CN107910516B - High-voltage lithium nickel manganese oxide composite positive electrode material for lithium battery, preparation process of high-voltage lithium nickel manganese oxide composite positive electrode material, lithium battery positive electrode and lithium battery - Google Patents
High-voltage lithium nickel manganese oxide composite positive electrode material for lithium battery, preparation process of high-voltage lithium nickel manganese oxide composite positive electrode material, lithium battery positive electrode and lithium battery Download PDFInfo
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- CN107910516B CN107910516B CN201711085449.2A CN201711085449A CN107910516B CN 107910516 B CN107910516 B CN 107910516B CN 201711085449 A CN201711085449 A CN 201711085449A CN 107910516 B CN107910516 B CN 107910516B
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention provides a high-voltage lithium nickel manganese oxide composite positive electrode material for a lithium battery, a preparation process of the high-voltage lithium nickel manganese oxide composite positive electrode material, a lithium battery positive electrode and the lithium battery. The positive electrode material is an xLNO/LNMO composite positive electrode material, is prepared by taking a small amount of LNO as a nucleating agent and sintering the LNMO through solid-phase reaction, and comprises the following steps: 1) uniformly mixing solutions at least containing lithium compounds, nickel compounds and manganese compounds to prepare solid gel; 2) sintering and annealing the solid gel to prepare LNMO; 3) mixing and grinding the LNMO, a niobium compound and another lithium compound, and sintering through solid-phase reaction to obtain the composite cathode material of the LNO and the LNMO. The xLNO/LNMO composite cathode material has high lithium ion conductivity, and can inhibit the formation of a passivation film on the interface of an electrode and electrolyte, so that the stability of the cathode is improved, and the cycle life of a battery at high multiplying power is improved.
Description
Technical Field
The invention relates to the field of rechargeable lithium ion batteries, in particular to a modification technology of a cathode material with high voltage in a lithium ion battery, belonging to a rechargeable lithium ion battery and a manufacturing method thereof.
Background
Currently, in the development of lithium ion battery materials, Lithium Nickel Manganese Oxide (LNMO) having a spinel structure is a type of positive electrode material that is receiving much attention. Because the material has a higher voltage plateau (4.7V vs. Li +/Li), it can provide high power output, its theoretical capacity is 147 Ah/kg, and power density is 658 Wh/kg; meanwhile, the material has the advantages of stable structure, good safety, rich raw materials, low price and environmental friendliness, and can be decomposed without toxicity after being used, so that the development and commercialization of the lithium nickel manganese oxide material have wide application prospects.
The electrochemical performance of a lithium nickel manganese oxide material depends on various factors of the material itself; such as the crystal structure of the material (the stoichiometric ratio of li, ni, mn), the particle morphology and size of the material, and the type of electrolyte used in the battery. At present, many problems to be solved still remain in the application of lithium nickel manganese oxide as a positive electrode material, such as: capacity fading under high-rate charge and discharge conditions is rapid, and cycle characteristics are poor. When the lithium-nickel-manganese-oxygen cathode material works in a high-voltage platform environment, a thick high-impedance passivation layer is formed on a contact interface of electrolyte and a cathode, so that the insertion and the extraction of lithium ions are limited, and meanwhile, fluorine ions existing in the commonly adopted lithium-phosphorus hexafluoride electrolyte can also react with the cathode to cause the corrosion and the dissolution of the lithium-nickel-manganese-oxygen cathode material, so that the service life of the battery is shortened.
In order to solve the above problems of the lithium nickel manganese oxide positive electrode material, the prior art has adopted improvement techniques including: adding a high molecular protective agent to avoid the reduction of the particle surface area caused by the agglomeration of the powder particles; lithium manganese oxide surface is coated with carbon to raise the electronic conductivity of the material and surface repairing technology or additive is used to maintain the stability of the interface between electrolyte and cathode.
Disclosure of Invention
The invention aims at the defects of the prior art and provides a high-voltage lithium nickel manganese oxide composite positive electrode material for a lithium battery, a preparation process thereof, a lithium battery positive electrode and the lithium battery.
Hair brushThe invention aims to provide a process method for improving the lithium ion conductivity of a lithium nickel manganese oxide material and simultaneously inhibiting the occurrence of oxidation side reactions of an electrolyte under a high-voltage platform, and mainly solves the problems of too fast capacity attenuation and poor battery cycle characteristics under the high-rate charge-discharge condition when the conventional lithium nickel manganese oxide is used as the anode of a lithium ion battery. The invention adopts specific solid gel technology to process to prepare LNMO with a spinel structure, and then uses a small amount of LiNbO3(LNO) is used as a nucleating agent, and the xLNO/LNMO composite positive electrode material with high lithium ion conductivity is prepared through high-temperature solid state reaction, and meanwhile, a passivation film can be inhibited from being formed on the interface of an electrode and electrolyte, so that the stability of the positive electrode structure is improved, and the cycle life of the battery at high rate is improved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
1. the invention provides a high-voltage lithium nickel manganese oxide composite positive electrode material for a lithium battery, which is an xLNO/LNMO composite positive electrode material and is prepared by mixing LNO and LNMO according to a certain proportion, taking LNO as a nucleating agent and sintering the LNMO and the LNMO through solid-phase reaction.
Optionally, in the positive electrode material, x =0.02-0.08, preferably x =0.04:1 in the xLNO/LNMO composite positive electrode material.
Optionally, in the above cathode material, the LNMO has a chemical formula of: LiNiyMn2-yO4Y is more than or equal to 0.2 and less than or equal to 0.8, and the spinel structure is adopted.
2. The invention also provides a preparation process of the high-voltage lithium nickel manganese oxide composite positive electrode material for the lithium battery, which comprises the following working procedures:
1) a step of uniformly mixing a solution containing at least a lithium compound, a nickel compound and a manganese compound to prepare a solid gel;
2) sintering the solid gel, and annealing after sintering to obtain LNMO;
3) mixing and grinding the LNMO, the niobium compound and the other lithium compound, and sintering through solid-phase reaction to obtain the composite cathode material of the LNO and the LNMO.
Based on the procedures, the transformation of the secondary structure and the particle morphology of the anode material is completed, and the prepared anode material can inhibit a passivation film formed between an electrode and electrolyte, so that the stability of the electrode structure is improved, and the high-rate cycle life of the battery is improved.
Optionally, in the preparation process of the positive electrode material, in the step 1), deionized water is used as a solvent, the water-soluble lithium compound, the water-soluble nickel compound and the water-soluble manganese compound are uniformly mixed, then citric acid is added for mixing, stirring is continued, and after the temperature is raised to 70-90 ℃, viscous gel is formed.
Optionally, in the preparation process of the cathode material, in the step 1), the molar ratio of lithium, nickel and manganese is 1: y (2-y), y is more than or equal to 0.2 and less than or equal to 0.8, preferably the molar ratio of lithium, nickel and manganese is 1:0.5:1.5, and the ratio of the total molar amount of lithium, nickel and manganese to the molar amount of citric acid is 1:1-1: 1.3.
Optionally, in the preparation process of the cathode material, in the step 2), the solid gel obtained in the step 1) is reacted at the high temperature of 900 ℃ for 8-12 hours, and then annealed at 700 ℃ for 4-6 hours.
Optionally, in the preparation process of the cathode material, in the step 3), the LNMO obtained in the step 2) is ball-milled and pulverized, and then is uniformly mixed with the niobium compound and the other lithium compound according to the molar ratio of LNO to LNMO of 0.02-0.08:1, and then is tableted, and is preheated to 600-700 ℃ under normal pressure for 4-6 hours; taking out, crushing, refining and tabletting again, heating to 800 ℃ again, preserving the heat for more than 20 hours, and cooling to room temperature; finally, ball milling, crushing and refining are carried out, and the particle size is controlled to be less than or equal to 10 mu m. The preferable particle size range is 1-5 μm, and the most preferable particle size range is 1.0. + -. 0.5. mu.m.
Optionally, in the above-mentioned preparation process of the cathode material, the purity of the lithium compound, the nickel compound, the manganese compound, the other lithium compound and the niobium compound is more than or equal to 99%.
Optionally, in the above preparation process of the cathode material, in the step 1), the lithium compound is lithium acetate, lithium nitrate, lithium hydroxide or lithium carbonate, the nickel compound is nickel acetate, nickel nitrate, nickel chloride or nickel sulfate, and the manganese compound is manganese acetate, manganese nitrate, manganese chloride or manganese sulfate. Preferably, the lithium compound is lithium acetate, the nickel compound is nickel acetate, and the manganese compound is manganese acetate.
Alternatively, in the above-described process for producing a positive electrode material, in step 3), the lithium compound is lithium carbonate or lithium acetate, and the niobium compound is niobium hydroxide or niobium pentoxide. Preferably, the lithium compound is lithium carbonate and the niobium compound is niobium pentoxide.
3. The invention also provides a lithium battery anode which comprises a substrate and a coating material arranged on the surface of the substrate, wherein the coating material comprises an anode material, a conductive material and a binder, and the anode material is prepared by adopting the high-voltage lithium nickel manganese oxide composite anode material for the lithium battery, taking LNO as a nucleating agent and sintering the LNO with LNMO through a solid-phase reaction.
Alternatively, in the above lithium battery positive electrode, the LNO and the LNMO are mixed in a molar ratio of 0.02 to 0.08:1, preferably in a molar ratio of 0.04: 1.
Alternatively, in the above-described lithium battery positive electrode, a material well known to those skilled in the art, such as aluminum foil, may be used for the substrate. The conductive material in the coating material is preferably carbon black, and the adhesive can be polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate or styrene-butadiene rubber. Preferably, the xLNO/LNMO composite cathode material is carbon black polyvinylidene fluoride =8:1: 1.
4. The lithium battery anode provided by the invention can be prepared by adopting the following method:
mixing the xLNO/LNMO composite anode material with carbon black and polyvinylidene fluoride according to the weight ratio of 8:1:1, and uniformly preparing into anode slurry by using an N-methyl-2-pyrrolidone solvent. Adjusting according to the characteristics of using equipment, testing the viscosity by using a rotational viscometer after the anode slurry is prepared, measuring the granularity by using a granularity meter, and measuring other physical indexes such as solid content, density and the like. The above positive electrode slurry was allowed to stand for 2 hours before use. The areal density of the coating was set at 180 g/m2. And uniformly coating the anode slurry on an aluminum foil with the thickness of 0.02 mm, and drying by adopting hot air circulation at the temperature of 80-150 ℃. Dry matterAnd (3) after drying, rolling by adopting 300 tons of pressure, and compacting the pole piece to obtain the required battery positive pole piece.
The coating thickness of the anode slurry is 0-1000 nm, and the preferable range is 0.1-100 nm.
5. The present invention also provides a lithium battery including: the lithium battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the diaphragm and the electrolyte are arranged between the positive electrode and the negative electrode, and the positive electrode of the lithium battery adopts the positive electrode of the lithium battery.
Optionally, the electrolyte is a lithium hexafluorophosphate system, the solvent is a mixture of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1:1, and 1M LiPF is dissolved in the mixed solution6。
Compared with the prior art, the high-voltage lithium nickel manganese oxide composite positive electrode material for the lithium battery, the preparation process thereof, the lithium battery positive electrode and the lithium battery have the following beneficial effects that:
the invention selects a solid lithium battery anode material with high ionic conductivity, adopts a specific solid gel technology to process to prepare LNMO with a spinel structure, and then LiNbO3(LNO) and LNMO carry out specific high-temperature solid-state reaction, and the lithium ion conduction and the electrochemical performance of the lithium nickel manganese oxide material are improved. The solid-state reaction comprises a two-phase synergistic nucleation process and a particle growth process, and a small amount of LNO serving as a nucleating agent and lithium nickel manganese oxide are subjected to a high-temperature sintering process to complete the transformation of a secondary structure and particle morphology. The xLNO/LNMO composite cathode material prepared by the invention has high lithium ion conductivity, and can inhibit the formation of a passivation film on the interface of an electrode and electrolyte, so that the stability of the cathode structure is improved, and the cycle life of a battery at high rate is improved.
Drawings
FIG. 1 is a diagram of electrochemical performance of cyclic voltammetry detection of different anode materials xLNO/LNMO in the present invention; (a) pure lithium nickel manganese oxide; (b)0.02 LNO/LNMO; (c) 0.04 LNO/LNMO; (d)0.06 LNO/LNMO.
FIG. 2 is a graph of the cycle test results of different anode materials xLNO/LNMO under 0.5C-20C high-rate discharge;
FIG. 3 shows the effect of the addition of LNO on the discharge capacity of the cell under different current densities of different cathode materials xLNO/LNMO in accordance with the present invention.
FIG. 4 is a graph of cell cycle test results for different positive electrode materials xLNO/LNMO in accordance with the present invention.
Detailed Description
The high-voltage lithium nickel manganese oxide composite positive electrode material for a lithium battery, the preparation process thereof, the lithium battery positive electrode and the lithium battery of the present invention are described in detail below with reference to the accompanying drawings 1 to 4. The scope of the present invention is not limited by the following examples.
Example one
1. Preparation of xLNO/LNMO composite positive electrode material for lithium battery
The invention relates to a high-voltage lithium nickel manganese oxygen composite positive electrode material for a lithium battery, which comprises the following steps:
1) taking lithium acetate, nickel acetate, manganese acetate and citric acid with the purity of more than or equal to 99% as raw materials, weighing the components according to the molar ratio of the lithium, the nickel and the manganese of 1:0.5:1.5, taking deionized water as a solvent, preparing the lithium acetate, the nickel acetate and the manganese acetate into a mixed aqueous solution, adding citric acid for complexing under the stirring state, wherein the ratio of the total molar amount of the lithium, the nickel and the manganese to the molar amount of the citric acid is 1:1, stirring at room temperature for 6 hours, and heating to 80 ℃ to form viscous gel.
2) Putting the obtained viscous gel into an oven, controlling the reaction at the high temperature of 850 ℃ for 10 hours, and then annealing at the temperature of 600 ℃ for 5 hours to obtain the LiNi with the spinel structure0.5Mn1.5O4。
3) The obtained LiNi0.5Mn1.5O4Ball-milling and grinding, uniformly mixing with niobium pentoxide and lithium carbonate with the purity of more than or equal to 99% according to a certain molar ratio after grinding, crushing and tabletting, preheating to 650 ℃ at normal pressure for 5 hours to ensure that the mixed powder fully undergoes solid-phase reaction to primarily generate xLNO/LNMO powder (x =0, 0.02, 0.04, 0.06 and 0.08); taking out, crushing, refining and tabletting again, taking LNO as a nucleating agent, heating to 750 ℃ again, preserving heat for 24 hours, cooling to room temperature, and taking out. Finally, theBall milling, crushing and refining to control the particle size to be less than or equal to 10 mu m. The preferable particle size range is 1-5 μm, and the most preferable particle size range is 1.0. + -. 0.5. mu.m.
2. Preparation of positive electrode for lithium battery
Mixing the xLNO/LNMO composite anode material prepared according to the step 1 with carbon black and polyvinylidene fluoride according to the weight ratio of 8:1:1, and uniformly preparing into anode slurry by using an N-methyl-2-pyrrolidone solvent. Adjusting according to the characteristics of used equipment, testing the viscosity by using a rotational viscometer after the preparation of the anode slurry is finished, wherein the tested viscosity is 13000 mPaS, measuring the granularity by using a granularity meter, wherein the tested granularity is 8 mu m at most, and measuring other physical indexes such as solid content, density and the like. The above positive electrode slurry was allowed to stand for 2 hours before use. The areal density of the coating was set at 180 g/m2. And uniformly coating the anode slurry on an aluminum foil with the thickness of 0.02 mm, and drying by adopting hot air circulation at the temperature of 80-150 ℃. And (3) after drying, rolling by adopting 300 tons of pressure, and compacting to obtain the required positive electrode for the lithium battery.
The coating thickness of the anode slurry is 0-1000 nm, and the preferable range is 0.1-100 nm.
3. Lithium battery
The lithium battery of the present invention comprises: a positive electrode for a lithium battery prepared in the above 2, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte.
The lithium battery to be tested is prepared by stamping the positive electrode for the lithium battery into a wafer electrode with the diameter of 1.2 cm, adopting a lithium foil to carry out performance test in a standard button battery (CR 2032) assembled by the electrode, adopting a lithium hexafluorophosphate system as electrolyte, mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC) according to the volume ratio of 1:1 as solvent, and dissolving 1M LiPF in the mixed solution6。
4. Lithium battery performance test
An xLNO/LNMO composite positive electrode material for lithium batteries (x =0, 0.02, 0.04, 0.06, 0.08), example with x =0, was used as a comparative example.
1) Cyclic voltammetry for electrochemical performance
FIG. 1 is a cyclic voltammetry characteristic diagram of xLNO/LNMO (x =0, 0.02, 0.04, 0.06) composite cathode material for lithium batteries at different mixture ratios, with a sweep rate of 0.1 mV/s and a voltage interval of 3.5-5.0V.
The effect of the addition of LNO on the lithium ion battery can be seen from the Cyclic Voltammogram (CV) described above: two typical oxidation-reduction peaks appear at 4.7V, corresponding to two reactions: ni3+→Ni2+，Ni4+→Ni3+Corresponding to the intercalation/deintercalation of lithium ions from tetrahedrons of cubic structure. And when the addition amount x =0.04, the two corresponding redox peaks tend to merge into a single peak, which indicates that the appropriate amount of LNO can reduce the elution of Mn ions in LNMO, and can achieve the effect of inhibiting the occurrence of LNMO structure variation, i.e., stabilizing the LNMO crystal structure.
2) High rate discharge cycle test
Fig. 2 is a high-rate discharge cycle test curve of xLNO/LNMO (x =0, 0.02, 0.04, 0.06) composite cathode material for lithium batteries in different proportions. The test result shows that the LNO addition has obvious influence on the high-rate discharge (5C-20C) of the LNMO, and the discharge power is obviously improved (the optimum value of the addition amount is x = 0.04).
3) Different current density discharge capacity test
Fig. 3 shows the effect of LNO addition (x =0, 0.02, 0.04, 0.06) on the discharge capacity of lithium batteries at different current densities. The result shows that the LNO addition has obvious influence on the discharge of the LNMO at high current density, and the discharge power is obviously improved (the optimal value of the addition amount is x = 0.04).
4) Lithium battery cycle test results
Fig. 4 shows the effect of LNO addition (x =0, 0.02, 0.04, 0.06) on lithium battery cycling stability. The 200-cycle test result shows that the addition of the LNO can obviously improve the cycle stability of the lithium ion battery, and the optimal addition amount of the LNO is 0.04.
The detection results prove that the high-rate performance and the electrode cycling stability of the lithium ion battery can be obviously improved by adding the lithium niobate/lithium nickel manganese oxide (xLNO/LNMO) cathode material prepared by LNO.
Example two
The invention relates to a high-voltage lithium nickel manganese oxygen composite positive electrode material for a lithium battery, which comprises the following steps:
1) lithium nitrate, nickel chloride, manganese sulfate and citric acid with the purity of more than or equal to 99 percent are taken as raw materials, and the components are weighed according to the molar ratio of the lithium to the nickel to the manganese of 1:0.2: 1.8. Using deionized water as a solvent, preparing lithium nitrate, nickel chloride and manganese sulfate into a mixed aqueous solution, adding citric acid for complexing under the stirring state, wherein the ratio of the total molar weight of the lithium, the nickel and the manganese to the molar weight of the citric acid is 1:1.1, stirring for 5 hours at room temperature, and heating to 70 ℃ to form viscous gel.
2) Putting the obtained viscous gel into an oven, controlling the reaction at the high temperature of 800 ℃ for 8 hours, and then annealing at the temperature of 500 ℃ for 4 hours to obtain the LiNi with the spinel structure0.2Mn1.8O4。
3) The obtained LiNi0.2Mn1.8O4Ball-milling and grinding, evenly mixing the ground powder with niobium hydroxide and lithium acetate with the purity of more than or equal to 99% according to a certain molar ratio, grinding and tabletting, preheating the mixture to 600 ℃ under normal pressure for 4 hours to ensure that the mixed powder fully undergoes solid-phase reaction to primarily generate xLNO/LNMO powder (x =0, 0.02, 0.04, 0.06 and 0.08); taking out, crushing, refining and tabletting again, taking LNO as a nucleating agent, heating to 700 ℃ again, preserving heat for 20 hours, cooling to room temperature, and taking out. Finally, ball milling, crushing and refining are carried out, and the particle size is controlled to be less than or equal to 10 mu m. The preferable particle size range is 1-5 μm, and the most preferable particle size range is 1.0. + -. 0.5. mu.m.
The preparation of the positive electrode for a lithium battery and the lithium battery are the same as in the first embodiment.
EXAMPLE III
The invention relates to a high-voltage lithium nickel manganese oxygen composite positive electrode material for a lithium battery, which comprises the following steps:
1) lithium hydroxide with the purity of more than or equal to 99%, nickel nitrate, manganese nitrate and citric acid are used as raw materials, and the components are weighed according to the molar ratio of the lithium to the nickel to the manganese of 1:0.4: 1.6. Using deionized water as a solvent, preparing lithium acetate, nickel acetate and manganese acetate into a mixed aqueous solution, adding citric acid for complexing under the stirring state, wherein the ratio of the total molar weight of the lithium, the nickel and the manganese to the molar weight of the citric acid is 1:1.2, stirring for 7 hours at room temperature, and heating to 90 ℃ to form viscous gel.
2) Putting the obtained viscous gel into an oven, controlling the reaction at the high temperature of 900 ℃ for 12 hours, and then annealing at the temperature of 700 ℃ for 6 hours to obtain the LiNi with the spinel structure0.4Mn1.6O4。
3) The obtained LiNi0.4Mn1.6O4Ball-milling and grinding, uniformly mixing the ground powder with niobium hydroxide and lithium carbonate with the purity of more than or equal to 99% according to a certain molar ratio, grinding and tabletting, preheating the mixture to 700 ℃ under normal pressure for 6 hours to ensure that the mixed powder fully undergoes solid-phase reaction to primarily generate xLNO/LNMO powder (x =0, 0.02, 0.04, 0.06 and 0.08); taking out, crushing, refining and tabletting again, taking LNO as a nucleating agent, heating to 800 ℃ again, preserving heat for 26 hours, cooling to room temperature, and taking out. Finally, ball milling, crushing and refining are carried out, and the particle size is controlled to be less than or equal to 10 mu m. The preferable particle size range is 1-5 μm, and the most preferable particle size range is 1.0. + -. 0.5. mu.m.
The preparation of the positive electrode for a lithium battery and the lithium battery are the same as in the first embodiment.
Example four
The invention relates to a high-voltage lithium nickel manganese oxygen composite positive electrode material for a lithium battery, which comprises the following steps:
1) lithium carbonate, nickel sulfate, manganese chloride and citric acid with the purity of more than or equal to 99 percent are taken as raw materials, and the components are weighed according to the molar ratio of the lithium to the nickel to the manganese of 1:0.8: 1.2. Using deionized water as a solvent, preparing lithium acetate, nickel acetate and manganese acetate into a mixed aqueous solution, adding citric acid for complexing under the stirring state, wherein the ratio of the total molar weight of the lithium, the nickel and the manganese to the molar weight of the citric acid is 1:1.3, stirring at room temperature for 6 hours, and heating to 75 ℃ to form viscous gel.
2) Placing the obtained viscous gel in an oven, controlling the reaction at 820 ℃ for 9 hours, and then annealing at 650 ℃ for 5 hours to obtain LiNi with a spinel structure0.8Mn1.2O4。
3) The obtained LiNi0.8Mn1.2O4Ball-milling and grinding, uniformly mixing with niobium pentoxide and lithium acetate with the purity of more than or equal to 99% according to a certain molar ratio after grinding and tabletting, then preheating to 640 ℃ under normal pressure for 5 hours to ensure that the mixed powder fully undergoes solid-phase reaction to primarily generate xLNO/LNMO powder (x =0, 0.02, 0.04, 0.06 and 0.08); taking out, crushing, refining and tabletting again, taking LNO as a nucleating agent, heating to 720 ℃ again, preserving heat for 22 hours, cooling to room temperature, and taking out. Finally, ball milling, crushing and refining are carried out, and the particle size is controlled to be less than or equal to 10 mu m. The preferable particle size range is 1-5 μm, and the most preferable particle size range is 1.0. + -. 0.5. mu.m.
In the preparation step 1), the lithium nickel manganese oxide composite positive electrode material of the present invention is formed into a viscous gel, which includes, but is not particularly limited to, a method of dissolving a metal alkoxide or a metal inorganic salt in alcohol or water, hydrolyzing the solution to form a sol directly or forming a sol by decondensation, and then removing an organic component by heat treatment to obtain a solid gel.
In the preparation process 1), the water-soluble lithium compound includes, but is not particularly limited to, lithium acetate, lithium nitrate, lithium hydroxide, or lithium carbonate, the water-soluble nickel compound includes, but is not particularly limited to, nickel acetate, nickel nitrate, nickel chloride, or nickel sulfate, and the water-soluble manganese compound includes, but is not particularly limited to, manganese acetate, manganese nitrate, manganese chloride, or manganese sulfate.
In the preparation process 3), the lithium compound includes, but is not specifically limited to, lithium carbonate and lithium acetate, and the niobium compound includes, but is not specifically limited to, niobium hydroxide and niobium pentoxide.
In addition, in the lithium battery positive electrode of the present invention, the substrate may be made of a material known to those skilled in the art, including, but not particularly limited to, aluminum foil. The conductive material in the coating material includes, but is not particularly limited to, carbon black, and the binder includes, but is not particularly limited to, polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene chloride, polyvinyl chloride, polymethyl methacrylate, or styrene-butadiene rubber.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. That is, all equivalent changes and modifications made according to the content of the claims of the present invention should be within the technical scope of the present invention.
In addition to the technical features described in the specification, the technology is known to those skilled in the art.
Claims (9)
1. The high-voltage lithium nickel manganese oxide composite positive electrode material for the lithium battery is characterized in that the positive electrode material is an xLNO/LNMO composite positive electrode material, and is prepared by mixing LNO and LNMO according to a certain proportion, taking the LNO as a nucleating agent, and sintering the LNMO through a solid-phase reaction;
in the xLNO/LNMO composite positive electrode material, x = 0.02-0.08;
when the cathode material is prepared, the preparation method comprises the following steps:
1) a step of uniformly mixing a solution containing at least a lithium compound, a nickel compound and a manganese compound to prepare a solid gel;
2) sintering the solid gel, and annealing after sintering to obtain LNMO;
3) mixing and grinding the LNMO, the niobium compound and the other lithium compound, and sintering through solid-phase reaction to obtain the composite cathode material of the LNO and the LNMO.
2. The high voltage lithium nickel manganese oxide composite positive electrode material for a lithium battery as claimed in claim 1, wherein the chemical formula of the LNMO is as follows: LiNiyMn2-yO4，0.2≤y≤0.8。
3. The process for preparing a high-voltage lithium nickel manganese oxide composite positive electrode material for a lithium battery as claimed in claim 1, comprising the steps of:
1) a step of uniformly mixing a solution containing at least a lithium compound, a nickel compound and a manganese compound to prepare a solid gel;
2) sintering the solid gel, and annealing after sintering to obtain LNMO;
3) mixing and grinding the LNMO, the niobium compound and the other lithium compound, and sintering through solid-phase reaction to obtain the composite cathode material of the LNO and the LNMO.
4. The preparation process of the high-voltage lithium nickel manganese oxide composite positive electrode material for the lithium battery as claimed in claim 3, wherein in the step 1), deionized water is used as a solvent, the water-soluble lithium compound, the water-soluble nickel compound and the water-soluble manganese compound are uniformly mixed, then citric acid is added for mixing, stirring is continued, and after the temperature is raised to 70-90 ℃, viscous gel is formed.
5. The preparation process of the high-voltage lithium nickel manganese oxide composite positive electrode material for the lithium battery as claimed in claim 4, wherein in the step 1), the molar ratio of lithium, nickel and manganese is 1: y (2-y), y is more than or equal to 0.2 and less than or equal to 0.8, and the ratio of the total molar amount of lithium, nickel and manganese to the molar amount of citric acid is 1:1-1: 1.3.
6. The process of claim 3 or 4, wherein in the step 2), the solid gel obtained in the step 1) is reacted at a high temperature of 900 ℃ for 8-12 hours and then annealed at 700 ℃ for 4-6 hours.
7. The process according to claim 3, wherein in the step 3), the LNMO obtained in the step 2) is ball milled and pulverized, then is uniformly mixed with the niobium compound and the other lithium compound according to the molar ratio of LNO to LNMO being 0.02-0.08:1, and then is tableted, and is preheated to 600-700 ℃ at normal pressure for 4-6 hours; taking out, crushing, refining and tabletting again, heating to 800 ℃ again, preserving the heat for more than 20 hours, and cooling to room temperature; finally, ball milling, crushing and refining are carried out, and the particle size is controlled to be less than or equal to 10 mu m.
8. A lithium battery positive electrode, which comprises a substrate and a coating material arranged on the surface of the substrate, wherein the coating material comprises a positive electrode material, a conductive material and a binder, and is characterized in that the positive electrode material adopts the high-voltage lithium nickel manganese oxygen composite positive electrode material for the lithium battery as claimed in claim 1.
9. A lithium battery, comprising: a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein the positive electrode for a lithium battery comprises the positive electrode for a lithium battery according to claim 8.
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