CN109962217B - Lithium manganese silicate coated nickel-cobalt-manganese ternary material and preparation method thereof - Google Patents

Lithium manganese silicate coated nickel-cobalt-manganese ternary material and preparation method thereof Download PDF

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CN109962217B
CN109962217B CN201711424783.6A CN201711424783A CN109962217B CN 109962217 B CN109962217 B CN 109962217B CN 201711424783 A CN201711424783 A CN 201711424783A CN 109962217 B CN109962217 B CN 109962217B
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manganese
lithium
cobalt
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ternary material
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CN109962217A (en
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许开华
惠科石
徐世国
张文艳
周晓燕
张明龙
李新章
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GEM Co Ltd China
Jingmen GEM New Material Co Ltd
GEM Wuxi Energy Materials Co Ltd
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Jingmen GEM New Material Co Ltd
GEM Wuxi Energy Materials Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a lithium manganese silicate coated nickel-cobalt-manganese ternary material and a preparation method thereof, wherein the chemical general formula of the material is Li(1+4n)NixCoyMn(1‑x‑y+n)SinO2+4nWherein x is more than or equal to 0.6 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.2, and n is more than or equal to 0 and less than or equal to 0.05; the method prepares a primary sintered product LiNixCoyMn(1‑x‑y)O2And then the primary sintered product LiNixCoyMn(1‑x‑y)O2Adding the lithium manganese silicate into a lithium manganese silicate coating solution, and finally sintering to obtain a lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material; thus, the invention utilizes the advantages of high capacity and high safety of the lithium manganese silicate to coat the lithium manganese silicate on the surface of the ternary material, thereby improving the capacity and safety of the material; and by combining the longer cycle life of the ternary material, a more ideal power battery anode material can be obtained.

Description

Lithium manganese silicate coated nickel-cobalt-manganese ternary material and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium manganese silicate coated nickel-cobalt-manganese ternary material and a preparation method thereof.
Background
Lithium ion batteries are widely used in communication, portable computers and electronic energy storage devices due to their high operating voltage, low self-discharge effect and good cycle performance; at present, compared with fuel vehicles, the endurance mileage of pure electric vehicles is still one of the short plates of pure electric vehicles, so that the capacity of the positive electrode material is urgently improved, and particularly, higher requirements are put forward on the energy density of the positive electrode material of the lithium ion battery, so that a new positive electrode material of the lithium ion battery needs to be developed.
In recent years, the anode material prepared by taking cobalt oxide and nickel oxide as raw materials is the most widely applied at present, but the material prepared by cobalt and nickel has problems to be solved in the aspects of safety, material source, preparation process and the like; for other positive electrode materials, there are also aspects that each need improvement, such as: LiMn2O4The price is low, the safety performance is good, but the theoretical capacity is not high, and the cycle performance and the thermal stability are poor; LiFePO4Although the lithium ion battery has good thermal stability and cycle performance, and higher specific energy and safety, the lower electronic conductivity and lithium ion diffusion rate become a great obstacle for the continuous research and application of the lithium ion battery; for this reason, Nyt en et al have proposed for the first time polyanionic silicate positive electrode materials, and lithium manganese silicate (Li2MnSiO4) is considered to be the most ideal positive electrode material for lithium ion batteries with its high specific capacity of 333 mAh/g.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a lithium manganese silicate coated nickel-cobalt-manganese ternary material and a preparation method thereof.
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li(1+4n)NixCoyMn(1-x-y+n)SinO2+4nWherein x is more than or equal to 0.6 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.2,0≤n≤0.05。
the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding NixCoyMn(1-x-y)(OH)2The ternary precursor and the lithium source are mixed with Ni according to the molar weight of the lithium sourcexCoyMn(1-x-y)(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn), then the mixture is sintered in the oxygen atmosphere, and finally the mixture is crushed and sieved to obtain a primary sintered product LiNixCoyMn(1-x-y)O2；
And 2, dissolving lithium salt in enough water, stirring for one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution until the content of Li in the solution is: si: the Mn molar ratio is 4: 1: 1, stirring for the second time and standing to obtain a lithium manganese silicate coating solution;
step 3, the primary sintered product LiNixCoyMn(1-x-y)O2And adding the solution into a lithium manganese silicate coating solution to obtain a second solution, and sintering the second solution to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material.
In the foregoing scheme, in the step 1, the lithium source is at least one of lithium carbonate, lithium hydroxide, or lithium oxalate.
In the scheme, the sintering temperature in the step 1 is 700-900 ℃, and the sintering time is 10-20 h.
In the scheme, the adding rate of the silicon dioxide and the manganese salt in the step 2 is 0.1-1.0 mol/L per hour.
In the scheme, in the step 2, the silicon dioxide is nano-scale powder, the particle size range of the silicon dioxide powder is 50-300 nm, the manganese salt is nano-scale particles, and the particle size range of the manganese salt particles is 50-1000 nm.
In the foregoing scheme, the lithium salt in step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide.
In the scheme, the primary stirring time in the step 2 is 1-2 hours, and the stirring temperature of the secondary stirring is 50-150 ℃.
In the scheme, the solid-liquid mass ratio of the second solution in the step 3 is 3: 1-1: 5.
In the scheme, the sintering temperature in the step 3 is 500-800 ℃, and the sintering time is 5-10 h.
Compared with the prior art, the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material and a preparation method thereof, and the chemical general formula of the material is Li(1+4n)NixCoyMn(1-x-y+n)SinO2+4nWherein x is more than or equal to 0.6 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.2, and n is more than or equal to 0 and less than or equal to 0.05; the method prepares a primary sintered product LiNixCoyMn(1-x-y)O2And then the primary sintered product LiNixCoyMn(1-x-y)O2Adding the lithium manganese silicate into a lithium manganese silicate coating solution, and finally sintering to obtain a lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material; therefore, the invention utilizes the advantages of high capacity and high safety of the lithium manganese silicate to coat the lithium manganese silicate on the surface of the ternary material, thereby improving the capacity and safety of the material; and by combining the longer cycle life of the ternary material, a more ideal power battery anode material can be obtained.
Drawings
Fig. 1 is a discharge characteristic comparison diagram of a lithium manganese silicate-coated nickel-cobalt-manganese ternary material and a preparation method thereof provided in embodiment 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the following embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li(1+4n)NixCoyMn(1-x-y+n)SinO2+4nWherein x is more than or equal to 0.6 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.2, and n is more than or equal to 0 and less than or equal to 0.05.
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding NixCoyMn(1-x-y)(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 10-20 h at 700-900 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNixCoyMn(1-x-y)O2；
Wherein the molar amount of the lithium source is equal to NixCoyMn(1-x-y)(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1-2 hours for one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at a rate of 0.1-1.0 mol/L per hour until the content of Li in the solution: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 50-150 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, in the step 2, the silicon dioxide is nano-scale powder, the granularity range of the silicon dioxide powder is 50-300 nm, the manganese salt is nano-scale particles, and the granularity range of the manganese salt particles is 50-1000 nm;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNixCoyMn(1-x-y)O2Adding the diluted lithium manganese silicate coating solution into the diluted lithium manganese silicate coating solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally, putting the evaporated second solution into a sintering furnace, and sintering at 500-800 ℃ for 5-to-upAnd obtaining the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material after 10 hours.
The invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material and a preparation method thereof, wherein the chemical general formula of the material is Li(1+4n)NixCoyMn(1-x-y+n)SinO2+4nWherein x is more than or equal to 0.6 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.2, and n is more than or equal to 0 and less than or equal to 0.05; the method prepares a primary sintered product LiNixCoyMn(1-x-y)O2And then the primary sintered product LiNixCoyMn(1-x-y)O2Adding the lithium manganese silicate into a lithium manganese silicate coating solution, and finally sintering to obtain a lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material; therefore, the invention utilizes the advantages of high capacity and high safety of the lithium manganese silicate to coat the lithium manganese silicate on the surface of the ternary material, thereby improving the capacity and safety of the material; and by combining the longer cycle life of the ternary material, a more ideal power battery anode material can be obtained.
The invention adopts a wet coating mode, so that the coating agent can be uniformly attached to the surface of the material, and the coating thickness is uniform; the sintering temperature is 500-800 ℃, so that lithium salt, manganese salt and silicon dioxide can react to generate lithium manganese silicate, and the lithium manganese silicate is coated on the surface of the nickel cobalt lithium manganate ternary material; meanwhile, the theoretical specific capacity of the coating material manganese silicate can reach 330330mAh/g, which is higher than the specific capacity of the current common ternary material of 270mAh/g, and the Si-O bond has higher thermal stability, so that the safety performance of the material can be improved; in addition, the Mn element in the lithium manganese silicate material is low in price and environment-friendly.
Example 1
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li1.04Ni0.6Co0.2Mn0.21Si0.01O2.04。
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.6Co0.2Mn0.2(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 15h at 800 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNi0.6Co0.2Mn0.2O2；
Wherein the molar amount of the lithium source is equal to NixCoyMn(1-x-y)(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1-2 hours for one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at a rate of 0.1mol/L per hour until the content of Li in the solution: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 100 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.6Co0.2Mn0.2O2Adding the diluted lithium manganese silicate coating solution into the obtained second solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally, putting the evaporated second solution into a sintering furnace, and sintering for 5 hours at 650 ℃ to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material.
The discharge performance of the coated 622 nickel cobalt manganese ternary material obtained by the method is compared with that of the traditional 622 nickel cobalt manganese ternary material, and a discharge characteristic comparison graph is shown in figure 1, as can be seen from the graph, a curve 1 is the coated 622 nickel cobalt manganese ternary material obtained by the method, the specific discharge capacity reaches 170mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, and a curve 2 is the traditional 622 nickel cobalt manganese ternary material, and the specific discharge capacity only reaches 159mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, so that the coating of the manganese lithium silicate obviously improves the theoretical specific capacity of the material
Example 2
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li1.08Ni0.6Co0.2Mn0.22Si0.02O2.08。
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.6Co0.2Mn0.2(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 15h at 800 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNi0.6Co0.2Mn0.2O2；
Wherein the molar amount of the lithium source is equal to Ni0.6Co0.2Mn0.2(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1-2 hours for one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at a rate of 0.5mol/L per hour until the content of Li in the solution: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 100 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.6Co0.2Mn0.2O2Adding into diluted lithium manganese silicate bagAnd covering the solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally placing the evaporated second solution into a sintering furnace, and sintering for 5 hours at 650 ℃ to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material.
The discharge performance of the coated 622 nickel cobalt manganese ternary material is compared with that of the traditional 622 nickel cobalt manganese ternary material, a discharge characteristic comparison graph is similar to that of the embodiment 1, the coated 622 nickel cobalt manganese ternary material obtained by the invention has the specific discharge capacity of 172mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, and the traditional 622 nickel cobalt manganese ternary material has the specific discharge capacity of only 159mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, so that the theoretical specific capacity of the material is obviously improved by coating the manganese silicate lithium.
Example 3
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li1.12Ni0.6Co0.2Mn0.23Si0.03O2.12。
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.6Co0.2Mn0.2(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 15h at 800 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNi0.6Co0.2Mn0.2O2；
Wherein the molar amount of the lithium source is equal to Ni0.6Co0.2Mn0.2(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1-2 hours for one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at a rate of 1.0mol/L per hour until the Li: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 100 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.6Co0.2Mn0.2O2Adding the diluted lithium manganese silicate coating solution into the obtained second solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally, putting the evaporated second solution into a sintering furnace, and sintering for 5 hours at 650 ℃ to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material.
The discharge performance of the coated 622 nickel cobalt manganese ternary material is compared with that of the traditional 622 nickel cobalt manganese ternary material, a discharge characteristic comparison graph is similar to that of the embodiment 1, the coated 622 nickel cobalt manganese ternary material obtained by the invention has the specific discharge capacity of 170mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, and the traditional 622 nickel cobalt manganese ternary material has the specific discharge capacity of only 159mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, so that the theoretical specific capacity of the material is obviously improved by coating the manganese silicate lithium.
Example 4
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li1.16Ni0.6Co0.2Mn0.24Si0.04O2.16。
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.6Co0.2Mn0.2(OH)2The ternary precursor is mixed with lithium source and oxygenSintering at 700 ℃ for 20h in gas atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNi0.6Co0.2Mn0.2O2；
Wherein the molar amount of the lithium source is equal to Ni0.6Co0.2Mn0.2(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1-2 hours for one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at a rate of 0.8mol/L per hour until the content of Li in the solution: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 100 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.6Co0.2Mn0.2O2Adding the diluted lithium manganese silicate coating solution into the obtained second solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally, putting the evaporated second solution into a sintering furnace, and sintering at 650 ℃ for 8 hours to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material.
The discharge performance of the coated 622 nickel cobalt manganese ternary material is compared with that of the traditional 622 nickel cobalt manganese ternary material, a discharge characteristic comparison graph is similar to that of the embodiment 1, the coated 622 nickel cobalt manganese ternary material obtained by the invention has the specific discharge capacity of 175mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, and the traditional 622 nickel cobalt manganese ternary material has the specific discharge capacity of only 159mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, so that the theoretical specific capacity of the material is obviously improved by coating the manganese silicate lithium.
Example 5
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li1.2Ni0.6Co0.2Mn0.25Si0.05O2.2。
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.6Co0.2Mn0.2(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 15h at 800 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNixCoyMn(1-x-y)O2；
Wherein the molar amount of the lithium source is equal to Ni0.6Co0.2Mn0.2(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1-2 hours for one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at a rate of 0.8mol/L per hour until the content of Li in the solution: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 100 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.6Co0.2Mn0.2O2Adding the diluted lithium manganese silicate coating solution into the obtained second solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, and finally evaporating the evaporated second solutionAnd (3) placing the lithium manganese silicate into a sintering furnace, and sintering for 8 hours at 650 ℃ to obtain the lithium nickel cobalt manganese silicate-coated lithium nickel manganese oxide ternary material.
The discharge performance of the coated 622 nickel cobalt manganese ternary material is compared with that of the traditional 622 nickel cobalt manganese ternary material, a discharge characteristic comparison graph is similar to that of the embodiment 1, the coated 622 nickel cobalt manganese ternary material obtained by the invention has the specific discharge capacity of 173mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, and the traditional 622 nickel cobalt manganese ternary material has the specific discharge capacity of only 159mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, so that the theoretical specific capacity of the material is obviously improved by coating the manganese silicate lithium.
Example 6
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li1.04Ni0.7Co0.1Mn0.21Si0.01O2.04Wherein x is more than or equal to 0.6 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.2, and n is more than or equal to 0 and less than or equal to 0.05.
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.7Co0.1Mn0.2(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 10 hours at 900 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNi0.7Co0.1Mn0.2O2；
Wherein the molar amount of the lithium source is equal to Ni0.7Co0.1Mn0.2(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1-2 hours for one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at a rate of 0.8mol/L per hour until the content of Li in the solution: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 100 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.7Co0.1Mn0.2O2Adding the diluted lithium manganese silicate coating solution into the obtained second solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally, putting the evaporated second solution into a sintering furnace, and sintering at 650 ℃ for 8 hours to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material.
Compared with the traditional 712 nickel-cobalt-manganese ternary material, the discharge performance of the obtained coated 712 nickel-cobalt-manganese ternary material is compared, and a discharge characteristic comparison graph is similar to that of the embodiment 1, the coated 712 nickel-cobalt-manganese ternary material obtained by the invention has the specific discharge capacity of 172mAh/g when 1C charging and 2C discharging are carried out under the conditions of 2.75-4.3V and normal temperature, while the traditional 712 nickel-cobalt-manganese ternary material has the specific discharge capacity of only 159mAh/g when 1C charging and 2C discharging are carried out under the conditions of 2.75-4.3V and normal temperature, so that the theoretical specific capacity of the material is obviously improved by coating the manganese lithium silicate.
Example 7
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li1.08Ni0.7Co0.1Mn0.22Si0.02O2.08。
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.7Co0.1Mn0.2(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 16h at 800 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNi0.7Co0.1Mn0.2O2；
Wherein the molar amount of the lithium source is equal to Ni0.7Co0.1Mn0.2(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1 hour once to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at the rate of 1.5mol/L per hour until the content of Li in the solution is: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 50 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.7Co0.1Mn0.2O2Adding the diluted lithium manganese silicate coating solution into the obtained second solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally, putting the evaporated second solution into a sintering furnace, and sintering for 7 hours at 650 ℃ to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material.
Compared with the traditional 712 nickel-cobalt-manganese ternary material, the discharge performance of the obtained coated 712 nickel-cobalt-manganese ternary material is compared, and a discharge characteristic comparison graph is similar to that of the embodiment 1, the coated 712 nickel-cobalt-manganese ternary material obtained by the invention has the specific discharge capacity of 173mAh/g when 1C charging and 2C discharging are carried out under the conditions of 2.75-4.3V and normal temperature, while the traditional 712 nickel-cobalt-manganese ternary material has the specific discharge capacity of only 159mAh/g when 1C charging and 2C discharging are carried out under the conditions of 2.75-4.3V and normal temperature, so that the theoretical specific capacity of the material is obviously improved by coating the manganese lithium silicate.
Example 8
The inventionThe embodiment provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, and the chemical general formula of the material is Li1.12Ni0.7Co0.1Mn0.23Si0.03O2.12。
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.7Co0.1Mn0.2(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 16h at 800 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNi0.7Co0.1Mn0.2O2；
Wherein the molar amount of the lithium source is equal to Ni0.7Co0.1Mn0.2(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1.2 hours at a time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at the rate of 1.5mol/L per hour until the content of Li in the solution: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 100 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.7Co0.1Mn0.2O2Adding the diluted lithium manganese silicate coating solution into the obtained second solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally, putting the evaporated second solution into a sintering furnace, sintering for 7 hours at 650 ℃ to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary materialAnd (5) feeding.
Compared with the traditional 712 nickel cobalt manganese ternary material, the discharge performance of the obtained coated 712 nickel cobalt manganese ternary material is compared, and the discharge characteristic comparison graph is similar to that of the embodiment 1, the coated 712 nickel cobalt manganese ternary material obtained by the invention has the specific discharge capacity of 171mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, while the traditional 712 nickel cobalt manganese ternary material has the specific discharge capacity of only 159mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, so that the theoretical specific capacity of the material is obviously improved by coating the manganese lithium silicate.
Example 9
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li1.16Ni0.7Co0.1Mn0.24Si0.04O2.16。
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.7Co0.1Mn0.2(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 16h at 800 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNi0.7Co0.1Mn0.2O2；
Wherein the molar amount of the lithium source is equal to Ni0.7Co0.1Mn0.2(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 2 hours once to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at the rate of 1.5mol/L per hour until the content of Li in the solution is: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 150 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.7Co0.1Mn0.2O2Adding the diluted lithium manganese silicate coating solution into the obtained second solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally, putting the evaporated second solution into a sintering furnace, and sintering for 7 hours at 650 ℃ to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material.
Compared with the traditional 712 nickel-cobalt-manganese ternary material, the discharge performance of the obtained coated 712 nickel-cobalt-manganese ternary material is compared, and a discharge characteristic comparison graph is similar to that of the embodiment 1, the coated 712 nickel-cobalt-manganese ternary material obtained by the invention has the specific discharge capacity of 172mAh/g when 1C charging and 2C discharging are carried out under the conditions of 2.75-4.3V and normal temperature, while the traditional 712 nickel-cobalt-manganese ternary material has the specific discharge capacity of only 159mAh/g when 1C charging and 2C discharging are carried out under the conditions of 2.75-4.3V and normal temperature, so that the theoretical specific capacity of the material is obviously improved by coating the manganese lithium silicate.
Example 10
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li1.2Ni0.7Co0.1Mn0.25Si0.05O2.2。
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.7Co0.1Mn0.2(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 10-20 h at 700-900 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNi0.7Co0.1Mn0.2O2；
Wherein the molar amount of the lithium source is equal to Ni0.7Co0.1Mn0.2(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1.8 hours at one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at the rate of 0.6mol/L per hour until the content of Li in the solution: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 100 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.7Co0.1Mn0.2O2Adding the diluted lithium manganese silicate coating solution into the obtained second solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally, putting the evaporated second solution into a sintering furnace, and sintering at 500 ℃ for 10 hours to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material.
Compared with the traditional 712 nickel-cobalt-manganese ternary material, the discharge performance of the obtained coated 712 nickel-cobalt-manganese ternary material is compared, and a discharge characteristic comparison graph is similar to that of the embodiment 1, the coated 712 nickel-cobalt-manganese ternary material obtained by the invention has the specific discharge capacity of 174mAh/g when 1C charging and 2C discharging are carried out under the conditions of 2.75-4.3V and normal temperature, while the traditional 712 nickel-cobalt-manganese ternary material has the specific discharge capacity of only 159mAh/g when 1C charging and 2C discharging are carried out under the conditions of 2.75-4.3V and normal temperature, so that the theoretical specific capacity of the material is obviously improved by coating the manganese lithium silicate.
Example 11
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li1.08Ni0.6Co0.2Mn0.22Si0.02O2.08。
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.6Co0.2Mn0.2(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 10-20 h at 700-900 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNi0.6Co0.2Mn0.2O2；
Wherein the molar amount of the lithium source is equal to Ni0.6Co0.2Mn0.2(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1.8 hours at one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at the rate of 0.6mol/L per hour until the content of Li in the solution: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 100 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.6Co0.2Mn0.2O2Adding the diluted lithium manganese silicate coating solution into the obtained second solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally, putting the evaporated second solution into a sintering furnace, and sintering for 7 hours at 700 ℃ to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material.
The discharge performance of the coated 622 nickel cobalt manganese ternary material is compared with that of the traditional 622 nickel cobalt manganese ternary material, a discharge characteristic comparison graph is similar to that of the embodiment 1, the coated 622 nickel cobalt manganese ternary material obtained by the invention has the specific discharge capacity of 174mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, and the traditional 622 nickel cobalt manganese ternary material has the specific discharge capacity of only 159mAh/g when 1C is charged and 2C is discharged under the conditions of 2.75-4.3V and normal temperature, so that the theoretical specific capacity of the material is obviously improved by coating the manganese lithium silicate.
Example 12
The embodiment of the invention provides a lithium manganese silicate coated nickel-cobalt-manganese ternary material, which has a chemical general formula of Li1.12Ni0.7Co0.1Mn0.23Si0.03O2.12。
The embodiment of the invention also provides a preparation method of the lithium manganese silicate coated nickel-cobalt-manganese ternary material, which is implemented by the following steps:
step 1, adding Ni0.7Co0.1Mn0.2(OH)2Uniformly mixing the ternary precursor with a lithium source, sintering for 10-20 h at 700-900 ℃ in an oxygen atmosphere, and finally crushing and sieving to obtain a primary sintered product LiNi0.7Co0.2Mn0.1O2；
Wherein the molar amount of the lithium source is equal to Ni0.7Co0.1Mn0.2(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn);
wherein the lithium source is at least one of lithium carbonate, lithium hydroxide or lithium oxalate;
and 2, dissolving lithium salt in enough water, stirring for 1.8 hours at one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution at the rate of 0.6mol/L per hour until the content of Li in the solution: si: the Mn molar ratio is 4: 1: 1, stirring for the second time at 100 ℃ and standing to obtain a lithium manganese silicate coating solution;
wherein, the silicon dioxide in the step 2 is nano-scale powder, and the manganese salt is nano-scale particles;
wherein, the lithium salt in the step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide;
step 3, the primary sintered product LiNi0.7Co0.1Mn0.2O2Adding the diluted lithium manganese silicate coating solution into the obtained second solution to obtain a second solution, controlling the solid-liquid mass ratio of the second solution to be 3: 1-1: 5, stirring and evaporating to dryness, finally, putting the evaporated second solution into a sintering furnace, and sintering for 5 hours at 800 ℃ to obtain the lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material.
Compared with the traditional 712 nickel-cobalt-manganese ternary material, the discharge performance of the obtained coated 712 nickel-cobalt-manganese ternary material is compared, and a discharge characteristic comparison graph is similar to that of the embodiment 1, the coated 712 nickel-cobalt-manganese ternary material obtained by the invention has the specific discharge capacity of 172mAh/g when 1C charging and 2C discharging are carried out under the conditions of 2.75-4.3V and normal temperature, while the traditional 712 nickel-cobalt-manganese ternary material has the specific discharge capacity of only 159mAh/g when 1C charging and 2C discharging are carried out under the conditions of 2.75-4.3V and normal temperature, so that the theoretical specific capacity of the material is obviously improved by coating the manganese lithium silicate.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.

Claims (10)

1. A preparation method of a lithium manganese silicate coated nickel-cobalt-manganese ternary material is characterized by comprising the following steps:
step 1, adding NixCoyMn(1-x-y)(OH)2The ternary precursor and the lithium source are mixed with Ni according to the molar weight of the lithium sourcexCoyMn(1-x-y)(OH)2The sum of the molar weight of nickel, cobalt and manganese in the ternary precursor is more than or equal to 1.00 and less than or equal to 1.10 of Li (Ni + Co + Mn), then the mixture is sintered in an oxygen atmosphere, and finally the mixture is crushed and sieved to obtain a primary sintered product LiNixCoyMn(1-x-y)O2；
And 2, dissolving lithium salt in enough water, stirring for one time to obtain a first solution, and then adding silicon dioxide and manganese salt into the first solution until the content of Li in the solution is: si: the Mn molar ratio is 4: 1: 1, stirring for the second time and standing to obtain a lithium manganese silicate coating solution;
step 3, the primary sintered product LiNixCoyMn(1-x-y)O2Adding the solution into a lithium manganese silicate coating solution to obtain a second solution, and sintering the second solution to obtain a lithium manganese silicate coated lithium nickel cobalt manganese oxide ternary material;
the chemical general formula of the lithium manganese silicate coated nickel-cobalt-manganese ternary material is Li(1+4n)NixCoyMn(1-x-y+n)SinO2+4nWherein x is more than or equal to 0.6 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.2, and n is more than or equal to 0 and less than or equal to 0.05.
2. The method according to claim 1, wherein the lithium manganese silicate-coated nickel-cobalt-manganese ternary material in step 1 is prepared by using at least one of lithium carbonate, lithium hydroxide and lithium oxalate as the lithium source.
3. The method for preparing the lithium manganese silicate coated nickel-cobalt-manganese ternary material according to claim 2, wherein the sintering temperature in the step 1 is 700-900 ℃ and the sintering time is 10-20 h.
4. The method for preparing lithium manganese silicate coated nickel cobalt manganese ternary material according to any one of claims 1 to 3, wherein the addition rate of the silicon dioxide and manganese salt in the step 2 is 0.1 to 1.0mol/L per hour.
5. The method as claimed in claim 4, wherein the silicon dioxide in step 2 is a nanoscale powder, the particle size of the silicon dioxide is 50-300 nm, the manganese salt is a nanoscale particle, and the particle size of the manganese salt is 50-1000 nm.
6. The method according to claim 5, wherein the lithium salt in step 2 is lithium hydroxide or lithium oxalate, and the manganese salt is one of manganese carbonate, manganese oxalate or manganese oxide.
7. The method for preparing lithium manganese silicate coated nickel cobalt manganese ternary material according to claim 6, wherein the time of the primary stirring in step 2 is 1-2 h, and the stirring temperature of the secondary stirring is 50-150 ℃.
8. The method for preparing the lithium manganese silicate coated nickel-cobalt-manganese ternary material according to claim 7, wherein the solid-liquid mass ratio of the second solution in the step 3 is 3: 1-1: 5.
9. The method for preparing the lithium manganese silicate coated nickel-cobalt-manganese ternary material according to claim 8, wherein the sintering temperature in the step 3 is 500-800 ℃, and the sintering time is 5-10 h.
10. The lithium manganese silicate coated nickel-cobalt-manganese ternary material is characterized in that the chemical general formula is Li(1+4n)NixCoyMn(1-x-y+n)SinO2+4nWherein x is more than or equal to 0.6 and less than or equal to 0.7, y is more than or equal to 0.1 and less than or equal to 0.2, and n is more than or equal to 0 and less than or equal to 0.05; the lithium manganese silicate-coated nickel-cobalt-manganese ternary material is prepared by the preparation method of the lithium manganese silicate-coated nickel-cobalt-manganese ternary material according to any one of claims 1 to 9.
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