CN111180688B - Micron-scale hollow porous sodium-ion battery positive electrode material and preparation method thereof - Google Patents
Micron-scale hollow porous sodium-ion battery positive electrode material and preparation method thereof Download PDFInfo
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- CN111180688B CN111180688B CN201911393479.9A CN201911393479A CN111180688B CN 111180688 B CN111180688 B CN 111180688B CN 201911393479 A CN201911393479 A CN 201911393479A CN 111180688 B CN111180688 B CN 111180688B
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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 micron-scale hollow porous sodium ion battery positive electrode material has a micron-scale hollow porous spherical structure and is formed by self-assembling a sheet structure, wherein the chemical formula of the micron-scale hollow porous spherical structure is Na x Mn 1‑y‑z Ni y Co z O 2 Wherein x is more than 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and y + z is more than or equal to 0 and less than or equal to 1; the invention also discloses a preparation method of the cathode material. The hollow structure of the anode material shortens the deintercalation path of sodium ions to the thickness of the sheet structure, and prevents agglomeration among the sheet structures; the porous structure of the material is beneficial to the contact of the material with a conductive agent and electrolyte, so that the conductivity of the electrode made of the material is improved; the micron hollow porous composite spherical sodium ion battery positive electrode material has good structural stability, and the battery assembled by the electrode made of the material has good rate performance; the method has simple process, the required equipment is consistent with the existing industrialized lithium cobaltate and nickel cobalt manganese ternary cathode material process, and the method can be directly used for production by the existing production line.
Description
Technical Field
The invention relates to a sodium ion battery anode material and a preparation method thereof, in particular to a micron-scale hollow sodium ion battery anode material and a preparation method thereof.
Background
With the rapid development of technology, lithium ion batteries have been widely used in electronic products. The lithium ion battery has the advantages of good cycle performance and high energy density, but because of less lithium resources, high price and potential safety hazard, the lithium ion battery is difficult to obtain larger-scale application.
The sodium element and the lithium element are in the same group, the physical and chemical properties are very similar, and the electrochemical reaction behaviors of the sodium element and the lithium element are also included. And sodium is the sixth element in the earth crust and is widely distributed in land and sea mainly in the form of salt, so that the sodium is abundant in resource and low in price, and a cheap raw material is provided for commercialization of the sodium-ion battery. However, the ionic radius of sodium is 1.02A, which is much higher than the lithium ionic radius (0.76A). The larger ionic radius causes the sodium ions to have lower migration rate in the process of charge and discharge deintercalation, thus showing poorer rate performance, and in addition, the deintercalation of the sodium ions can also cause the collapse of the material structure, thus showing poor electrochemical performance.
In order to improve the electrochemical performance of the sodium ion battery, researchers usually modify the sodium ion battery by designing a bulk phase structure, coating the surface of the sodium ion battery, and doping the sodium ion battery.
CN108987708A discloses a positive electrode material of a sodium ion battery, a preparation method thereof and the sodium ion battery 2 Coated with Na 0.67 Ni 0.167 Co 0.167 Mn 0.67 O 2 The mass of the coating layer of the sodium ion cathode material is 1-10% of that of the matrix; the preparation method comprises coprecipitation, sodium source presintering and zirconium source calcining.
CN108899538A discloses a ternary sodium-ion battery anode material, a preparation method thereof and a sodium-ion battery, wherein the general formula of the anode material is Na 0.67 [Ni 0.167 Co 0.167 Mn 0.67 ] 1-x Ti x O 2 Wherein, 0<x<1; is spherical particles with a laminated structure; the preparation method comprises coprecipitation, presintering and sodium source titanium source calcination.
CN108565457A discloses a positive electrode material of a sodium ion battery and the positive electrode materialThe chemical formula of the positive electrode material is Na x Ni 0.167 Co 0.167 Mn 0.67 O 2 Wherein x is more than or equal to 0.5 and less than or equal to 0.8, and the manganese and nickel are in spherical particles, wherein the concentrations of the manganese and the nickel are in gradient distribution along the radial direction; the preparation method comprises coprecipitation, presintering and sodium source calcination.
The positive electrode material of the sodium ion battery in the invention still has the problems of poor structural stability and low rate capability after being modified.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a micron-scale hollow porous sodium-ion battery positive electrode material and a preparation method thereof; the cathode material has a hollow porous spherical structure formed by self-assembly of a unique sheet structure, the battery assembled by the electrode made of the cathode material has good rate performance and good structural stability, the preparation method is simple, and the cathode material can be directly produced by the existing production line.
The technical scheme adopted by the invention for solving the technical problem is that the micron-scale hollow porous sodium-ion battery anode material has a chemical formula of Na x Mn 1-y-z Ni y Co z O 2 Wherein x is more than 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, and y + z is more than or equal to 0 and less than or equal to 1, and the micron-sized hollow porous spherical structure is formed by self-assembling a sheet structure.
Preferably, the diameter of the hollow porous spherical structure is 8-15 μm.
Preferably, the particle size of the sheet structure is 0.5-1.5 μm; the thickness of the sheet structure is 50-100 nm.
Preferably, x: y is 1-10: 1; and x: z is 1-10: 1.
The invention relates to a preparation method of a micron-scale hollow porous sodium-ion battery anode material, which is characterized by comprising the following steps of:
(1) under the condition of stirring, adding alkali liquor and a nickel-cobalt-manganese salt solution into a reactor, adjusting the pH value by using a pH value regulator, and carrying out a first-stage reaction; then, regulating the pH value to be higher by using a pH value regulator, carrying out second-stage reaction, carrying out solid-liquid separation after the reaction is finished, and washing and drying the precipitate to obtain a precursor;
(2) mixing the obtained precursor with a sodium source, and carrying out two-stage calcination: the first stage of calcination is carried out at the temperature of less than 600 ℃, and the second stage of calcination is carried out at the temperature of more than or equal to 920 ℃, thus obtaining the catalyst.
Preferably, in the step (1), the nickel-cobalt-manganese salt solution is prepared by dissolving nickel salt, cobalt salt and manganese salt in water.
Preferably, the nickel salt is sulfate and hydrate thereof, nitrate and hydrate thereof, chloride and hydrate thereof, acetate and hydrate thereof or oxalate and hydrate thereof.
Preferably, the cobalt salt is sulfate and hydrate thereof, nitrate and hydrate thereof, chloride and hydrate thereof, acetate and hydrate thereof or oxalate and hydrate thereof.
Preferably, the manganese salt is sulfate and hydrate thereof, nitrate and hydrate thereof, chloride and hydrate thereof, acetate and hydrate thereof or oxalate and hydrate thereof.
Preferably, the water is deionized water.
Preferably, in the step (1), the molar ratio of nickel ions to cobalt ions in the nickel-cobalt-manganese salt solution is 1: 0.8-1.2.
Preferably, in the step (1), the molar ratio of nickel ions to manganese ions in the nickel-cobalt-manganese salt solution is 1: 4-8.
Preferably, in the step (1), the concentration of the metal cation in the nickel-cobalt-manganese salt solution is 0.1-5 mol/L, and more preferably 1-2 mol/L.
Preferably, in the step (1), the alkali solution is obtained by dissolving one or more of sodium hydroxide, ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate and hydrate thereof in water, and is more preferably dissolved in deionized water.
Preferably, in the step (1), the concentration of the alkali liquor is 0.001-3 mol/L, and more preferably 1-2 mol/L.
Preferably, in the step (1), the ratio of the sum of the molar weight of the nickel salt, the cobalt salt and the manganese salt to the molar weight of the solute in the alkali liquor is 1: 0.5-100, and more preferably 1: 1-5.
Preferably, in the step (1), the rate of adding the alkali liquor into the reactor is 1-5L/h.
Preferably, in the step (1), the salt solution is added into the reactor at a rate of 1-5L/h.
Preferably, in the step (1), the pH regulator is 12wt% of ammonium bicarbonate or 12wt% of ammonia water.
Preferably, in step (1), the pH is adjusted to be: maintaining the pH value at 6-8; the reaction time of the first stage is 2-8 h; the pH value is adjusted to be: keeping the pH value at 8.1-10; the reaction time of the second stage is 2-6 h. Lower pH at the early stage favors the formation of a fluffy inner core, while higher pH favors the formation of a dense outer layer.
Preferably, in the step (1), the reaction temperature is 40-60 ℃.
Preferably, in step (1), the atmosphere of the reaction is nitrogen, argon, or air.
Preferably, in the step (1), the stirring speed is 100-250 r/min; stirring is used to control the progress of the reaction.
Preferably, in step (1), the solid-liquid separation is filtration or centrifugation.
Preferably, in the step (1), the drying temperature is 80-120 ℃, and the drying time is 3-12 h.
Preferably, in the step (2), the sodium source is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate, and the molar ratio of metal ions in the sodium source to the sum of nickel, cobalt and manganese metal ions in the precursor is 0.1-1: 1.
Preferably, in the step (2), the calcination is performed in an oxygen atmosphere or an air atmosphere.
Preferably, in the step (2), the technological parameters of the first stage of calcination are that the temperature is raised to 450-550 ℃ at the speed of 3-7 ℃/min, and the calcination is carried out for 4-5 h.
Preferably, in the step (2), the process parameters of the second stage of calcination are that after the first stage of calcination, the temperature is raised to 930-1000 ℃ at the speed of 3-7 ℃/min, the calcination is carried out for 5-12 h, and the furnace cooling is carried out.
The proper temperature rise speed can keep the spherical structure of the material, and a product with better crystallinity can be obtained by proper calcination mechanism and time duration, so that the electrochemical performance of the material is improved. Meanwhile, the sintering temperature and the sintering time are related to the migration degree of nickel, cobalt and manganese, so that the material has a specific appearance.
The principle of the invention is as follows: according to the method, the precursor with compact outside and loose inside is obtained by controlling the pH value of the coprecipitation reaction system. And in the initial stage of the reaction, the pH value of the reaction system is controlled to be kept at a lower level, crystal nuclei are formed in the reaction system and are agglomerated to form a loose inner core, and then the reaction system is controlled to keep a higher pH value, so that a compact shell is formed on the outer layer of the loose inner core. During calcination, the kirkendall effect causes the migration velocity of Ni, Co, and Mn to the outer surface to be greater than the migration velocity of O to the inside, so that the inside of the particle becomes a hollow structure. In addition, the difference in sintering temperature and sintering time causes the difference in the position of the final distribution of Ni, Co and Mn. When calcined at a temperature greater than 920 ℃, Ni, Co and Mn just migrate to the outer surface to form flat sheets; if the material is calcined under the condition of lower temperature, acicular bulges are formed on the surface of the material. Due to the difference of the growth rates of the crystal faces, a plurality of holes are formed on the surface of the particle, and finally, a hollow porous sphere structure is formed. In the structure, the deintercalation path of sodium ions in the charging and discharging process is only the thickness (50-100 nm) of the sheet structure, and the contact of the material with the conductive agent and the electrolyte is increased by the porous structure, so that a battery assembled by electrodes made of the material has better rate performance, and meanwhile, the material has better stability in the charging and discharging process due to the unique three-dimensional structure of the battery.
Compared with the prior art, the invention has the following beneficial effects: (1) the micron-sized hollow porous sodium ion battery positive electrode material has a micron-sized hollow porous spherical structure formed by self-assembling a unique sheet structure; (2) the structure of the hollow sphere shortens the deintercalation path of sodium ions to the thickness of the sheet structure, and prevents agglomeration among the sheet structures; (3) the porous structure of the material is beneficial to the contact of the material with a conductive agent and electrolyte, so that the conductivity of the electrode made of the material is improved; (4) the micron hollow porous composite spherical sodium ion battery anode material has good structural stability, and the battery assembled by the electrode made of the material has good rate performance. (5) The method has simple process, the required equipment is consistent with the existing industrialized lithium cobaltate and nickel cobalt manganese ternary cathode material process, and the lithium cobaltate and nickel cobalt manganese ternary cathode material can be directly produced by the existing production line.
Drawings
FIG. 1 is an SEM image of a micron-scale hollow porous positive electrode material of a sodium-ion battery obtained in example 1 of the invention;
FIG. 2 is an SEM image of a micrometer-scale hollow porous positive electrode material of a sodium-ion battery obtained in example 1 of the invention;
FIG. 3 is an electrochemical performance diagram of a battery assembled by electrodes made of the micron-scale hollow porous sodium-ion battery cathode material obtained in example 1 of the present invention at 0.1C magnification;
FIG. 4 is an electrochemical performance diagram of a battery assembled by electrodes made of the micron-sized hollow porous positive electrode material of the sodium-ion battery obtained in example 1 of the present invention at 0.2C magnification;
FIG. 5 is an electrochemical performance diagram of a battery assembled by electrodes made of the micron-scale hollow porous sodium-ion battery cathode material obtained in example 1 of the present invention at 0.5C magnification;
FIG. 6 is an electrochemical performance diagram of a battery assembled by electrodes made of the micron-scale hollow porous sodium-ion battery cathode material obtained in example 1 of the present invention at a 1C rate;
fig. 7 is an electrochemical performance diagram of a battery assembled by electrodes made of the micron-scale hollow porous sodium-ion battery cathode material obtained in example 1 of the invention at a 2C rate.
Detailed Description
The present invention will be further described with reference to the following examples and drawings.
In the following examples, the specific discharge capacity was measured by a novyi charge-discharge tester.
All raw materials used are, unless otherwise specified, those commonly available on the market.
Example 1
(1) Weighing 5mol of nickel sulfate hexahydrate, 5mol of cobalt sulfate heptahydrate and 20mol of manganese sulfate monohydrate, dissolving the nickel sulfate hexahydrate, the 5mol of cobalt sulfate heptahydrate and the 20mol of manganese sulfate monohydrate in 20L of deionized water to form 1.5mol/L mixed solution, and preparing 1.5mol/L sodium carbonate solution, wherein the ratio of the sum of the molar weight of nickel salt, cobalt salt and manganese salt to the molar weight of sodium carbonate is 1: 1; taking a 50L reaction kettle as a reactor, respectively adding 20L of mixed solution and 20L of sodium carbonate solution into the reaction kettle at the speed of 2L/h through a peristaltic pump, and stirring at the speed of 200r/min at the temperature of 50 ℃ to carry out coprecipitation reaction; simultaneously adding 12wt% of ammonium bicarbonate to adjust the pH value of the reaction solution to 8.0, adjusting the pH value to 8.5 after reacting for 6 hours, reacting for 4 hours again, and washing, filtering and drying the obtained precipitate to obtain nickel-cobalt-manganese carbonate; the drying temperature is 90 ℃, and the drying time is 8 hours;
(2) according to the proportion of Na: weighing sodium carbonate and nickel, cobalt and manganese carbonate, mixing the sodium carbonate and the nickel, cobalt and manganese carbonate in a mortar, uniformly mixing, placing the mixture in a muffle furnace, adopting two-stage calcination, heating to 500 ℃ at the speed of 5 ℃/min, calcining for 4h, then continuously heating to 950 ℃ at the speed of 5 ℃/min, calcining for 10h, and cooling with the furnace to obtain the micron-scale hollow porous sodium-ion battery anode material Na 0.44 Mn 2/3 Co 1/6 Ni 1/6 O 2 。
The material obtained in this example was subjected to SEM test, and the results are shown in fig. 1 and 2. As can be seen from the figure, the obtained cathode material was a hollow porous sphere structure with a diameter of 10 μm formed by self-assembly of a sheet structure with a thickness of 1.5 μm, and the sheet structure had a thickness of 70 nm.
The micron-scale hollow porous sodium ion battery anode material obtained in the embodiment is used for preparing an electrode and then assembled into a button cell, and the method comprises the following specific steps:
weighing 0.08g of the micron-scale hollow porous sodium ion battery positive electrode material obtained in the embodiment according to the mass ratio (active material: conductive agent: binder =8:1: 1), weighing 0.01g of acetylene black as a conductive agent and 0.01g of polyvinylidene fluoride as a binder, placing the materials in a mortar for mixing, adding N-methyl pyrrolidone as a dispersing agent after mixing uniformly, coating the mixture on an aluminum foil after mixing again to prepare a positive electrode sheet, and assembling the positive electrode sheet into a CR2025 button cell by taking metal sodium as a negative electrode in a glove box in an inert protective atmosphere.
After the assembled battery is kept stand for 12 hours, an electrochemical performance test is carried out, as shown in figures 3-7: the specific discharge capacity at the rate of 0.1C is 133mAh/g, the specific discharge capacity at the rate of 0.2C is 127mAh/g, the specific discharge capacity at the rate of 0.5C is 116mAh/g, the specific discharge capacity at the rate of 1C is 95mAh/g, and the specific discharge capacity at the rate of 2C is 72mAh/g, which indicates that the battery prepared by adopting the electrode prepared from the micron-scale hollow porous sodium ion battery anode material has good rate performance.
Example 2
(1) Weighing 1.5mol of nickel acetate tetrahydrate, 1.5mol of cobalt acetate tetrahydrate and 12mol of manganese acetate tetrahydrate, dissolving the nickel acetate tetrahydrate, the 1.5mol/L cobalt acetate tetrahydrate and the 12 mol/L manganese acetate in 10L of deionized water to form 1.5mol/L mixed solution, then preparing an alkali liquor, wherein the alkali liquor simultaneously contains 1.5mol/L sodium hydroxide and 0.002 mol/L ammonia water, the ratio of the sum of the molar amounts of nickel salt, cobalt salt and manganese salt to the molar amount of solute is 1:2, taking a 50L reaction kettle as a reactor, respectively adding 10L mixed solution and 20L alkali liquor into the reaction kettle at the speeds of 1L/h and 2L/h through a peristaltic pump, and stirring at the temperature of 60 ℃ at the speed of 250r/min to perform coprecipitation reaction; adjusting the pH value of the reaction solution to 7.5 by adding 12wt% of ammonia water, reacting for 4 hours, adjusting the pH value to 9, reacting for 6 hours, and performing suction filtration and drying on the obtained precipitate to obtain nickel-cobalt-manganese hydroxide; the drying temperature is 110 ℃, and the drying time is 10 hours;
(2) according to the proportion of Na: weighing sodium hydroxide and hydroxide of nickel, cobalt and manganese according to the molar ratio of Ni, Co and Mn of 1:1, mixing the sodium hydroxide and the hydroxide of nickel, cobalt and manganese in a mortar, adding the mixture into a muffle furnace after uniformly mixing, adopting two-stage calcination, heating to 550 ℃ at the speed of 4 ℃/min, calcining for 5 hours, then continuously heating to 960 ℃ at the speed of 4 ℃/min, calcining for 9 hours, and cooling along with the furnace to obtain the micron-scale hollow porous sodium-ion battery positive electrode material NaMn 0.8 Co 0.1 Ni 0.1 O 2 。
SEM test of the material obtained in the embodiment shows that the obtained cathode material is a hollow porous sphere structure with the diameter of 8 μm formed by self-assembly of a 0.7 μm sheet structure, and the thickness of the sheet structure is 60 nm.
The micron-scale hollow porous sodium ion battery anode material obtained in the embodiment is used for preparing an electrode and then assembled into a button cell, and the method comprises the following specific steps:
weighing 0.08g of the micron-scale hollow porous sodium ion battery positive electrode material obtained in the embodiment according to the mass ratio (active material: conductive agent: binder =8:1: 1), weighing 0.01g of acetylene black as a conductive agent and 0.01g of polyvinylidene fluoride as a binder, placing the materials in a mortar for mixing, adding N-methyl pyrrolidone as a dispersing agent after mixing uniformly, coating the mixture on an aluminum foil after mixing again to prepare a positive electrode sheet, and assembling the positive electrode sheet into a CR2025 button cell by taking metal sodium as a negative electrode in a glove box in an inert protective atmosphere.
After the assembled battery is kept stand for 12 hours, the electrochemical performance test is carried out: the specific discharge capacity under the multiplying power of 0.1C reaches 135mAh/g, the specific discharge capacity under the multiplying power of 0.2C is 130mAh/g, the specific discharge capacity under the multiplying power of 0.5C is 121mAh/g, the specific discharge capacity under the multiplying power of 1C is 99mAh/g, and the specific discharge capacity under the multiplying power of 2C is 80mAh/g, which indicates that the multiplying power performance of the battery assembled by the electrode prepared from the hollow porous sodium-ion battery anode material with the micron scale is good.
Example 3
(1) Weighing 5mol of nickel oxalate dihydrate, 5mol of cobalt oxalate dihydrate and 20mol of manganese chloride tetrahydrate, and dissolving the nickel oxalate dihydrate, the cobalt oxalate dihydrate and the 20mol of manganese chloride tetrahydrate in 20L of deionized water to form 1.5mol/L mixed solution; then preparing an alkali liquor, wherein the alkali liquor simultaneously contains 2mol/L of sodium carbonate and 0.002 mol/L of ammonia water, and the ratio of the sum of the molar weight of nickel salt, cobalt salt and manganese salt to the molar weight of solute of the alkali liquor is 1: 1.5; taking a 50L reaction kettle as a reactor, adding 20L of mixed solution and 22.5L of alkali liquor into the reaction kettle at the speed of 2L/h and 2.25L/h respectively through a peristaltic pump, and stirring at the speed of 220r/min at the temperature of 52 ℃ to carry out coprecipitation reaction; adjusting the pH value of the reaction solution to 7.5 by adding 12wt% of ammonia water, reacting for 4h, adjusting the pH value to 8.5, reacting for 6h, and performing suction filtration and drying on the obtained precipitate to obtain nickel-cobalt-manganese carbonate; the drying temperature is 120 ℃, and the drying time is 4 hours;
(2) according to the proportion of Na: weighing sodium carbonate and carbonate of nickel, cobalt and manganese, mixing the sodium carbonate and the carbonate of nickel, cobalt and manganese in a mortar, uniformly mixing, putting the mixed material into a muffle furnace, heating up to 530 ℃ at the speed of 6 ℃/min, calcining for 5h, heating up to 980 ℃ at the speed of 6 ℃/min, calcining for 12h, and cooling along with the furnace to obtain the micron-scale hollow porous sodium-ion battery anode material Na 0.67 Ni 0.17 Co 0.17 Mn 0.66 O 2 。
SEM test of the material obtained in this example shows that the obtained cathode material is a hollow porous sphere structure with a diameter of 13 μm formed by self-assembly of a sheet structure with a thickness of 1.2 μm, and the thickness of the sheet structure is 90 nm.
The micron-scale hollow porous sodium ion battery anode material obtained in the embodiment is used for preparing an electrode and then assembled into a button cell, and the method comprises the following specific steps:
weighing 0.08g of the micron-scale hollow porous sodium ion battery positive electrode material obtained in the embodiment according to the mass ratio (active material: conductive agent: binder =8:1: 1), weighing 0.01g of acetylene black as a conductive agent and 0.01g of polyvinylidene fluoride as a binder, placing the materials in a mortar for mixing, adding N-methyl pyrrolidone as a dispersing agent after mixing uniformly, coating the mixture on an aluminum foil after mixing again to prepare a positive electrode sheet, and assembling the positive electrode sheet into a CR2025 button cell by taking metal sodium as a negative electrode in a glove box in an inert protective atmosphere.
After the assembled battery is kept stand for 12 hours, the electrochemical performance test is carried out: the specific discharge capacity under the multiplying power of 0.1C is 136mAh/g, the specific discharge capacity under the multiplying power of 0.2C is 128mAh/g, the specific discharge capacity under the multiplying power of 0.5C is 122mAh/g, the specific discharge capacity under the multiplying power of 1C is 98mAh/g, the specific discharge capacity under the multiplying power of 2C is 82mAh/g, and the battery manufactured by the electrode made of the hollow porous sodium ion battery anode material with the micron scale has good multiplying power performance.
Claims (14)
1. The micron-scale hollow porous sodium-ion battery positive electrode material is characterized by having a chemical formula ofNa x Mn 1-y- z Ni y Co z O 2 Wherein x is more than 0 and less than or equal to 1, y is more than 0 and less than 1, z is more than 0 and less than 1, and y + z is more than 0 and less than 1, and the hollow porous spherical structure is a micron-sized hollow porous spherical structure and is formed by self-assembling a sheet-shaped structure;
the diameter of the hollow porous spherical structure is 8-15 microns, the particle size of the sheet structure is 0.5-1.5 microns, and the thickness of the sheet structure is 50-100 nm; in the micrometer-scale hollow porous sodium ion battery positive electrode material, the deintercalation path of sodium ions in the charge-discharge process is the thickness of a sheet structure;
the preparation method of the micron-scale hollow porous sodium-ion battery positive electrode material comprises the following steps:
(1) under the condition of stirring, adding alkali liquor and a nickel-cobalt-manganese salt solution into a reactor, adjusting the pH value by using a pH value regulator, and carrying out a first-stage reaction; then, regulating the pH value to be higher by using a pH value regulator, carrying out second-stage reaction, carrying out solid-liquid separation after the reaction is finished, and washing and drying the precipitate to obtain a precursor;
(2) mixing the precursor with a sodium source, and carrying out two-stage calcination: the first stage of calcination is carried out at the temperature of less than 600 ℃, and the second stage of calcination is carried out at the temperature of more than or equal to 920 ℃, so as to obtain the micron-scale hollow porous sodium-ion battery anode material;
in the step (1), the pH value is adjusted to be: maintaining the pH value at 6-8; the reaction time of the first stage is 2-8 h; the pH value is adjusted to be: keeping the pH value at 8.1-10; the reaction time of the second stage is 2-6 h;
in the step (1), the reaction temperature is 40-60 ℃;
in the step (2), calcining is carried out in an oxygen atmosphere or an air atmosphere, and the technological parameters of the first stage of calcining are that the temperature is raised to 450-550 ℃ at the speed of 3-7 ℃/min, and calcining is carried out for 4-5 h; and the technological parameters of the second stage of calcination are that after the first stage of calcination, the temperature is raised to 930-1000 ℃ at the speed of 3-7 ℃/min, the calcination is carried out for 5-12 h, and the calcination is carried out along with the furnace cooling.
2. The micron-scale hollow porous sodium-ion battery positive electrode material according to claim 1, wherein x: y is 1-10: 1; and x: z is 1-10: 1.
3. The micron-scale hollow porous sodium-ion battery cathode material according to claim 1, wherein in the step (1), the nickel-cobalt-manganese salt solution is prepared by dissolving nickel salt, cobalt salt and manganese salt in deionized water; the nickel salt is sulfate and hydrate thereof, nitrate and hydrate thereof, chloride and hydrate thereof, acetate and hydrate thereof or oxalate and hydrate thereof; the cobalt salt is sulfate and hydrate thereof, nitrate and hydrate thereof, chloride and hydrate thereof, acetate and hydrate thereof or oxalate and hydrate thereof; the manganese salt is sulfate and hydrate thereof, nitrate and hydrate thereof, chloride and hydrate thereof, acetate and hydrate thereof or oxalate and hydrate thereof.
4. The micron-scale hollow porous sodium-ion battery cathode material according to any one of claims 1 to 3, wherein in the step (1), the molar ratio of nickel ions to cobalt ions in the nickel-cobalt-manganese salt solution is 1: 0.8-1.2; the molar ratio of nickel ions to manganese ions in the nickel-cobalt-manganese salt solution is 1: 4-8; the concentration of metal cations in the nickel-cobalt-manganese salt solution is 0.1-5 mol/L.
5. The micron-scale hollow porous sodium-ion battery cathode material according to claim 4, wherein in the step (1), the concentration of metal cations in the nickel-cobalt-manganese salt solution is 1-2 mol/L.
6. The micron-scale hollow porous sodium-ion battery cathode material according to claim 3, wherein in the step (1), the alkali liquor is obtained by dissolving one or more of sodium hydroxide, ammonia water, sodium carbonate, sodium bicarbonate, ammonium bicarbonate and hydrate thereof in water; the concentration of the alkali liquor is 0.001-3 mol/L; the ratio of the sum of the molar weight of the nickel salt, the cobalt salt and the manganese salt to the molar weight of the solute of the alkali liquor is 1: 0.5-100.
7. The micron-scale hollow porous sodium-ion battery positive electrode material according to claim 6, wherein in the step (1), the concentration of the alkali liquor is 1-2 mol/L; the ratio of the sum of the molar weight of the nickel salt, the cobalt salt and the manganese salt to the molar weight of the solute of the alkali liquor is 1: 1-5.
8. The micron-scale hollow porous sodium-ion battery cathode material according to any one of claims 1 to 3, wherein in the step (1), the rate of adding the alkali liquor into the reactor is 1-5L/h; the rate of adding the salt solution into the reactor is 1-5L/h; the pH value regulator is 12wt% of ammonium bicarbonate or 12wt% of ammonia water.
9. The micron-scale hollow porous sodium-ion battery cathode material according to any one of claims 1 to 3, wherein in the step (1), the reaction atmosphere is nitrogen, argon or air; the stirring speed is 100-250 r/min; the solid-liquid separation is filtration or centrifugation; the drying temperature is 80-120 ℃, and the drying time is 3-12 h.
10. The micron-scale hollow porous sodium-ion battery cathode material according to any one of claims 1 to 3, wherein in the step (2), the sodium source is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the molar ratio of metal ions in the sodium source to the sum of nickel, cobalt and manganese metal ions in the precursor is 0.1-1: 1.
11. The micron-scale hollow porous sodium-ion battery cathode material according to claim 4, wherein in the step (2), the sodium source is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the molar ratio of metal ions in the sodium source to the sum of nickel, cobalt and manganese metal ions in the precursor is 0.1-1: 1.
12. The micron-scale hollow porous sodium-ion battery cathode material according to claim 6, wherein in the step (2), the sodium source is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the molar ratio of metal ions in the sodium source to the sum of nickel, cobalt and manganese metal ions in the precursor is 0.1-1: 1.
13. The micron-scale hollow porous sodium-ion battery cathode material according to claim 8, wherein in the step (2), the sodium source is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the molar ratio of metal ions in the sodium source to the sum of nickel, cobalt and manganese metal ions in the precursor is 0.1-1: 1.
14. The micron-scale hollow porous sodium-ion battery cathode material according to claim 9, wherein in the step (2), the sodium source is one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate; the molar ratio of metal ions in the sodium source to the sum of nickel, cobalt and manganese metal ions in the precursor is 0.1-1: 1.
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