CN109860561B - Lithium-manganese-boron-rich hollow microsphere and preparation method and application thereof - Google Patents
Lithium-manganese-boron-rich hollow microsphere and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a lithium-rich manganese-boron hollow microsphere and a preparation method and application thereof. The preparation method comprises the following steps: dispersing Ni-Co-B alloy microspheres in water, adding a manganese source and a precipitator, adjusting the pH, and carrying out hydrothermal reaction to obtain MnCO3@ Ni-Co-B precursor; mixing MnCO3And mixing the @ Ni-Co-B precursor with a lithium source, and calcining by stages to obtain the lithium-rich manganese-boron hollow microsphere. The hollow microsphere can be used as a positive electrode material, and has high capacity, high rate performance and good cycling stability.
Description
Technical Field
The invention relates to a hollow microsphere, in particular to a preparation method of a lithium-manganese-boron-rich hollow microsphere, belonging to the technical field of material preparation.
Background
The secondary lithium ion battery has the advantages of high specific energy, light weight, environmental friendliness, diversified applications and the like, and is an excellent substitute for fossil fuels. In recent years, with the rapid development of new energy automobiles and energy storage networks, the technology of secondary lithium ion batteries is developed in a leap manner and gradually becomes a mature commercial energy source. At present, the core problem limiting the application of lithium ion batteries is the safety, low-temperature performance and other main performance parameters of the batteries, especially the high-low temperature performance, cycle life and safety of the anode material.
The lithium-rich manganese-based material is a layered oxide anode material with alpha-NaFeO-like structure2R belonging to the hexagonal system3-mThe space group has the specific capacity of more than 250mAh/g and the high working voltage of more than 4.3V, and the high specific capacity of the space group enables the material to have wide application prospect in the fields of electrodynamic force automobiles and the like.
Among the lithium-rich manganese-based materials, the lithium-rich material has a high energy density, but has poor rate performance, and interface side reactions and structural transformation are easy to occur in the circulation process, so that the capacity of the battery is rapidly attenuated. The current modification to the problem mainly adopts a doping and surface coating method, but does not achieve the essential improvement effect.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a positive electrode material having a high capacity, a high rate capability, a good cycle stability, and a long life.
In order to achieve the technical purpose, the invention provides a preparation method of lithium manganese boron-rich hollow microspheres, which comprises the following steps:
dispersing Ni-Co-B alloy microspheres in 30-80 mL of water, adding 2-20 mmol of manganese source and a proper amount of precipitator, adjusting the pH to 3-7, and carrying out hydrothermal reaction at 120-180 ℃ for 4-12 h to obtain MnCO3@ Ni-Co-B precursor;
mixing MnCO3Mixing the precursor of @ Ni-Co-B with a lithium source, calcining for 2h-8h at 400-500 ℃ in air atmosphere, and then calcining for 5h-20h at 750-900 ℃ to obtain the lithium-manganese-boron-rich hollow microsphere xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)y。
In a specific embodiment of the invention, the obtained lithium-rich manganese-boron hollow microsphere xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yWherein x is 0.2-0.8 and y is 1, 1.03, 1.05, 1.07, 1.09 or 1.12.
The preparation method of the invention realizes gradient distribution of manganese-rich on the surface and nickel-rich in the interior by utilizing the kirkendall effect to obtain xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yA hollow microsphere structure.
Wherein the manganese on the surface can utilize Mn4+The structure stability of the method protects a charge exchange area in the electrochemical reaction process and reduces the ion migration resistance. Inner core rich in Ni2+Can effectively improve the generation of spinel phase in the charging and discharging process and improve the coulombic efficiency and the capacity exertion of the material. In addition, boron can greatly improve the ionic conductivity of the inner layer material, so that the particles in the hollow microspheres can also play a higher role.
In addition, the preparation method can regulate and control the gradient distribution of manganese and nickel through the calcining temperature and the heat preservation time, so that the process parameters are easier to regulate and have stronger controllability.
In the preparation method of the present invention, the kirkendall effect (kirkendall effect) is a diffusion phenomenon that occurs in metal ions in a solid substance. Because the precursor core is Ni-Co-B alloy microsphere and the surface is wrapped by the manganese-rich outer layer, the concentration difference and the charge difference of metal elements are formed, and because one Ni layer2+To be associated with a Mn4+The valence state of +3 can be ensured only by combination, so that Mn is driven by concentration difference and charge difference to move to the inner core, and Ni, Co and B elements move to the outer layer, and a hollow microsphere structure with gradient distribution is formed through ion migration.
In one embodiment of the invention, the Ni-Co-B alloy microspheres are prepared according to the following steps:
adding a nickel source and a cobalt source into a sodium hydroxide solution, adding a stabilizer, and stirring for 0.5h to obtain a metal hydroxide sol; wherein the molar ratio of the nickel source to the cobalt source is 1: 1; adding 1-5mmol of nickel source into 100mL of sodium hydroxide solution;
and (2) putting the metal hydroxide sol into ultrasonic and stirring conditions, dropwise adding 10mL of hydroboron aqueous solution to obtain black precipitate, and washing, filtering and drying the black precipitate to obtain the Ni-Co-B alloy microspheres.
In the preparation method of the invention, Ni, Co and B elements are uniformly precipitated by a chemical plating method, thereby ensuring the uniform distribution of B element doping.
In one embodiment of the present invention, a method for preparing lithium manganese boron-rich hollow microspheres may comprise:
the method comprises the following steps: adding a nickel source and a cobalt source into a sodium hydroxide solution, adding a stabilizer, and stirring to obtain a metal hydroxide sol; wherein the molar ratio of the nickel source to the cobalt source is 1: 1; every 1mmol-5mmol of the nickel source is added to 100mL of sodium hydroxide solution.
In the first step, the nickel source is nickel sulfate [ NiSO ]4]Nickel acetate [ Ni (Ac)2]Nickel nitrate [ Ni (NO) ]3)2]One or a combination of two or more of them.
In step one, the cobalt source used is cobalt sulfate [ CoSO ]4]Cobalt acetate [ Co (Ac)2]Cobalt nitrate [ Co (NO)3)2]One or a combination of two or more of them.
In the first step, the mass concentration of the adopted sodium hydroxide solution is 0.02M-0.2M. For example, the sodium hydroxide solution may be used at a mass concentration of 0.05M, 0.08M, 0.1M, 0.15M, or 0.18M.
In step one, the purpose of the stabilizer is to stabilize the sol system. The adopted stabilizer can be one or the combination of more than two of polyethylene glycol (PEG), lactic acid and ammonium citrate.
In the first step, 0.1g to 0.5g of stabilizer is added to each 100mL of sodium hydroxide solution.
In step one, the stirring time may be 0.5 h.
In one embodiment of the present invention, a method for preparing lithium manganese boron-rich hollow microspheres may comprise:
step two: and (2) placing the metal hydroxide sol in an ultrasonic and stirring strong dispersion environment, dropwise adding 10mL of hydroboron aqueous solution to obtain black precipitate, and washing, filtering and drying the black precipitate to obtain the Ni-Co-B alloy microspheres.
In the second step, the aqueous solution of borohydride is added in the strong dispersion environment of ultrasound and stirring, so that the aqueous solution of borohydride (reducing agent) is contacted with the viscous metal hydroxide sol in a relatively dispersed manner, and the reaction is more uniform.
In step two, the power of the ultrasound can be 20-100W.
In the second step, the stirring speed can be 300r/min-1200 r/min.
In the second step, the dropping speed is 1 drop/1 s-1 drop/15 s.
In the second step, the aqueous solution of borohydride is formed by adding borohydride into water and stirring for 0.5 h. Wherein, the concentration of the aqueous solution of borohydride can be 0.01mol/L-0.1 mol/L.
In step two, the borohydride may be lithium borohydride (LiBH)4) Sodium borohydride (NaBH)4) Potassium borohydride (KBH)4) One or a combination of two or more of them.
According to the preparation method, the Ni-Co-B alloy microspheres with the boron (B) elements uniformly distributed are prepared through the first step and the second step, and the alloy microspheres are used as hard templates for subsequently synthesizing the hollow microspheres, so that the prepared hollow microspheres have hollow structures and are made of the lithium-rich ternary (Ni-Co-Mn) material doped with borate.
According to the invention, the B element, Ni and Co are uniformly mixed at an atomic level through the first step and the second step to form the alloyed microsphere, as shown in figures 1 and 2, the doping of borate at the atomic level can greatly improve the cycling stability of the material and the electrochemical activity. As can be seen from the EDX-mapping of FIG. 1, B, Ni and Co are uniformly dispersed at the atomic level, which shows that various elements in the precursor are uniformly mixed in the microscopic range.
In one embodiment of the present invention, a method for preparing lithium manganese boron-rich hollow microspheres may comprise:
step three: dispersing Ni-Co-B alloy microspheres in 30-80 mL of water, adding 2-20 mmol of manganese source and a proper amount of precipitator, adjusting the pH to 3-7, and carrying out hydrothermal reaction at 120-180 ℃ for 4-12 h to obtain MnCO3@ Ni-Co-B precursor.
In the third step, manganese source may be manganese sulfate [ MnSO ]4]Manganese acetate [ Mn (Ac)2]Manganese nitrate [ Mn (NO)3)2]One or a combination of two or more of them.
In the third step, the precipitator makes manganese element precipitate on the surface of the Ni-Co-B alloy microsphere to form a manganese-rich outer layer. Wherein the addition amount of the precipitator is 1-5 times of the mass of the manganese source.
In step three, the precipitant used may be urea and/or melamine.
In one embodiment of the present invention, a method for preparing lithium manganese boron-rich hollow microspheres may comprise:
step four: mixing MnCO3Mixing the precursor of @ Ni-Co-B with a lithium source, calcining for 2h-8h at 400-500 ℃ in air atmosphere, and then calcining for 5h-20h at 750-900 ℃ to obtain the lithium-manganese-boron-rich hollow microsphere xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)y。
In the fourth step, the spherical structure can be prevented from cracking due to the excessively high temperature rise speed by the sectional calcination.
And in the fourth step, after mixing with a lithium source, carrying out fractional calcination, and forming hollow microspheres with Mn elements enriched on the surface layer and in gradient distribution by utilizing the Cokendall effect. As shown in EDX-mapping of fig. 3, the content of Ni and Mn elements in the core of the spherical particles is low because the spheres are hollow structures; the Ni element is enriched more in the shell layer, the Mn element is enriched on the surface of the shell layer of the hollow microsphere, and the two elements are distributed in a gradient manner on the thickness scale.
In step four, the lithium source used may be lithium hydroxide (LiOH), lithium carbonate (Li)2CO3) Lithium nitrate (LiNO)3) One or a combination of two or more of them.
In the fourth step, the amount of the lithium source added is based on the total amount of the metals manganese, cobalt and nickel. Wherein the molar ratio of the sum of Mn + Co + Ni) to Li is 1: y (1+0.33 x).
The invention also provides an xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yThe hollow microspheres, wherein x is 0.2-0.8, y is 1, 1.03, 1.05, 1.07, 1.09 or 1.12, are prepared by the preparation method of the lithium-rich manganese-boron hollow microspheres.
xLi of the invention2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yThe particle size of the hollow microsphere is 2-40 μm, and the thickness of the hollow shell is 2-20 μm.
The granularity of the hollow microsphere and the thickness of the hollow shell layer can be biased according to the requirements of power and energy density, and the process parameters are adjusted to control the hollow microsphere.
The invention also provides a positive electrode material, which is prepared from the xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yHollow microspheres.
The cathode material of the invention can be used as the cathode of a battery, wherein the battery comprises but is not limited to a lithium ion battery.
The preparation method of the invention firstly obtains Ni-Co-B alloy microspheres with uniformly distributed B elements by a chemical plating method, and synthesizes the lithium-rich manganese-boron hollow microspheres by taking the alloy microspheres as hard templates. The chemical plating method enables the B element, Ni and Co to be evenly mixed at an atomic level to form alloy microspheres, and the doping of the atomic borate can greatly improve the cycling stability of the material and the electrochemical activity.
The preparation method of the invention utilizes the Cokendall effect to form a hollow sphere structure with Mn elements enriched on the surface layer and in gradient distribution, ensures a good electrochemical reaction interface by utilizing the high stability of the Mn elements, and can obtain more electrochemical reaction active sites by utilizing the hollow configuration, so that the capacity of the material is higher.
The preparation method has the advantages of simple process, good stability and easy regulation and control of process parameters.
xLi obtained by the production method of the present invention2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yThe hollow microsphere has a specific discharge capacity of more than 262mAh/g and a capacity retention ratio of more than 91% after 50 times of circulation under a voltage window of 2-4.8V and a multiplying power of 0.2C.
Drawings
FIG. 1 is an EDX-Mapping chart of an alloy microsphere in an embodiment of the invention.
FIG. 2 is an SEM image of alloy microspheres in an embodiment of the invention.
FIG. 3 is an EDX-Mapping chart of hollow microspheres in one embodiment of the present invention.
FIG. 4 is 0.5Li of example 12MnO3·0.5LiNi0.33Co0.33Mn0.33O1.95·(BO3)0.03Scanning electron micrographs of hollow microspheres.
Fig. 5 is a graph of cycle performance at 0.2C rate of the positive electrode material of example 1.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1
This example provides 0.5Li2MnO3·0.5LiNi0.33Co0.33Mn0.33O1.95·(BO3)0.03Hollow microspheres obtained byPrepared by the following steps.
The method comprises the following steps: weighing 3mmol of NiSO4And 3mmol of Co (Ac)2100mL of 0.05M NaOH solution was added, 0.3g of PEG was added, and the mixture was stirred for 0.5 hour to form a stable sol.
Step two: weighing 0.6mmol of KBH4After dissolving with 15mL of deionized water, the mixture is magnetically stirred for 0.5h to form a stable solution.
Step three: putting the sol obtained in the step one into a stirring environment with 100w ultrasound and 500r/min, and dropwise adding KBH obtained in the step two at the speed of 1 drop/3 s4And (3) reacting the solution for 30min to obtain black precipitate, washing and filtering the precipitate, and drying to obtain the Ni-Co-B alloy microspheres.
Step four: ultrasonically dispersing the Ni-Co-B alloy microspheres obtained in the third step into 80mL of deionized water, and adding 12mmol of MnSO4And 6g of urea, adjusting the pH value to 6.5 by using ammonia water, transferring the mixture into a 100mL hydrothermal kettle, and reacting for 6 hours at 125 ℃ to obtain MnCO3@ Ni-Co-B precursor.
Step five: mixing the precursor and LiOH according to a molar ratio of 1:1.05, calcining for 5 hours at 450 ℃ in an air atmosphere, and then calcining for 12 hours at 800 ℃ to obtain 0.5Li2MnO3·0.5LiNi0.33Co0.33Mn0.33O1.95·(BO3)0.03Hollow microspheres. The structure is shown in fig. 4.
The first discharge specific capacity of the hollow microsphere of the embodiment is 262mAh/g under an electrochemical window of 2-4.8V and a multiplying power of 0.2C, and the retention rate of the specific capacity after 50 cycles is 91%, as shown in FIG. 5.
Example 2
This example provides a 0.4Li2MnO3·0.6LiNi0.33Co0.33Mn0.33O1.97·(BO3)0.02Hollow microspheres, which are prepared by the following steps.
The method comprises the following steps: weighing 1mmol of Ni (Ac)2And 1mmol of CoSO4100mL of 0.2M NaOH solution was added, 0.5g of lactic acid was added, and the mixture was stirred for 0.5 hour to form a stable sol.
Step two: weighing 0.1mmol of LiBH4After dissolving with 10mL of deionized water, the mixture is magnetically stirred for 0.5h to form a stable solution.
Step three: putting the sol in the step one into an environment of 20w ultrasound and 1200r/min stirring, and dropwise adding KBH in the step two4And (3) reacting the solution to obtain black precipitate, washing and filtering the black precipitate, and drying to obtain the Ni-Co-B alloy microspheres.
Step four: ultrasonically dispersing the Ni-Co-B alloy microspheres obtained in the third step into 30mL of deionized water, and adding 3mmol of MnSO4And 1g of urea, adjusting the pH value to 3 by using ammonia water, transferring the mixture into a 100mL hydrothermal kettle, and reacting for 12h at 180 ℃ to obtain MnCO3@ Ni-Co-B precursor.
Step five: mixing the precursor with LiNO3Mixing at a molar ratio of 1:1.09, calcining at 500 deg.C for 2 hr in air atmosphere, and calcining at 900 deg.C for 5 hr to obtain 0.4Li2MnO3·0.6LiNi0.33Co0.33Mn0.33O1.97·(BO3)0.02Hollow microspheres.
The first discharge specific capacity of the hollow microsphere of the embodiment is 255mAh/g under an electrochemical window of 2-4.8V and a multiplying power of 0.2C, and the specific capacity retention rate is 82% after 50 times of circulation.
Example 3
This example provides a 0.25Li2MnO3·0.75LiNi0.33Co0.33Mn0.33O1.925·(BO3)0.05Hollow microspheres, which are prepared by the following steps.
The method comprises the following steps: weighing 5mmol of NiSO4And 5mmol of Co (NO)3100mL of 0.2M NaOH solution was added, 0.1g of ammonium citrate was added, and the mixture was stirred for 0.5 hour to form a stable sol.
Step two: weighing 1mmol of NaBH4After dissolving with 30mL of deionized water, the solution is magnetically stirred for 0.5h to form a stable solution.
Step three: putting the sol obtained in the step one into an environment of 50w ultrasound and 300r/min stirring, and dropwise adding the KBH obtained in the step two4Solution, reaction to obtainAnd (4) carrying out black precipitation, washing, suction filtering and drying the black precipitation to obtain the Ni-Co-B alloy microspheres.
Step four: ultrasonically dispersing the Ni-Co-B alloy microspheres obtained in the third step into 50mL of deionized water, and adding 10mmol of MnSO4And 5g of melamine, adjusting the pH value to 7 by using ammonia water, transferring the mixture into a 100mL hydrothermal kettle, and reacting for 6h at 180 ℃ to obtain MnCO3@ Ni-Co-B precursor.
Step five: mixing a precursor with Li2CO3Mixing at a molar ratio of 1:0.535, calcining at 400 ℃ for 8h in an air atmosphere, and then calcining at 750 ℃ for 20h to obtain 0.25Li2MnO3·0.75LiNi0.33Co0.33Mn0.33O1.925·(BO3)0.05Hollow microspheres.
The first discharge specific capacity of the hollow microsphere is 234mAh/g under the electrochemical window of 2-4.8V and the multiplying power of 0.2C, and the specific capacity retention rate is 88.5% after 50 times of circulation.
Example 4
This example provides 0.6Li2MnO3·0.4LiNi0.33Co0.33Mn0.33O1.96·(BO3)0.04Hollow microspheres, which are prepared by the following steps.
The method comprises the following steps: weighing 3mmol of NiSO4And 3mmol of Co (NO)3100mL of 0.16M NaOH solution was added, and a stabilizer (0.1g of PEG and 0.1g of lactic acid) was added and stirred for 0.5h to form a stable sol.
Step two: 0.9mmol of LiBH was weighed4After dissolving with 20mL of deionized water, the solution is magnetically stirred for 0.5h to form a stable solution.
Step three: putting the sol obtained in the first step into an environment of 70w ultrasound and 800r/min stirring, and dropwise adding NaBH obtained in the second step4Reacting the solution to obtain black precipitate, washing, filtering, and drying to obtain the Ni-Co-B alloy microspheres.
Step four: ultrasonically dispersing the Ni-Co-B alloy microspheres obtained in the third step into 60mL of deionized water, and adding 16.5mmol of MnSO42g of urea and 3g of melamine, the pH being adjusted to 4 with ammonia.5, transferring the mixture to a 100mL hydrothermal kettle, and reacting for 7h at 150 ℃ to obtain MnCO3@ Ni-Co-B precursor.
Step five: mixing the precursor with LiNO3Mixing at a molar ratio of 1:1.12, calcining at 420 deg.C for 6h in air atmosphere, and calcining at 800 deg.C for 15h to obtain 0.6Li2MnO3·0.4LiNi0.33Co0.33Mn0.33O1.96·(BO3)0.04Hollow microspheres.
The first discharge specific capacity of the hollow microsphere is 270mAh/g under the electrochemical window of 2-4.8V and the multiplying power of 0.2C, and the specific capacity retention rate is 79.5% after 50 times of circulation.
Example 5
This example provides 0.1Li2MnO3·0.9LiNi0.33Co0.33Mn0.33O1.98·(BO3)0.015Hollow microspheres, which are prepared by the following steps.
The method comprises the following steps: weighing 4mmol of NiSO4And 4mmol of Co (NO)3100mL of 0.2M NaOH solution was added, and a stabilizer (0.2g of lactic acid and 0.2g of ammonium citrate) was added and stirred for 0.5h to form a stable sol.
Step two: 0.2mmol of NaBH was weighed4After dissolving with 15mL of deionized water, the mixture is magnetically stirred for 0.5h to form a stable solution.
Step three: putting the sol obtained in the first step into a strong stirring environment of 45w ultrasound and 350r/min, and dropwise adding NaBH obtained in the second step4Reacting the solution to obtain black precipitate, washing, filtering, and drying to obtain the Ni-Co-B alloy microspheres.
Step four: ultrasonically dispersing the Ni-Co-B alloy microspheres obtained in the third step into 40mL of deionized water, and adding 5.3mmol of MnSO41g of urea and 1g of melamine, adjusting the pH value to 3.5 by using ammonia water, transferring the mixture into a 100mL hydrothermal kettle, and reacting for 6 hours at 160 ℃ to obtain MnCO3@ Ni-Co-B precursor.
Step five: mixing the precursor and LiOH according to a molar ratio of 1:1.09, calcining for 5 hours at 460 ℃ in an air atmosphere, and then calcining for 16 hours at 780 ℃ to obtain 0.1Li2MnO3·0.9LiNi0.33Co0.33Mn0.33O1.98·(BO3)0.015Hollow microspheres.
The first discharge specific capacity of the hollow microsphere is 255mAh/g under the electrochemical window of 2-4.8V and the multiplying power of 0.2C, and the specific capacity retention rate is 86.8% after 50 times of circulation.
Claims (19)
1. The preparation method of the lithium-rich manganese-boron hollow microsphere is characterized by comprising the following steps of:
dispersing Ni-Co-B alloy microspheres in 30-80 mL of water, adding 2-20 mmol of manganese source and a proper amount of precipitator, adjusting the pH to 3-7, and carrying out hydrothermal reaction at 120-180 ℃ for 4-12 h to obtain MnCO3The precursor is prepared from @ Ni-Co-B, and the precipitator enables manganese elements to precipitate on the surface of the Ni-Co-B alloy microsphere to form a manganese-rich outer layer;
subjecting the MnCO to3Mixing the precursor of @ Ni-Co-B with a lithium source, calcining for 2h-8h at 400-500 ℃ in air atmosphere, and then calcining for 5h-20h at 750-900 ℃ to obtain the lithium-manganese-boron-rich hollow microsphere xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yX is 0.2-0.8, y =1, 1.03, 1.05, 1.07, 1.09, or 1.12.
2. The preparation method according to claim 1, wherein the Ni-Co-B alloy microspheres are prepared by the following steps:
adding a nickel source and a cobalt source into a sodium hydroxide solution, adding a stabilizer, and stirring to obtain a metal hydroxide sol; wherein the molar ratio of the nickel source to the cobalt source is 1: 1; adding every 1mmol-5mmol of nickel source into 100mL of sodium hydroxide solution;
and (2) putting the metal hydroxide sol under the conditions of ultrasound and stirring, dropwise adding 10mL of hydroboron aqueous solution to obtain black precipitate, and washing, filtering and drying the black precipitate to obtain the Ni-Co-B alloy microspheres.
3. The preparation method according to claim 2, wherein the nickel source is one or a combination of two or more of nickel sulfate, nickel acetate and nickel nitrate;
the mass concentration of the sodium hydroxide solution is 0.02M-0.2M.
4. The method according to claim 2 or 3, wherein the cobalt source is one or a combination of two or more of cobalt sulfate, cobalt acetate, and cobalt nitrate.
5. The method according to claim 2 or 3, characterized in that the concentration of said aqueous solution of borohydride is between 0.01 and 0.1 mol/L.
6. The preparation method according to claim 2 or 3, wherein the borohydride used in the aqueous solution of borohydride is one or a combination of two or more of lithium borohydride, sodium borohydride and potassium borohydride.
7. The method of claim 2, wherein the power of the ultrasound is 20W to 100W.
8. The method of claim 2 or 7, wherein the stirring speed is 300r/min to 1200 r/min.
9. The method according to claim 2 or 7, characterized in that the dropping speed of the aqueous solution of borohydride is 1 drop/1 s-1 drop/15 s.
10. The method according to claim 2, wherein the stabilizer is one or more of polyethylene glycol, lactic acid and ammonium citrate.
11. The method according to claim 2 or 10, wherein 0.1g to 0.5g of the stabilizer is added per 100mL of the sodium hydroxide solution.
12. The method according to claim 2 or 10, wherein the manganese source is one or a combination of two or more of manganese sulfate, manganese acetate and manganese nitrate.
13. The process according to claim 2 or 10, characterized in that the precipitating agent is urea and/or melamine.
14. The method according to claim 13, wherein the precipitant is added in an amount of 1 to 5 times by mass based on the manganese source.
15. The method according to claim 1, wherein the lithium source is one or a combination of two or more of lithium hydroxide, lithium carbonate, and lithium nitrate.
16. The production method according to claim 1 or 15, characterized in that the molar ratio of the sum of Mn, Co and Ni to Li is 1: y (1+0.33 x).
17. xLi2MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yHollow microspheres, characterized in that they are prepared by the method of preparation of lithium manganese boron rich hollow microspheres according to any one of claims 1-16, wherein x is 0.2-0.8, y =1, 1.03, 1.05, 1.07, 1.09 or 1.12.
18. The hollow microsphere according to claim 17, wherein the particle size of the hollow microsphere is from 2 μm to 40 μm and the thickness of the hollow shell is from 2 μm to 20 μm.
19. A positive electrode material comprising the xLi according to claim 17 or 182MnO3·(1-x)LiNi0.33Co0.33Mn0.33O2-1.5y·(BO3)yHollow microspheres.
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| CN104953110A (en) * | 2015-06-25 | 2015-09-30 | 中南大学 | Rich-lithium-manganese-based cathode material used for lithium ion battery of hollow structure and preparation method thereof |
| CN105185979A (en) * | 2015-06-25 | 2015-12-23 | 中南大学 | Hollow structure lithium-ion battery positive electrode material and preparation method thereof |
| CN106340641A (en) * | 2016-11-17 | 2017-01-18 | 兰州理工大学 | Preparation method of hollow spherical nickel-cobalt-lithium manganate capable of adjusting pore diameters automatically |
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| CN104037402A (en) * | 2014-06-19 | 2014-09-10 | 合肥国轩高科动力能源股份公司 | Method for preparing hollow nickle-manganese composite oxide balls |
| CN104953110A (en) * | 2015-06-25 | 2015-09-30 | 中南大学 | Rich-lithium-manganese-based cathode material used for lithium ion battery of hollow structure and preparation method thereof |
| CN105185979A (en) * | 2015-06-25 | 2015-12-23 | 中南大学 | Hollow structure lithium-ion battery positive electrode material and preparation method thereof |
| CN106450278A (en) * | 2016-11-03 | 2017-02-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Ternary positive electrode material with hollow microsphere structure, preparation method and application |
| CN106340641A (en) * | 2016-11-17 | 2017-01-18 | 兰州理工大学 | Preparation method of hollow spherical nickel-cobalt-lithium manganate capable of adjusting pore diameters automatically |
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