, 5 and 10C were about 248, 201, 163 and 133 mAh/g, respectively; as shown in fig. 8, the capacity retention rate was 91.5% after 200 cycles at 1C; as shown in fig. 9, the capacity retention rate after 400 cycles at 3C was 89.0%.
Example 2:
weighing manganese sulfate, nickel nitrate and cobalt acetate according to a molar ratio of Mn to Ni to Co = 0.5 to 0.15 to 0.1, weighing a certain amount of crystal nucleation control agent (cetyl trimethyl ammonium bromide to polyvinyl alcohol =1 to 1 mol/mol), dissolving the raw materials in deionized water to prepare a solution M with a total concentration of manganese nickel cobalt of 1 mol/L and a concentration of the crystal nucleation control agent of 0.2 mol/L, adding a 2 mol/L precipitator (sodium bicarbonate to ammonium carbonate =1 to 1 mol/mol) and a 1 mol/L complexing agent (ammonium bicarbonate to ammonia water =1 to 2 mol/mol) into the solution M by adopting a coprecipitation method, controlling the molar ratio of mixed metal salt, the crystal nucleation control agent, the carbonate precipitator and the complexing agent to be 1 to 0.05 to 0.4, carrying out suction filtration at a stirring speed of 1000 revolutions per minute and at a temperature of 10 ℃ for 8 hours, and carrying out reaction for 8 hours after the reaction is finishedAnd repeatedly washing, removing impurities, and drying to obtain the manganese nickel cobalt carbonate spherical precursor. Weighing lithium carbonate and a manganese nickel cobalt carbonate spherical precursor according to a molar ratio of 1.25:0.75, uniformly mixing in a liquid phase mixing mode, wherein a liquid phase mixed solvent is absolute ethyl alcohol, the mass ratio of the total solid salt to the solvent is 1:1, placing the mixture into a muffle furnace air atmosphere, and calcining for 12 hours from room temperature to 900 ℃ at a heating rate of 3 ℃/min to obtain the spherical lithium-rich manganese-based positive electrode material. Adding a certain amount of spherical lithium-rich manganese-based positive electrode material into deionized water, controlling the solid-liquid mass ratio to be 1:5, putting the mixed solid-liquid into a stainless steel hot kettle with a polytetrafluoroethylene lining, and heating at 160 DEG CoC, carrying out hydrothermal treatment for 5 hours, filtering and collecting a sample after the reaction is finished, and carrying out a muffle furnace 250oCDrying in the air for 12 h to obtain the lithium-rich manganese-based material subjected to hydro-thermal treatment, namely the lithium-rich manganese-based anode material with high tap density, high multiplying power and long service life, wherein the chemical formula is L i1.25Mn0.5Ni0.15Co0.1O2. The spherical lithium-rich manganese-based cathode material prepared by the embodiment has a uniform spherical shape, and is specifically represented by a spherical particle size of about 4 μm and a tap density of about 2.5 g/cm3. The XRD curve of the material prepared in this example shows the characteristic peak of the superlattice, which indicates that the synthetic material is a lithium-rich manganese-based material. Atomic scale high resolution scanning transmission electron microscope shows that about 5 nm nickel-lithium mixed arrangement layer exists on the surface of secondary particles of the material before hydrothermal treatment, the nickel-lithium mixed arrangement proportion is 5.5%, and the nickel-lithium mixed arrangement layer on the surface after hydrothermal treatment<2 nm, the nickel-lithium mixed discharge ratio is 1.8%, and the lithium ion diffusion coefficient of the lithium-rich manganese-based cathode material with high tap density, high multiplying power and long service life obtained by hydrothermal treatment is 7.3 × 10-13cm2And s. Under 0.1C, the discharge specific capacity of the obtained material at 2-4.8V can reach 285 mAh/g; the discharge specific capacities of the materials prepared in the embodiment under 1, 3, 5 and 10C are respectively about 236 mAh/g, 191, 153 and 115 mAh/g; the capacity retention rate after 200 cycles at 1C was 89.5%; the capacity retention after 400 cycles at 3C was 87.4%.
Example 3:
weighing manganese chloride, nickel nitrate and cobalt sulfate according to the molar ratio of Mn to Ni to Co = 0.7 to 0.15 to 0.05, and weighing a certain amount of manganese chloride, nickel nitrate and cobalt sulfateDissolving the raw materials in deionized water to prepare a solution M with the total concentration of manganese and nickel cobalt being 1.5 mol/L and the concentration of the crystal nucleation control agent being 0.05 mol/L, adding a solution of 2 mol/L precipitator (sodium carbonate: sodium bicarbonate: ammonium carbonate =1:1:1 mol/mol) and 0.5 mol/L ammonium bicarbonate complexing agent into the solution M by adopting a coprecipitation method, controlling the molar ratio of mixed metal salt, the crystal nucleation control agent, the carbonate precipitator and the complexing agent to be 1:0.2:1:0.3, stirring at the speed of 1000 revolutions per minute and under the condition of 15 ℃ for 5 hours, performing suction filtration after the reaction is finished, repeatedly washing, removing impurities, drying to obtain a manganese nickel cobalt spherical precursor, weighing lithium carbonate and uniformly mixing the lithium carbonate with solid phase, placing the mixture into a muffle furnace air atmosphere, heating from 4 ℃/min to 10 min to obtain a manganese nickel cobalt spherical precursor, placing the manganese nickel cobalt spherical precursor into a polytetrafluoroethylene-based sintered stainless steel kettle, calcining the manganese nickel cobalt spherical precursor, and heating the sintered lithium-nickel cobalt spherical precursor to obtain a solid-nickel cobalt spherical stainless steel material, and calcining the manganese-nickel-cobalt-based stainless steel material, wherein the solid phase stainless steel material is calcined in the muffle furnace air atmosphere, the polytetrafluoroethylene-nickel-cobalt spherical stainless steel material, theoC, carrying out hydrothermal treatment for 5 hours, filtering and collecting a sample after the reaction is finished, and carrying out hydrothermal treatment in a muffle furnace 300oCDrying in the air for 12 h to obtain the lithium-rich manganese-based material subjected to hydro-thermal treatment, namely the lithium-rich manganese-based anode material with high tap density, high multiplying power and long service life, wherein the chemical formula is L i1.1Mn0.7Ni0.15Co0.05O2. The spherical lithium-rich manganese-based cathode material prepared by the embodiment has a uniform spherical shape, and is specifically represented by a spherical particle size of about 5 μm and a tap density of about 2.8 g/cm3. The XRD curve of the material prepared in this example shows the characteristic peak of the superlattice, which indicates that the synthetic material is a lithium-rich manganese-based material. Atomic scale high resolution scanning transmission electron microscope shows that about 4nm nickel-lithium mixed arrangement layer exists on the surface of secondary particles of the material before hydrothermal treatment, the nickel-lithium mixed arrangement proportion is 4.5%, and the nickel-lithium mixed arrangement layer on the surface after hydrothermal treatment<1 nm, the nickel-lithium mixed discharge ratio is 1.5%, and the lithium ion diffusion coefficient of the lithium-rich manganese-based cathode material with high tap density, high multiplying power and long service life obtained by hydrothermal treatment is 7.6 × 10-13cm2And s. Under 0.1C, the discharge specific capacity of the obtained material at 2-4.8V can reach 295 mAh/g; the discharge specific capacities of the materials prepared in the embodiment under 1, 3, 5 and 10C are about 239, 198, 154 and 112 mAh/g respectively; the capacity retention rate after 200 cycles at 1C was 88.7%; the capacity retention after 400 cycles at 3C was 86.9%.
Claims (5)
1. A preparation method of a lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life is disclosed, wherein the chemical formula of the positive electrode material is L i [ L i ]a(MnxNiyCoz)1−a]O2Wherein, 0<a<0.5，x+y+z=1，0≤y<x，0≤z<x，x<1, y is more than or equal to 0 and less than or equal to 0.5, and z is more than or equal to 0 and less than or equal to 0.5; the method is characterized in that: the method comprises the following steps:
the method comprises the following steps: the preparation method of the manganese nickel cobalt carbonate spherical precursor by adopting a coprecipitation method comprises the following specific steps:
(1) according to the formula L i [ L ia(MnxNiyCoz)1−a]O2Weighing soluble manganese salt, nickel salt and cobalt salt with corresponding molar ratios and a certain amount of crystal nucleation control agent, and dissolving the raw materials in deionized water to prepare a solution M with the total concentration of manganese and nickel cobalt being 0.5-5 mol/L and the concentration of the crystal nucleation control agent being 0.05-0.5 mol/L;
(2) preparing a carbonate precipitant and a complexing agent into a solution B with the solubility of the carbonate precipitant being 0.5-5 mol/L and the concentration of the complexing agent being 0.1-0.5 mol/L by using deionized water;
(3) adding the solution B into the solution M under strong stirring, and controlling the molar ratio of the mixed metal salt, the crystal nucleation control agent, the carbonate precipitator and the complexing agent to be 1: 0.05-0.2: 1: 0.1-0.5, reacting for 3-10 h under the conditions that the stirring speed is 500-1500 revolutions per minute and the temperature is 10-25 ℃ to obtain a manganese nickel cobalt carbonate spherical precursor;
step two: uniformly mixing and calcining a manganese nickel cobalt carbonate spherical precursor and a lithium source to obtain a spherical lithium-rich manganese-based anode material, which comprises the following specific steps:
(1) uniformly mixing the manganese-nickel-cobalt carbonate spherical precursor with a lithium source;
(2) heating the mixture from room temperature to 600-900 ℃ at the heating rate of 1-5 ℃/min, and calcining for 6-15 h to obtain the spherical lithium-rich manganese-based positive electrode material;
step three: carrying out hydrothermal post-treatment on the spherical lithium-rich manganese-based positive electrode material, and specifically comprising the following steps:
(1) adding a certain amount of spherical lithium-rich manganese-based positive electrode material into deionized water, and controlling the solid-liquid mass ratio to be 1: 1-5, putting the mixed solid and liquid into a stainless steel water heating kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal treatment at a certain temperature for a certain time;
(2) and after the reaction is finished, filtering and collecting the sample, putting the sample into a muffle furnace, and drying the sample in the air at the temperature of 100-300 ℃ for 12 hours to obtain the lithium-rich manganese-based anode material with high tap density, high multiplying power and long service life.
2. The preparation method of the lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life as claimed in claim 1, characterized in that: in the first step, the manganese salt is one or a mixture of manganese sulfate, manganese formate, manganese acetate, manganese oxalate, manganese chloride or manganese nitrate; the nickel salt is one or a mixture of nickel sulfate, nickel formate, nickel acetate, nickel oxalate, nickel chloride or nickel nitrate; the cobalt salt is one or a mixture of more of cobalt sulfate, cobalt formate, cobalt acetate, cobalt oxalate, cobalt chloride or cobalt nitrate; the crystal nucleation control agent is one or a mixture of more of triton, polyvinylpyrrolidone, cetyl trimethyl ammonium bromide and polyvinyl alcohol; the carbonate precipitant is one or more of sodium carbonate, sodium bicarbonate and ammonium carbonate; the complexing agent is one or a mixture of more of ammonium bicarbonate, ammonium bisulfate, ammonium sulfate and ammonia water.
3. The preparation method of the lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life as claimed in claim 1, characterized in that: in the second step, the lithium source is one or a mixture of more of lithium hydroxide, lithium acetate, lithium nitrate, lithium ethoxide, lithium formate, lithium carbonate and lithium chloride; the mixing mode adopted when the manganese nickel cobalt carbonate spherical precursor is mixed with the lithium source is liquid phase mixing or solid phase mixing, the liquid phase mixed solvent is absolute ethyl alcohol, and the mass ratio of the total solid salt to the solvent is 1: 1.
4. the preparation method of the lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life as claimed in claim 1, characterized in that: in the third step, the hydrothermal treatment temperature is 120-220%oC; the hydrothermal treatment time is 5-10 h.
5. The preparation method of the lithium-rich manganese-based positive electrode material with high tap density, high multiplying power and long service life as claimed in claim 1, characterized in that: in the second and third steps, the particle size of the lithium-rich manganese-based positive electrode material is 3-5 mu m, and the tap density is 2.4-2.8 g/cm3。
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| CN108832118A (en) * | 2018-06-25 | 2018-11-16 | 西南交通大学 | MnO2The preparation method of intermediate and preparation method thereof and lithium-rich manganese-based anode material |
| CN110718686A (en) * | 2018-07-11 | 2020-01-21 | 西北大学 | Preparation method of lithium-rich manganese-based positive electrode material and preparation method of precursor thereof |
| CN109346718B (en) * | 2018-09-21 | 2020-12-18 | 山东省科学院能源研究所 | Single crystal nickel cobalt lithium manganate precursor and preparation method and application thereof |
| CN111430701B (en) * | 2019-11-29 | 2022-10-25 | 蜂巢能源科技有限公司 | Lithium-rich carbonate precursor and preparation method and application thereof |
| CN111434617B (en) * | 2019-12-27 | 2022-05-27 | 蜂巢能源科技有限公司 | Aluminum-coated precursor and preparation method and application thereof |
| CN111498908A (en) * | 2020-04-27 | 2020-08-07 | 中信大锰矿业有限责任公司 | Preparation method of quasi-spherical manganese-rich ternary precursor |
| CN112290009A (en) * | 2020-10-30 | 2021-01-29 | 清华大学深圳国际研究生院 | Manganese-based lithium-rich oxide cathode material, preparation method thereof and electrochemical device using manganese-based lithium-rich oxide cathode material |
| CN112436135B (en) * | 2020-11-20 | 2022-07-26 | 国联汽车动力电池研究院有限责任公司 | Cathode material and preparation method and application thereof |
| CN112652763A (en) * | 2020-12-22 | 2021-04-13 | 哈尔滨工业大学 | High-capacity, high-rate and high-tap-density sodium ion battery positive electrode material and preparation method thereof |
| CN114906881A (en) * | 2022-04-29 | 2022-08-16 | 浙江格派钴业新材料有限公司 | Preparation method of cation-substituted modified spherical-like sodium nickel manganese oxide positive electrode material |
| CN114843474A (en) * | 2022-05-17 | 2022-08-02 | 天能新能源(湖州)有限公司 | High-rate lithium ion battery positive electrode material and preparation method thereof |
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