CN111987310A - Active metal oxide multiple-modification cathode material and preparation method thereof - Google Patents
Active metal oxide multiple-modification cathode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an active metal oxide multiple modification anode material and a preparation method thereof, and synthesizes LiNixMnyO2·nGa2O3The positive electrode material is characterized in that x, y and n are mole numbers, and x is more than or equal to 0.8<1，0<y≤0.2，x+y＝1，0<n≤0.05，Ga2O3Is an active oxide. The surface of the anode material is coated with a uniform coating layer, and the thickness of the coating layer is about 2.5-3.5 nm. The experimental preparation method comprises the following steps: mixing galliumThe source is coated on the surface of a precursor or a positive electrode material, and after the precursor is mixed with lithium, the precursor is sintered at high temperature to obtain metal ion Ga3+Surface doped and Ga2O3And the surface of the anode material is coated. The invention improves LiNixMnyO2Rate capability and cycle performance of the positive electrode material; the method has the advantages of simple preparation process, low cost and less environmental pollution, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of lithium ion battery anode materials, in particular to an active metal oxide multiple modification anode material and a preparation method thereof.
Background
Cobalt has a long standing price due to its scarcity and strategic value. The reduction of the cobalt content becomes the first measure for reducing the cost of the nickel cobalt lithium aluminate (NCA) or nickel cobalt lithium manganate (NCM) anode material, and the development of high nickel cobalt-free material becomes the inevitable trend; the cobalt content is reduced while the nickel content is high, so that the energy density of the battery can be effectively improved, and the production cost can be reduced; jeff Dahn team early research finds LiNi0.9Co0.05Al0.05O2And LiNi0.95Al0.05O2、LiNi0.95Mn0.05O2The electrochemical performance of the anode material is very close, and the anode material is expected to contain no cobalt any more.
Along with the increase of the content of nickel, the capacity and the energy density of the lithium ion battery are correspondingly improved; however, the increase of nickel content has adverse effects on the cycle performance and thermal stability of the battery, mainly manifested by the loss of charge-discharge capacity and the large capacity attenuation in high temperature environment, and this disadvantage limits the application of high-nickel cobalt-free cathode materials.
The modification of the anode material mainly comprises doping and cladding, and the doping and cladding can change the performance of the material and increase the conductivity, the cycle stability and the safety. However, the problem of poor cycle performance and rate performance cannot be effectively solved by a single modification method, and although the coated oxide can reduce the side reaction of the material and the electrolyte, the oxide does not have electrochemical activity and reduces the specific discharge capacity and energy density; meanwhile, the rate performance can be improved by doping the metal elements, but the cycling stability of the material is not improved too much.
Therefore, aiming at the defects in the prior art, the rate capability and the cycle performance of the cathode material are simultaneously improved, and the provision of the active metal oxide multiple modification cathode material and the preparation method thereof is particularly important.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides an active metal oxide multiple-modification cathode material and a preparation method thereof. The battery assembled by the positive electrode material has excellent rate performance and cycle performance; the method has the advantages of simple preparation process, low cost and less environmental pollution, and is suitable for industrial production.
One of the above objects of the present invention is achieved by the following technical means:
an active metal oxide multiple-modification anode material and a preparation method thereof, synthesizing LiNixMnyO2·nGa2O3The positive electrode material is characterized in that x, y and n are mole numbers, and x is more than or equal to 0.8<1，0<y≤0.2，x+y＝1，0<n≤0.05，Ga2O3Is an active oxide, and forms a uniform coating layer with a thickness of 2.5-3.5 nm.
The technical scheme adopted for further solving the technical problems is as follows:
an active metal oxide multiple modification anode material and a preparation method thereof are prepared by the following steps:
(1) in terms of molar ratio, firstly, 2-5 moL/L of NiSO4·6H2O、MnSO4·H2Uniformly mixing O (Ni: Mn ═ x: y), and simultaneously adding 5.5-7.5 mol/L of NaOH solution and NH serving as a complexing agent3·H2And adding the O solution (5-7 mol/L) into the reaction tanks respectively. Adjusting the pH value to 10.5-11.0, and the concentration of ammonia water to 1-2.5 mol/L. Coprecipitation reaction is carried out, and pure water is used for filtering, washing and drying to obtain precursor NixMny(OH)2。
(2) In terms of mole ratios, as Ga: weighing gallium source according to the proportion of (Ni + Mn) ═ 2n:1, adding a certain amount of organic solvent, and fully mixing; the precursor material Ni prepared in the step (1) isxMny(OH)2Slowly adding the mixture into the mixed solution, adjusting the solid-to-liquid ratio of the solution to be 1: 5-15, and magnetically heating and stirring to obtain black slurry; and vacuum drying is carried out to ensure that the gallium source is uniformly adsorbed on the precursor material NixMny(OH)2Surface to obtain Ni adsorbed by gallium sourcexMny(OH)2A precursor material.
(3) In terms of mole ratio, Ni adsorbed by lithium source and gallium sourcexMny(OH)2The metal ion ratio of the precursor material is Li: (Ni + Mn) is 1-1.2: 1, and Ni adsorbed by the gallium source obtained by the treatment of the step (2)xMny(OH)2Uniformly mixing the precursor material and a lithium source, and mixing for 10-15 hours in a mixing tank; performing two-stage sintering in an oxygen atmosphere, heating and pretreating at 500-700 ℃ for 3-8 h, then sintering at 800-900 ℃ for 10-20 h, naturally cooling to 100 ℃ and taking out a sample to obtain an active metal oxide multiple modified cathode material LiNixMnyO2·nGa2O3。
Preferably, the active metal oxide multiple-modification cathode material and the preparation method thereof are prepared by the following steps:
(1) in terms of molar ratio, firstly, 2-5 moL/L of NiSO4·6H2O、MnSO4·H2Uniformly mixing O (Ni: Mn ═ x: y), and simultaneously adding 5.5-7.5 mol/L of NaOH solution and NH serving as a complexing agent3·H2And adding the O solution (5-7 mol/L) into the reaction tanks respectively. Adjusting the pH value to 10.5-11.0, and the concentration of ammonia water to 1-2.5 mol/L. Coprecipitation reaction is carried out, and pure water is used for filtering and drying to obtain precursor NixMny(OH)2。
(2) In terms of molar ratio, lithium source and Ni prepared in the step (1)xMny(OH)2The metal ion ratio of the precursor material is Li: (Ni + Mn) in a ratio of 1 to 1.2:1, adding NixMny(OH)2Uniformly mixing the precursor material and a lithium source, and mixing for 10-15 hours in a mixing tank; performing two-stage sintering in an oxygen atmosphere, heating and pretreating at 500-700 ℃ for 3-8 h, then sintering at 800-900 ℃ for 10-20 h, naturally cooling to 100 ℃ and taking out a sample to obtain the cathode material LiNixMnyO2。
(3) In terms of mole ratios, as Ga: (Ni)Weighing gallium source in the proportion of + Mn) to 2n:1, adding a certain amount of organic solvent, and fully mixing; LiNi which is the positive electrode material prepared in the step (2)xMnyO2Slowly adding the mixture into the mixed solution, adjusting the solid-to-liquid ratio of the solution to be 1: 5-15, and magnetically heating and stirring for 3-5 hours to obtain black slurry; and vacuum drying, sintering at 600-700 ℃ for 10-15 h, naturally cooling to 100 ℃ and taking out a sample to obtain the active metal oxide multiple modified cathode material LiNixMnyO2·nGa2O3。
Preferably, the gallium source is any one or more of gallium nitrate and gallium sulfate.
Preferably, the organic solvent is any one or more of ethanol, methanol and propanol.
Preferably, the lithium source is one or more of lithium hydroxide, lithium carbonate or lithium nitrate.
Preferably, the stirring temperature is 80-85 ℃ and the time is 3-4 h.
Preferably, the vacuum degree of vacuum drying is 0-0.1 MPa, the temperature is 70-130 ℃, and the time is 4-15 h.
In summary, the technical scheme of the invention has the following beneficial effects:
(1) an active metal oxide multiple-modified anode material and a preparation method thereof synthesize LiNixMnyO2·nGa2O3And (3) a positive electrode material. The invention leads the surface of the anode material to be coated with uniform Ga through effective and feasible surface multiple modification2O3And the coating layer and the positive electrode material are doped with gallium. The method can effectively reduce the side reaction between the anode material and the electrolyte, enhance the structural stability of the material, and comprehensively improve the cycle stability and the rate capability of the anode material.
(2) The positive electrode material obtained by the invention is assembled into a battery, the first discharge gram capacity reaches 201.5mAh/g under 2.75-4.6V and 1C, the capacity is 166.03mAh/g after 200 cycles under 1C, and the capacity retention rate reaches 82.4%; LiNi illustrating the inventionxMnyO2·nGa2O3Positive electrode materialThe material has better cycle stability and high-rate discharge performance.
(3) The method has the advantages of simple preparation process, low cost and less environmental pollution, and is suitable for industrial production.
Drawings
FIG. 1 is a TEM image of a positive electrode material obtained in example 3 of the present invention;
FIG. 2 is an XRD pattern of a positive electrode material obtained in example 2 of the present invention;
FIG. 3 is a high-magnification SEM image of a positive electrode material obtained in example 3 of the present invention;
FIG. 4 is a low-magnification SEM image of the cathode material obtained in example 3 of the present invention;
fig. 5 is a graph of cycle performance of the positive electrode materials of example 3 of the present invention and comparative example 1.
Detailed Description
The invention is further illustrated below with reference to examples and figures.
Example 1
(1) In terms of molar ratio, 2moL/L of 0.9moL of NiSO4·6H2O, 0.1moL MnSO4·H2O (Ni: Mn ═ 9:1) was uniformly mixed, and at the same time, a NaOH solution (6.8mol/L) and NH as a complexing agent were added3·H2O solution (6.5mol/L) was added to the reaction tanks, respectively. The pH value is adjusted to 10.5, and the ammonia concentration is 1 mol/L. Coprecipitation reaction is carried out, and pure water is used for filtering, washing and drying to obtain precursor Ni0.9Mn0.1(OH)2。
(2) In terms of mole ratios, as Ga: weighing gallium nitrate 0.023mol according to the proportion that (Ni + Mn) is 0.023:1, adding a certain amount of absolute ethyl alcohol, and fully mixing; ni is taken as 1mol of precursor material prepared in the step (1)0.9Mn0.1(OH)2Slowly adding into the mixed solution, adjusting the solid-to-liquid ratio of the solution to be 1:10, heating and stirring at 80 ℃ by magnetic force for 3h to obtain black slurry; and vacuum drying at 100 deg.C for 10h to make gallium source be uniformly adsorbed on precursor material Ni0.9Mn0.1(OH)2Surface to obtain Ni adsorbed by gallium source0.9Mn0.1(OH)2A precursor material.
(3) In moleIn terms of ratio, lithium nitrate and Ni absorbed by gallium source0.9Mn0.1(OH)2The metal ion ratio of the precursor material is Li: 1mol of Ni adsorbed by the gallium source obtained by the treatment of the step (2) is added into the gallium source with the proportion of (Ni + Mn) 1.1:10.9Mn0.1(OH)2Uniformly mixing the precursor material with 1.1mol of lithium nitrate, mixing for 11.5h in a mixing tank, performing two-stage sintering in an oxygen atmosphere, heating and pretreating for 4.5h at 630 ℃, then sintering for 11.5h at 820 ℃, naturally cooling to 100 ℃, taking out a sample, and obtaining the active metal oxide multiple modified cathode material LiNi0.9Mn0.1O2·0.01Ga2O3。
The metal oxide multiple modified cathode material obtained in this example was characterized and detected, and its composition was LiNi0.9Mn0.1O2·0.01Ga2O3A particle diameter of 2 to 3 μm and Ga on the surface2O3The formed coating layer has uniform thickness; presence of LiNi0.9Mn0.1O2And Ga2O3Two phases.
The positive electrode material obtained in the embodiment is used to assemble a button cell of CR 2025. The first discharge gram capacity of the battery reaches 201.1mAh/g within the voltage range of 2.75-4.6V and under the multiplying power of 1C, the capacity is 158.67mAh/g after 100 cycles under the multiplying power of 1C, and the capacity retention rate reaches 78.9%.
Example 2
(1) In terms of molar ratio, 3moL/L of 0.9moL of NiSO4·6H2O, 0.1moL MnSO4·H2O (Ni: Mn ═ 9:1) was uniformly mixed, and at the same time, a NaOH solution (6mol/L) and NH as a complexing agent were added3·H2O solution (6mol/L) is added into the reaction tanks respectively. The pH was adjusted to 10.6 and the ammonia concentration was 1.5 mol/L. Coprecipitation reaction is carried out, and pure water is used for filtering, washing and drying to obtain precursor Ni0.9Mn0.1(OH)2。
(2) In terms of mole ratios, as Ga: weighing 0.022mol of gallium sulfate according to the proportion of (Ni + Mn) ═ 0.044:1, adding a certain amount of methanol, fully mixing, and mixing 1mol of precursor material Ni prepared in the step (1)0.9Mn0.1(OH)2Slowly adding into the mixed solution, adjusting the solid-to-liquid ratio of the solution to 1:12, heating to 82 deg.C, and magnetically stirring for 3.2h to obtain black slurry; and vacuum drying at 90 deg.C for 11h to make gallium source be uniformly adsorbed on precursor material Ni0.9Mn0.1(OH)2Surface to obtain Ni adsorbed by gallium source0.9Mn0.1(OH)2A precursor material.
(3) In terms of molar ratio, lithium hydroxide and Ni adsorbed by gallium source0.9Mn0.1(OH)2The metal ion ratio of the precursor material is Li: the gallium source obtained by the treatment of the step (2) is adsorbed with 1mol of Ni according to the proportion of (Ni + Mn) 1.2:10.9Mn0.1(OH)2Uniformly mixing the precursor material with 1.2mol of lithium hydroxide, mixing for 13h in a mixing tank, performing two-stage sintering in an oxygen atmosphere, heating and pretreating for 5h at 640 ℃, then sintering for 13h at 810 ℃, naturally cooling to 100 ℃ and taking out a sample to obtain the active metal oxide multiple modified cathode material LiNi0.9Mn0.1O2·0.02Ga2O3。
The metal oxide multiple modified cathode material obtained in this example was characterized and detected, and the XRD pattern of the cathode material is shown in fig. 2, and its composition is LiNi0.9Mn0.1O2·0.02Ga2O3(ii) a The particle size is 2 to 3 μm, and Ga is on the surface2O3The formed coating layer has uniform thickness; presence of LiNi0.9Mn0.1O2And Ga2O3Two phases.
The positive electrode material obtained in the embodiment is used for assembling a button cell of CR 2025. The first discharge gram capacity of the battery reaches 202.3mAh/g within the voltage range of 2.75-4.6V and under the multiplying power of 1C, the capacity is 161.23mAh/g after 200 cycles under the multiplying power of 1C, and the capacity retention rate reaches 79.7%.
Example 3
(1) In terms of molar ratio, 2.5moL/L of 0.9moL of NiSO4·6H2O, 0.1moL MnSO4·H2O (Ni: Mn ═ 9:1) was uniformly mixed, and at the same time, a NaOH solution (6.8mol/L) and a complexing agentNH3·H2O solution (6.2mol/L) was added to the reaction tanks, respectively. The pH value is adjusted to 10.8, and the ammonia concentration is 2 mol/L. Coprecipitation reaction is carried out, and pure water is used for filtering and drying to obtain precursor Ni0.9Mn0.1(OH)2。
(2) In terms of mole ratios, as Ga: weighing 0.064mol of gallium nitrate according to the proportion of (Ni + Mn) ═ 0.064:1, adding a certain amount of propanol, fully mixing, and adding 1mol of precursor material Ni prepared in the step (1)0.9Mn0.1(OH)2Slowly adding into the mixed solution, adjusting the solid-to-liquid ratio of the solution to be 1:13, heating and stirring at 83 ℃ by magnetic force for 3.5h to obtain black slurry; and vacuum drying at 95 ℃ for 12h to ensure that the gallium source is uniformly adsorbed on the precursor material Ni0.9Mn0.1(OH)2Surface to obtain Ni adsorbed by gallium source0.9Mn0.1(OH)2A precursor material.
(3) In terms of molar ratio, lithium acetate and Ni adsorbed by gallium source0.9Mn0.1(OH)2The metal ion ratio of the precursor material is Li: 1mol of Ni adsorbed by the gallium source obtained by the treatment of the step (2) is added into the gallium source with the proportion of (Ni + Mn) 1.1:10.9Mn0.1(OH)2Uniformly mixing the precursor material with 1.1mol of lithium acetate, mixing for 13h in a mixing tank, sintering in an oxygen atmosphere for two sections, heating and pretreating for 6h at 640 ℃, sintering for 15h at 840 ℃, naturally cooling to 100 ℃ and taking out a sample to obtain the active metal oxide multiple modified cathode material LiNi0.9Mn0.1O2·0.03Ga2O3。
The metal oxide multiple modified cathode material obtained in this example was characterized and detected, and its composition was LiNi0.9Mn0.1O2·0.03Ga2O3The electron microscope images of the cathode material are shown in figures 1, 3 and 4, the particle size of the cathode material is 2-3 mu m, and Ga is arranged on the surface of the cathode material2O3The formed coating layer has uniform thickness. Presence of LiNi0.9Mn0.1O2And Ga2O3Two phases.
The positive electrode material obtained in the embodiment is used for assembling a button cell of CR 2025. Mixing the aboveThe battery discharges a gram of capacity of 201.5mAh/g for the first time within the voltage range of 2.75-4.6V and under the multiplying power of 1C, the capacity is 166.03mAh/g after 200 cycles under the multiplying power of 1C, and the capacity retention rate reaches 82.4%; LiNi illustrating the inventionxMnyO2·nGa2O3The positive electrode material has better cycle stability and high-rate discharge performance (particularly, refer to a curve shown in fig. 4).
Comparative example 1
(1) In terms of molar ratio, 4moL/L of 0.9moL of NiSO4·6H2O, 0.1moL MnSO4·H2O (Ni: Mn ═ 9:1) was uniformly mixed, and at the same time, a NaOH solution (7mol/L) and NH as a complexing agent were added3·H2O solution (6.5mol/L) was added to the reaction tanks, respectively. The pH was adjusted to 10.9 and the ammonia concentration was 2.2 mol/L. Coprecipitation reaction is carried out, and pure water is used for filtering and drying to obtain precursor Ni0.9Mn0.1(OH)2。
(2) In terms of molar ratio, lithium nitrate and Ni0.9Mn0.1(OH)2The metal ion ratio of the precursor material is Li: 1mol of Ni treated in step (2) at a ratio of (Ni + Mn) 1.1:10.9Mn0.1(OH)2Uniformly mixing the precursor material with 1.1mol of lithium nitrate, mixing for 11.5h in a mixing tank, performing two-stage sintering in an oxygen atmosphere, heating and pretreating at 620 ℃ for 6h, then sintering at 850 ℃ for 15h, naturally cooling to 100 ℃, taking out a sample, and obtaining the cathode material LiNi0.9Mn0.1O2。
The positive electrode material obtained in this example was characterized and tested, and its composition was LiNi0.9Mn0.1O2Having a particle diameter of 2.5 to 3.5 μm and being in the presence of LiNi0.9Mn0.1O2A phase of the mixture.
The positive electrode material obtained in the embodiment is used for assembling a button cell of CR 2025. When the battery is used in a voltage range of 2.75-4.6V and at a multiplying power of 1C, the first discharge capacity reaches 201.8mAh/g, the capacity is 158.61mAh/g after 200 cycles at 1C, and the capacity retention rate reaches 78.6% (see a curve shown in figure 4 specifically).
In summary, by Ga3+Surface ofDoped and Ga2O3The surface-coated cathode material is greatly improved in cycle performance and rate performance.
Claims (3)
1. An active metal oxide multiple-modification anode material and a preparation method thereof, synthesizing LiNixMnyO2·nGa2O3The positive electrode material is characterized in that x, y and n are mole numbers, and x is more than or equal to 0.8<1，0<y≤0.2，x+y＝1，0<n≤0.05，Ga2O3Is an active oxide, and forms a uniform coating layer with a thickness of 2.5-3.5 nm.
2. The active metal oxide multiple-modification cathode material and the preparation method thereof according to claim 1: the preparation method is characterized by comprising the following steps:
(1) in terms of molar ratio, firstly, 2-5 moL/L of NiSO4·6H2O、MnSO4·H2Uniformly mixing O (Ni: Mn ═ x: y), and simultaneously adding 5.5-7.5 mol/L of NaOH solution and NH serving as a complexing agent3·H2And adding the O solution (5-7 mol/L) into the reaction tanks respectively. Adjusting the pH value to 10.5-11.0, and the concentration of ammonia water to 1-2.5 mol/L. Coprecipitation reaction is carried out, and pure water is used for filtering, washing and drying to obtain precursor NixMny(OH)2。
(2) In terms of mole ratios, as Ga: weighing gallium source according to the proportion of (Ni + Mn) ═ 2n:1, adding a certain amount of organic solvent, and fully mixing; the precursor material Ni prepared in the step (1) isxMny(OH)2Slowly adding the mixture into the mixed solution, adjusting the solid-to-liquid ratio of the solution to be 1: 5-15, and magnetically heating and stirring to obtain black slurry; and vacuum drying to make gallium source be uniformly adsorbed on precursor material NixMny(OH)2Surface to obtain Ni adsorbed by gallium sourcexMny(OH)2A precursor material.
(3) In terms of mole ratio, Ni adsorbed by lithium source and gallium sourcexMny(OH)2The metal ion ratio of the precursor material is Li: (Ni + Mn) is 1-1.2: 1, and the product is obtained by the treatment of the step (2)Adsorbed Ni from gallium sourcexMny(OH)2Uniformly mixing the precursor material and a lithium source, and mixing for 10-15 hours in a mixing tank; performing two-stage sintering in an oxygen atmosphere, heating and pretreating at 500-700 ℃ for 3-8 h, then sintering at 800-900 ℃ for 10-20 h, naturally cooling to 100 ℃ and taking out a sample to obtain an active metal oxide multiple modified cathode material LiNixMnyO2·nGa2O3。
3. The active metal oxide multiple-modification cathode material and the preparation method thereof according to claims 1 and 2, characterized in that: in the step (2), the gallium source is any one or more of gallium nitrate and gallium sulfate; the organic solvent is any one or more of ethanol, methanol and propanol; stirring at 75-85 ℃ for 3-5 h; more preferably, the stirring temperature is 80-85 ℃, and the time is 3-4 h; vacuum drying is carried out in a vacuum box, the vacuum degree is 0-minus 0.1MPa, the temperature is 70-130 ℃, and the drying time is 4-15 h; in the step (3), the lithium source is any one or more of lithium fluoride, lithium carbonate, lithium acetate, lithium nitrate and lithium hydroxide.
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