CN112591804B - Transition metal oxide material and preparation method thereof - Google Patents

Transition metal oxide material and preparation method thereof Download PDF

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CN112591804B
CN112591804B CN202011446801.2A CN202011446801A CN112591804B CN 112591804 B CN112591804 B CN 112591804B CN 202011446801 A CN202011446801 A CN 202011446801A CN 112591804 B CN112591804 B CN 112591804B
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transition metal
metal oxide
oxide material
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sodium
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CN112591804A (en
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姜美丹
廖小珍
李林森
钱冠男
马紫峰
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Zhejiang Sodium Innovation Energy Co ltd
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Shanghai Jiaotong University
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    • C01G53/00—Compounds of nickel
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    • 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
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Abstract

The invention discloses a transition metal oxide material and a preparation method thereof. The preparation method of the transition metal oxide material provided by the invention comprises the following steps: under the condition of molten salt melting, the mixture of a sodium source and an oxygen-containing transition metal source is sintered at high temperature to prepare the transition metal oxide material NaxMeO2(ii) a The temperature of the high-temperature sintering is 700-1000 ℃, and the time of the high-temperature sintering is 10-15 h; the molten salt is sodium molybdate; the sodium source is selected from sodium carbonate and/or sodium hydroxide; wherein Me is one or more selected from transition metal elements. The transition metal oxide material has the advantages of simple preparation method, low production cost, no toxicity, no harm, short time and low energy consumption, the prepared material is single crystal particles, the crystallinity is high, the interface stability is good, the side reaction is reduced, and the battery capacity and the cycling stability are good when the material is used as the anode material of the sodium ion battery.

Description

Transition metal oxide material and preparation method thereof
Technical Field
The invention relates to a transition metal oxide material and a preparation method thereof.
Background
With the rapid development of science and technology, the dependence of people on power resources in daily life is greatly improved. Therefore, the large-scale energy storage equipment is very important, and the sodium ion battery technology which is green, environment-friendly, abundant in resource and low in cost is expected to become a popular column for future energy storage application.
However, sodium ion batteries also present many challenges, and it is currently most critical to find electrode materials that have high capacity and are stable. Layered transition metal oxide NaxMeO2The (Me is transition metal) has a layered structure (mainly P2 and O3 types), each unit cell of the transition metal oxide is octahedron, the common lamellar layers of the transition metal oxide form an oxygen layer, the interlayer spacing is larger, and the desorption of sodium ions is facilitated, so that the material is an ideal sodium storage material and is applied to a positive electrode material of a sodium ion battery.
At present, the layered transition metal oxide material is mainly prepared by a high-temperature solid-phase method, and is prepared by mixing sodium salt and transition metal oxide and then sintering at high temperature. However, Na obtained by this conventional methodxMeO2The product has impurity phase and forms secondary polycrystalline particles with nano-particle agglomeration, and the secondary particle structure is easy to crack and damage in the long-term charge-discharge cycle process due to large specific surface area and more side reactions, so that the cycle stability is reduced, and the application of the product in the aspect of sodium ion battery anode materials is severely limited. The Chinese patent application CN109301238A discloses a high-performance sodium-ion battery cathode material and a preparation method thereof, wherein the high-crystallinity cathode material can be obtained by a sodium salt-melting method, but a ternary transition metal system is used, the cost is high in the actual process production, an organic solvent is required to be dispersed in the preparation process and then subjected to secondary grinding and sintering, the organic solvent has certain toxicity, the steps are complicated, and the time consumption is long.
Disclosure of Invention
The invention aims to overcome the defects of high cost, complicated steps, insufficient safety and environmental protection of a preparation method of a layered transition metal oxide material for a sodium-ion battery by a molten salt method in the prior art, and provides a transition metal oxide material and a preparation method thereof. The preparation method of the transition metal oxide material is simple, the production cost is low, the material is non-toxic and harmless, the time is short, the energy consumption is low, the prepared material is single crystal particles, the crystallinity is high, and the interface stability is good.
The invention solves the technical problems through the following technical scheme:
a method of preparing a transition metal oxide material, comprising the steps of:
under the condition of molten salt melting, the mixture of a sodium source and an oxygen-containing transition metal source is sintered at high temperature to prepare the transition metal oxide material NaxMeO2(ii) a The temperature of the high-temperature sintering is 700-1000 ℃, and the time of the high-temperature sintering is 10-15 h; the molten salt is sodium molybdate; the sodium source is selected from sodium carbonate and/or sodium hydroxide;
wherein Me is one or more selected from transition metal elements.
In the present invention, the sodium source is preferably sodium carbonate.
In the present invention, the oxygen-containing transition metal source is preferably selected from transition metal oxides or transition metal sources that can generate transition metal oxides at temperatures below 700 ℃, such as transition metal hydroxides or transition metal carbonates. More preferably a transition metal oxide.
In the present invention, the transition metal may be selected from transition metals conventional in the art, for example, one or more selected from manganese, nickel and titanium, and further for example, two selected from manganese, nickel and titanium, preferably manganese and nickel.
When the transition metal is Mn, the oxygen-containing transition metal source may be selected from oxygen-containing manganese sources conventional in the art, such as manganese oxide, manganese hydroxide or manganese carbonate, such as manganese dioxide or manganese carbonate, preferably manganese dioxide (MnO)2)。
When the transition metal is Ni, the oxygen-containing transition metal source may be selected from oxygen-containing nickel sources conventional in the art, such as nickel oxide, nickel hydroxide or nickel carbonate, preferably nickel hydroxide (Ni (OH)2) Nickel oxide or nickel carbonate, more preferably nickel hydroxide.
When the transition metal is Ti, the oxygen-containing transition metal source may be selected from oxygen-containing titanium sources conventional in the art, such as titanium dioxide, preferably nano-sized titanium dioxide.
In the present invention, the mole number of the sodium source may be the mole number of the sodium source conventional in the art, for example, 0.01 to 0.02mol, preferably 0.0102 to 0.0153 mol.
In the present invention, preferably, the ratio of the number of moles of the molten salt to the total number of moles of the oxygen-containing transition metal source is 1: (2-4), more preferably 1: 3. wherein the oxygen-containing transition metal source is preferably present in a molar amount of 0.02 to 0.03mol, for example 0.0205 or 0.0267 mol.
In the invention, the molten salt provides a liquid environment for the reaction and plays a role of a fluxing agent.
In the present invention, the number of moles of the molten salt is preferably 0.01 mol.
In the invention, the crystal form of the transition metal oxide material comprises P2 Na2/3MeO2Or NaMeO type O32. Wherein, P2 type Na2/3MeO2Preferably Na2/3Ni1/3Mn2/3O2NaMeO type O32Preferably NaNi1/3Mn1/2Ti1/6O2。
When the transition metal oxide material is of the type P2, the raw material in the process for producing the transition metal oxide material is preferably sodium carbonate Na2CO3Manganese dioxide (MnO)2) Nickel hydroxide (Ni (OH))2) And sodium molybdate (Na)2MoO4) And (4) forming.
When the transition metal oxide material is of the O3 type, the raw material of the process for producing the transition metal oxide material is preferably sodium carbonate Na2CO3Manganese dioxide (MnO)2) Nickel hydroxide (Ni (OH))2) Nano titanium dioxide (TiO)2) And sodium molybdate (Na)2MoO4) And (4) forming.
In the invention, the sodium source, the oxygen-containing transition metal source, the transition metal hydroxide and the molten salt can be solid samples according to the conventional practice in the field, and are generally placed in a moisture-proof cabinet for storage, so as to avoid water absorption.
In the present invention, preferably, the raw material in the preparation method of the transition metal oxide material further comprises a doped metal element N, wherein N is selected from one or more of Al, Fe, Li, Ti, Zn, Cu and Mg, such as one or more of Al, Fe, Li, Ti and Mg, further such as Al, Fe, Li, Ti or Mg, preferably Al, Fe, Ti or Mg.
The source of the doped metal element N is preferably a nanoscale material, such as nanoscale alumina or nanoscale titania.
When the doped metal element is Fe, the raw material source of the Fe is preferably nanoscale Fe2O3Said nanoscale Fe2O3Preferably 30nm, said nanoscale Fe2O3The number of moles of (b) is preferably 0.00167 mol.
When the doped metal element is Al, the raw material source of the Al is preferably nano-alumina, the grain size of the nano-alumina is preferably 20nm, and the mole number of the nano-alumina is preferably 0.00167 mol.
When the doped metal element is Ti, the raw material source of the Ti is preferably nano-scale titanium dioxide, the particle size of the nano-scale titanium dioxide is preferably 20nm, and the mole number of the nano-scale titanium dioxide is preferably 0.005 mol.
When the doped metal element is Mg, the raw material source of Mg is preferably MgO, and the mole number of MgO is preferably 0.003 mol.
When the doped metal element is Li, the source of the Li is preferably Li2CO3The Li2CO3The number of moles of (B) is preferably 0.00045 mol.
In the present invention, when Me is selected from two transition metals and is doped with a metal element N, the transition metal oxide material is prepared by using the general chemical formula Nax(TyMzN1-y-z)O2Represents;
wherein T, M is one of transition metal elements Me respectively. In general, the doping elements N and T, M are different elements.
Wherein x is the ratio of the mole number of the sodium element to the total mole number of T, M and N, and the value range of x is as follows: 0< x.ltoreq.1, preferably 0< x.ltoreq.0.8, for example 1/3, 2/3 or 1.
Y is the ratio of the mole number of the T element to the total mole number of T, M and N, and the value range of y is as follows: 0. ltoreq. y.ltoreq.1, preferably 0. ltoreq. y.ltoreq. 1/3, for example 1/3, 2/9 or 1/6.
The z is the ratio of the mole number of the M element to the total mole number of T, M and N, and the value range of z is as follows: 0. ltoreq. z.ltoreq.1, preferably 0. ltoreq. z.ltoreq. 2/3, for example 1/3, 1/9, 2/3, 2/9 or 1/6.
Preferably, said Nax(TyMzN1-y-z)O2Selected from Na2/3Ni2/9Al1/9Mn2/3O2Or Na2/3Ni1/6Ti1/6Mn2/3O2。
In the present invention, the preparation method of the transition metal oxide material may further include a step of proportioning the raw materials according to a conventional method in the art, and preferably, the raw materials are proportioned according to a stoichiometric ratio. Under the proportion, the two react completely, the raw materials are saved, the cleaning is free from pollution, and the obtained product washing filtrate is colorless.
In the present invention, the mixture of the sodium source and the oxygen-containing transition metal source may be obtained by a mixing operation conventional in the art, preferably a milling mixing.
In the present invention, the temperature of the high-temperature sintering is preferably 800-.
In the present invention, the time of the high-temperature sintering is preferably 13 to 15 hours, such as 14 and 15 hours.
In the present invention, the step of high-temperature sintering preferably includes raising the temperature from room temperature to the temperature of high-temperature sintering.
Wherein the rate of temperature increase may be a rate of temperature increase conventional in the art; preferably 5 deg.C/min.
In the present invention, after the high-temperature sintering, a step of reducing the temperature is preferably further included. The cooling operation is preferably natural cooling. The rate of cooling is preferably 3 ℃/min. The temperature reduction is preferably to 300 ℃.
Wherein, preferably, a washing step is further included after the temperature reduction step for washing away the molten salt.
The washing agent may be a washing agent conventional in the art, such as water, preferably deionized water.
The number of washing is preferably 2 to 3. When the washing times are less than 2, the molten salt washing is possibly incomplete, and the battery performance is influenced; the washing times of more than 3 times may cause elution of sodium ions and manganese ions.
Preferably, the washing with water further comprises washing with absolute ethyl alcohol, which is beneficial to accelerating subsequent drying.
Wherein, the washing step preferably further comprises the operations of removing the filtrate and drying.
The filtrate removal procedure may be any conventional in the art, such as centrifugation. The rotation speed of the centrifugation can be the rotation speed of the centrifugation which is conventional in the field, preferably 4500r/min, the time of the centrifugation is preferably 30s, and the product and the filtrate can be better separated.
The drying temperature may be a temperature of drying conventional in the art, preferably 80 ℃, and the drying time is preferably 1 h.
Preferably, after the drying step, a heat treatment step is further included. The temperature of the heat treatment is preferably 650-800 ℃; more preferably 750 deg.c.
Wherein the time of the heat treatment is preferably 8-11h, more preferably 10h, to remove water and optimize the material structure.
The heat treatment operation may be a heat treatment operation conventional in the art, for example, in a tube furnace under an oxygen atmosphere.
In a preferred embodiment of the present invention, the method for preparing the transition metal oxide material comprises: the high-temperature sintering temperature is 900 or 1000 ℃, and the high-temperature sintering time is 15 h.
In another preferred embodiment of the present invention, the method for preparing the transition metal oxide material comprises the steps of: heating to 900 ℃ from room temperature at a speed of 5 ℃/min, maintaining for 15h, then cooling to 300 ℃ at a speed of 3 ℃/min, and naturally cooling to room temperature to obtain the layered transition metal oxide material product coated by the molten salt.
Further, the invention also provides a transition metal oxide material which is prepared by the preparation method of the transition metal oxide material.
Further, the invention also provides a positive electrode material of a sodium battery, which comprises the transition metal oxide material.
Furthermore, the invention also provides an application of the transition metal oxide material in the preparation of a sodium-ion battery.
Further, the invention also provides a sodium ion battery, which comprises the transition metal oxide material.
Further, the invention also provides a preparation method of the sodium-ion battery positive electrode material, which comprises the following steps: mixing the transition metal oxide material with conductive carbon, a binder and a solvent, and drying to obtain the material.
Wherein, before mixing the transition metal oxide material with the conductive carbon, the binder and the solvent, the transition metal oxide material is sieved. The mesh number may be conventional in the art, preferably 400 mesh.
Wherein the conductive carbon may be a conductive carbon conventional in the art, preferably Super P.
The binder may be a binder conventional in the art, and is preferably polyvinylidene fluoride (PVDF).
Preferably, the mass ratio of the transition metal oxide material, the conductive carbon and the binder is 8: 1: 1.
among them, the solvent may be a solvent conventional in the art, and preferably 1-methyl-2-pyrrolidone (NMP). The mixture may be slurried by adding a solvent.
Wherein, after the addition of the solvent, a stirring step can be further included as usual in the art, and the stirring time is preferably 5 minutes. Stirring to obtain slurry.
Wherein, after the stirring step, the slurry can be uniformly coated on an aluminum foil according to the conventional method in the field and dried.
Wherein the aluminum foil coated with the black slurry may be further sliced after drying as is conventional in the art. For example, cut into circular pole pieces having a diameter of 10 mm.
Wherein, after slicing, the pole piece can be dried in vacuum according to the routine in the field. The temperature of the vacuum drying is preferably 120 ℃, and the time of the vacuum drying is preferably 12 hours, so that the positive pole piece of the sodium-ion battery is prepared.
In the present invention, the room temperature generally means 20 ℃. + -. 5 ℃, for example 25 ℃.
The positive progress effects of the invention are as follows:
(1) the sodium salt raw material is easy to obtain and has rich resources, the synthesis process is simple, the cost is low, therefore, the invention provides the preparation method of the layered transition metal oxide sodium ion battery anode material with low cost, no toxicity, no harm and high performance, and the prepared non-water-sensitive layered transition metal oxide sodium ion battery anode material has good application prospect.
(2) Further, the preparation method of the sodium-ion layered transition metal oxide material provided by the invention has the advantages that the high-temperature reaction is carried out in the liquid environment provided by the molten salt, compared with the solid environment, the molten state is favorable for the full mixing of reactants and the rapid diffusion of ions, the single crystal particles with uniform chemical composition, good crystal form and high phase purity can be obtained by realizing short reaction time, the prepared material has high crystallinity and better interface stability, the occurrence of side reactions is reduced, and the battery capacity and the cycling stability are high when the material is used as the positive electrode material of a sodium-ion battery.
(3) P2 Na prepared by the preparation method of the invention2/3Ni1/3Mn2/3O2O3 type NaNi1/3Mn1/2Ti1/6O2The material has excellent electricity when being applied to the positive pole of the sodium-ion batteryChemical properties.
Drawings
FIG. 1a shows Na form P2 prepared by the molten salt method of example 12/3Ni1/3Mn2/3O2SEM picture of (1); FIG. 1b, FIG. 1c, and FIG. 1d show the effects of example 8 in which the molten salt is Na2MoO4Preparing P2 type Na from NaCl and NaBr2/3Ni1/3Mn2/3O2SEM image of (d).
FIG. 1e shows Na form P2 prepared in comparative example 1 (high temperature solid phase method)2/3Ni1/3Mn2/3O2SEM image of (d).
FIG. 2 shows P2-Na prepared from example 1 (molten salt method) and comparative example 1 (high temperature solid phase method)2/3Ni1/3Mn2/3O2XRD pattern (where PDF54-0894 is Na2/3Ni1/3Mn2/3O2Standard XRD pattern).
FIG. 3 is a graph showing the charge and discharge cycle characteristics of the layered transition metal oxide materials prepared in example 1 and comparative example 1 in a battery at a voltage range of 2.0 to 4.0V, at a magnification of 0.1C for the first three cycles, and at a magnification of 1C for the subsequent cycles.
FIG. 4 is a graph showing a comparison of charge and discharge cycle characteristics of batteries fabricated using layered transition metal oxide materials obtained in example 1 and comparative example 1, wherein the voltage range is 2.0-4.3V and the rate is 0.1C.
FIG. 5a shows NaNi prepared in example 21/3Mn1/2Ti1/6O2SEM image of the product.
FIG. 5b shows NaNi prepared in example 21/3Mn1/2Ti1/6O2SEM image (magnification) of the product.
FIG. 5c shows NaNi O3 form prepared in example 21/3Mn1/2Ti1/6O2The voltage range is 2.0-4.3V when the voltage is used in a battery charge-discharge cycle performance diagram.
FIG. 5d shows NaNi O3 form prepared in example 21/3Mn1/2Ti1/6O2The method is used for a charge-discharge curve chart of the battery under different multiplying powers.
FIG. 6 Na prepared in example 30.5Ni0.15Co0.2Mn0.65O2Used in battery charge-discharge cycle performance diagram, voltage range is 1.7-4.3V, multiplying power is 1C, 2C
FIG. 7 shows effects of examples 7 different sodium sources prepared P2 type Na2/3Ni1/3Mn2/3O2The voltage range is 2-4.3V when the voltage is used for a battery charge-discharge cycle performance comparison chart.
FIG. 8 shows effects of example 8 different molten salts prepared Na form P22/3Ni1/3Mn2/3O2The voltage range is 2-4.3V when the voltage is used for a battery charge-discharge cycle performance comparison chart.
Figure 9 is an XRD pattern of P2 type material prepared from different doped metals of effect example 9.
FIG. 10a is a graph showing the effect of example 9, comparing the charge-discharge cycle performance of materials prepared by doping different metals (Fe, Al, Ti) with that of undoped materials, with a voltage range of 2-4.3V and a multiplying power of 0.1C.
FIG. 10b is a graph comparing the charge and discharge cycle performance of the Mg-doped and undoped materials used in the battery of Effect example 9, with a voltage range of 2-4.3V, the first two cycles of 0.1C activation, and a magnification of 1C.
FIG. 10C is a graph comparing the charge-discharge cycle performance of the material obtained by doping Li with and without doping in example 9, with a voltage range of 2-4.3V and a magnification of 0.1C.
FIG. 11 shows effects of examples 10 different sintering temperatures for P2 type Na2/3Ni1/3Mn2/3O2The method is used for a battery charge-discharge cycle performance diagram, the voltage range is 2-4V, the first two circles are activated at 0.1C, and the multiplying power is 1C.
FIG. 12 shows effects of example 11, in which Na 2 type P was prepared as a material at 1000 ℃ for different sintering times (10h, 15h)2/3Ni1/3Mn2/3O2The method is used for a battery charge-discharge cycle performance diagram, the voltage range is 2-4V, the first two circles are activated at 0.1C, and the multiplying power is 1C.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In the following examples and comparative examples, the electrochemical performance test method was as follows:
the layered transition metal oxide materials prepared in the examples or comparative examples were sieved with a 400 mesh molecular sieve, and mixed with conductive carbon (Super P) and polyvinylidene fluoride (PVDF) as a binder in a ratio of 8: 1:1, adding a proper amount of 1-methyl-2-pyrrolidone (NMP) solvent to enable the mixture to be in a slurry state, stirring for 5 minutes, uniformly coating the slurry on an aluminum foil, drying, punching the aluminum foil coated with the black slurry into a circular pole piece with the diameter of 10mm by using a slicing machine, putting the pole piece into a vacuum oven, and carrying out vacuum drying at 120 ℃ for 12 hours to obtain the positive pole piece of the sodium-ion battery. The prepared electrode sheet is used as a working electrode, metal sodium is used as a counter electrode, and a button cell is assembled in a glove box filled with argon atmosphere by using 0.8M NaPF6-PC/EMC/FEC (wherein the volume ratio of PC/EMC is 1:1, and FEC is 2% of the total mass of salt and solvent). And then carrying out electrochemical performance test on the battery, wherein the test voltage range is 2.0-4.0V or 2.0-4.3V.
Example 1
The present embodiment relates to a P2-type layered transition metal oxide material Na2/3Ni1/3Mn2/3O2The preparation method (molten salt method) comprises the following steps:
(1) 0.0102mol of each raw material was weighed in a stoichiometric ratio (2% more added to prevent loss of sodium source during sintering) (sodium carbonate (Na)2CO3) 0.02mol of manganese dioxide (MnO)2) 0.01mol of nickel hydroxide (Ni (OH))2) And 0.01mol fused salt sodium molybdate (Na)2MoO4)；
(2) Manually and uniformly mixing the weighed raw materials in an agate mortar to obtain solid mixed powder;
(3) the solid mixed powder was sintered in a muffle furnace in the following procedure: heating from room temperature to 900 deg.C within 174min, maintaining for 15h, cooling to 300 deg.C at 3 deg.C/min, and naturally cooling to room temperature to obtain molten salt coated Na-electric layered transition metal oxide2/3Ni1/3Mn2/3O2A product;
(4) washing the product with deionized water, separating water and product with centrifuge, removing molten salt, and removing colorless filtrate. Finally, washing with ethanol for one time;
(5) then the washed product is thermally treated for 10 hours at 750 ℃ in a tubular furnace in oxygen atmosphere to remove water and optimize the lattice structure of the material, and the layered transition metal oxide material Na is obtained2/3Ni1/3Mn2/3O2。
Example 2
The embodiment relates to a layered transition metal oxide material NaNi of O3 type1/3Mn1/2Ti1/6O2The preparation method (molten salt method) comprises the following steps:
(1) weighing raw materials and molten salt sodium molybdate according to stoichiometric ratio: 0.0153mol (2% more added to prevent loss of sodium source during sintering) (sodium carbonate (Na)2CO3) 0.02mol of manganese dioxide (MnO)2) 0.01mol of nickel hydroxide (Ni (OH))2) 0.005mol of nanoscale titanium dioxide (TiO)2) And 0.01mol of fused salt sodium molybdate (Na)2MoO4)；
(2) Uniformly mixing, placing in a muffle furnace, sintering at 1000 ℃ for 10h, washing the molten salt with deionized water, centrifuging after washing with water, wherein the filtrate obtained in the first time is colorless, the filtrate obtained in the second time is yellow and transparent, the filtrate obtained in the third time is light yellow and transparent, and the filtrate obtained in the fourth time is colorless and transparent after washing with ethanol;
(3) then the product after water washing is thermally treated for 10 hours at 750 ℃ in a tubular furnace in oxygen atmosphere to remove water and optimize the lattice structure of the material, and the layered transition metal oxide material NaNi is obtained1/3Mn1/2Ti1/6O2。
Example 3Na0.5Ni0.15Co0.2Mn0.65O2Preparation of the Material
This example relates to Na0.5Ni0.15Co0.2Mn0.65O2The preparation method of the material comprises the following steps:
(1) 0.00752mol (2% more added to prevent loss of sodium source during sintering) of each raw material was weighed in a stoichiometric ratio to obtain sodium carbonate (Na)2CO3)、0.0195mol manganese dioxide (MnO)2) 0.0045mol of nickel hydroxide (Ni (OH))2) 0.006mol of cobalt hydroxide and 0.01mol of fused salt sodium molybdate (Na)2MoO4)。
The subsequent steps were the same as in example 1.
Example 4
The embodiment relates to an Al-doped P2-type layered transition metal oxide material Na2/3Ni2/9Al1/9Mn2/3O2The preparation method (molten salt method) comprises the following steps:
(1) weighing the following raw materials in a stoichiometric ratio: 0.0102mol of sodium carbonate (Na)2CO3) 0.02mol of manganese dioxide (MnO)2) 0.0067mol of Nickel hydroxide (Ni (OH)2) And 0.00167mol nanoscale alumina (20 nm).
(2) The weighed raw materials were dry-milled in a ball mill pot (400rpm, 4h) to obtain a powder and 0.01mol of sodium molybdate (Na)2MoO4) And (3) manually mixing the materials evenly in an agate mortar to obtain solid mixed powder.
(3) The solid mixed powder was sintered in a muffle furnace in the following procedure: raising the temperature from room temperature to 1000 ℃ at a speed of 5 ℃/min, maintaining for 15h, then reducing the temperature to 300 ℃ at a speed of 3 ℃/min, and naturally cooling to room temperature to obtain the layered transition metal oxide sodium ion battery anode material Na coated by the molten salt2/3Ni2/9Al1/9Mn2/3O2And (3) obtaining the product.
(4) Washing the product with deionized water, separating water and product with a centrifuge, removing molten salt, washing the filtrate with ethanol, and oven drying. Then the product after water washing is thermally treated for 10 hours at 750 ℃ in a tubular furnace in oxygen atmosphere to remove water and optimize the lattice structure of the material, and the Al-doped layered transition metal oxide material Na is obtained2/3Ni2/9Al1/ 9Mn2/3O2。
Example 5
This example relates to a Ti-doped P2-type layered transition metal oxide material, Na2/3Ni1/6Ti1/6Mn2/3O2Preparation method of (1)(molten salt method) comprising the steps of:
(1) weighing the following raw materials in a stoichiometric ratio: 0.0102mol of sodium carbonate (Na)2CO3) 0.02mol of manganese dioxide (MnO)2) 0.005mol of Nickel hydroxide (Ni (OH))2) And 0.005mol of nanoscale titanium dioxide (20 nm).
(2) The weighed raw materials are dry-milled in a ball milling pot at 400rpm for 4 hours to obtain powder and 0.01mol of sodium molybdate (Na)2MoO4) And (3) manually mixing the materials evenly in an agate mortar to obtain solid mixed powder.
(3) The solid mixed powder was sintered in a muffle furnace in the following procedure: raising the temperature from room temperature to 1000 ℃ at a speed of 5 ℃/min, maintaining for 15h, then reducing the temperature to 300 ℃ at a speed of 3 ℃/min, and naturally cooling to room temperature to obtain the layered transition metal oxide sodium ion battery anode material Na coated by the molten salt2/3Ni1/6Ti1/6Mn2/3O2And (3) obtaining the product.
(4) Washing the product with deionized water, separating water and product with centrifuge, removing molten salt, and removing colorless filtrate. Then the water-washed product is thermally treated for 10 hours at 750 ℃ in a tubular furnace in oxygen atmosphere to remove water and optimize the lattice structure of the material, thus obtaining the Ti-doped layered transition metal oxide material Na2/3Ni1/6Ti1/6Mn2/3O2。
Comparative example 1 high temperature solid phase Process preparation
This comparative example relates to a P2-type layered transition metal oxide material Na2/3Ni1/3Mn2/3O2The preparation method (high temperature solid phase method) comprises the following steps:
(1) mixing raw materials (sodium carbonate (Na)2CO3) Manganese dioxide (MnO)2) And nickel hydroxide (Ni (OH)2) ) are weighed in stoichiometric proportions.
(2) Adding a proper amount of ethanol and agate beads into the weighed mixture in an agate ball milling tank, sealing, carrying out ball milling at the speed of 300rpm for 3 hours, and drying to obtain solid mixed powder;
(3) tabletting the solid mixed powder, and making into tablet in muffle furnaceSintering the mixture in a procedure to obtain the layered transition metal oxide sodium-ion battery anode material Na2/3Ni1/3Mn2/3O2。
Effect example 1 SEM, XRD characterization (molten salt method v.s. high temperature solid phase method)
FIG. 1a shows P2-Na prepared in example 12/3Ni1/3Mn2/3O2FIG. 1e is a SEM photograph of P2-Na prepared by the high temperature solid phase method of comparative example 12/3Ni1/3Mn2/3O2SEM image of (d).
FIG. 2 is P2-Na prepared by the molten salt method of example 1 and the high temperature solid phase method of comparative example 12/3Ni1/3Mn2/3O2XRD pattern. FIGS. 5a and 5b show NaNi prepared in example 21/3Mn1/2Ti1/6O2SEM image and magnification of the product.
Therefore, the sodium-electric layered transition metal oxide material prepared by the method is single crystal particles, and has high crystallinity and better interface stability.
Effect example 2 comparison of electrochemical properties (molten salt method v.s. high temperature solid phase method)
Fig. 3 is a graph comparing the cycle performance of the layered transition metal oxide materials prepared in example 1 and comparative example 1 for a battery, with a voltage range of 2.0 to 4.0V, a magnification of 0.1C for the first three rounds, and a magnification of 1C for the subsequent rounds. FIG. 4 is a graph showing the comparison of cycle performances of batteries fabricated using layered transition metal oxide materials obtained in example 1 and comparative example 1, wherein the voltage range is 2.0-4.3V and the rate is 0.1C. The results of comparing electrochemical properties when the materials prepared in example 1 and comparative example 1 were used in a battery are shown in table 1 below.
Table 1 comparison of electrochemical properties of materials prepared in example 1 and comparative example 1 when used in a battery
Figure BDA0002824954700000131
Figure BDA0002824954700000141
Thus, Na P2 form, prepared in example 1, was observed2/3Ni1/3Mn2/3O2When the voltage range is 2-4V, the first circle 0.1C discharge capacity is 91.43mAh g-1After three cycles of 0.1C activation, the first cycle discharge capacity of 1C was 84.26mAh g-1The capacity retention rate of 96.5% after 200 cycles of 1C charge-discharge cycle and the capacity of 81.35mAh g-1. The capacity is 92.7mAh g after 0.1C multiplying power circulation for 50 circles under the voltage range of 2-4.3V-1Is superior to the performance of the material prepared by the solid phase method.
Effect example 3
The NaNi O3 type prepared in example 2 was added1/3Mn1/2Ti1/6O2And preparing the product into a pole piece, and assembling the pole piece into a button cell to perform electrochemical performance test. FIG. 5c shows NaNi O3 form prepared in example 21/3Mn1/2Ti1/6O2The prepared battery charge-discharge performance graph (voltage range is 2.0-4.3V).
As can be seen from FIGS. 5c and 5d, NaNi O31/3Mn1/2Ti1/6O2The first-circle discharge capacity is 117.3mAh g when the voltage range is 2-4.3V-1And the capacity is 79mAh g after 1C charging and discharging for 30 circles-1And the capacity is 76.5mAh g after 60 circles of charging and discharging of 1C-1And the capacity retention rate of 60 cycles of 1C circulation is 88.9 percent.
Effect example 4
Na obtained in example 30.5Ni0.15Co0.2Mn0.65O2The test method is used for electrochemical performance test.
FIG. 6 shows that the resulting material showed good performance at 1C, 2C cycles with a discharge rate in the voltage range of 1.7-4.3V, especially the first cycle discharge capacity at 2C (118.4 mAh.g.)-1) In the case of a large number, the cycle stability is good (capacity retention rate of 96.9% at 100 cycles of 2C cycle).
Effect example 5 electrochemical performance test after doping with Al
The transition metal oxide material P2-Na obtained in example 4 was added2/3Ni2/9Al1/9Mn2/3O2And (4) preparing a pole piece, assembling the button cell and carrying out electrochemical performance test. As can be seen in FIG. 10a, P2-Na2/3Ni2/9Al1/9Mn2/3O2The first-circle discharge capacity is 168mAh g under the multiplying power of 0.1C when the voltage range is 2-4.3V-1The capacity retention rate of 25 cycles is 84.7 percent, and the ratio of P2-Na2/ 3Ni1/3Mn2/3O2The capacity retention rate (57%) is high.
Effect example 6 electrochemical Performance test after doping with Ti
The product P2-Na obtained in example 5 was added2/3Ni1/2Ti1/6Mn2/3O2And (5) manufacturing a pole piece and assembling the button cell. As can be seen in FIG. 10a, P2-Na2/3Ni1/2Ti1/6Mn2/3O2The first-cycle discharge capacity is 122.64mAh g under the multiplying power of 0.1C when the voltage range is 2-4.3V-1The capacity retention rate of 22 cycles is 94.7 percent, and the ratio of P2-Na2/3Ni1/3Mn2/3O2The corresponding capacity retention (57%) is high.
Effect example 7 different sources of sodium (Na)2CO3、NaOH、NaCH3COO) of
(1) 0.0102mol (Na) of each raw material was weighed in a stoichiometric ratio2CO3Or NaOH or NaCH3COO), 0.02mol manganese dioxide (MnO)2) 0.01mol of nickel hydroxide (Ni (OH))2) And 0.01mol fused salt sodium molybdate (Na)2MoO4)；
The subsequent steps and conditions were the same as in example 1 to prepare Na form P22/3Ni1/3Mn2/3O2。
FIG. 7 shows the preparation of Na form P2 from different sodium sources2/3Ni1/3Mn2/3O2Comparative graph of Battery cycling Performance from Na2CO3The first-circle discharge capacity of the prepared material for the charge-discharge cycle performance of the battery is more than that of NaOH and NaCH at 0.1C3COO; when the sodium source is NaCH3At COO, the first cycle discharge capacity is lower than that of comparative example 1 (solid phase method). Correspondingly preparing Na from different sodium sources2/3Ni1/3Mn2/3O2Comparative data of electrochemical properties of materials are shown in table 2 below.
TABLE 2 Na from different sources2/3Ni1/3Mn2/3O2Electrochemical performance of material
Figure BDA0002824954700000151
Figure BDA0002824954700000161
Effect example 8 different molten salts (Na)2MoO4NaCl, NaBr) in a sample
(1) Weighing the following raw materials in a stoichiometric ratio: 0.0102mol of sodium carbonate (Na)2CO3) 0.02mol of manganese dioxide (MnO)2) 0.01mol of nickel hydroxide (Ni (OH))2) And 0.01mol fused salt sodium molybdate (Na)2MoO4) (or 0.01mol NaCl, or 0.01mol NaBr);
the subsequent steps are the same as example 1, and P2 Na is prepared2/3Ni1/3Mn2/3O2。
As shown in SEM images of fig. 1b, 1c, and 1d, when sodium molybdate was used as the molten salt, the prepared material had a single crystal grain structure, and when NaCl or NaBr was used as the molten salt, the prepared material had an agglomeration phenomenon. FIG. 8 shows Na form P2 prepared with different molten salts2/3Ni1/3Mn2/3O2The battery cycle performance is compared with the figure, and the voltage range is 2-4.3V. As can be seen from FIG. 8, when the molten salt is Na2MoO4The prepared material is used for the first-circle discharge capacity of the charge-discharge cycle performance of the battery and is larger than NaCl and NaBr. Na prepared from different molten salts2/3Ni1/3Mn2/3O2Electrochemical properties of the materials are shown in table 3 below.
TABLE 3Na prepared with different molten salts2/3Ni1/3Mn2/3O2Electrochemical performance of material
Figure BDA0002824954700000162
Effect example 9 Effect of different doping metals on Properties (Fe, Al, Ti, Mg, Li)
(1) 0.0102mol (sodium carbonate (Na) was weighed out as each raw material in a stoichiometric ratio2CO3) 0.02mol of manganese dioxide (MnO)2) 0.01mol of nickel hydroxide (Ni (OH))2) And 0.01mol fused salt sodium molybdate (Na)2MoO4) And oxides of respective metal elements (0.00167mol Fe)2O3(30nm), or 0.00167mol of nanoscale aluminum oxide (20nm), or 0.005mol of nanoscale titanium dioxide (20nm), or 0.003mol of MgO, or 0.00045mol of Li2CO3)；
The subsequent steps are the same as example 1, and Na is prepared respectively2/3Ni2/9Fe1/9Mn2/3O2、Na2/3Ni2/9Al1/9Mn2/3O2、Na2/3Ni1/6Ti1/6Mn2/3O2、Na2/3Ni0.23Mg0.1Mn2/3O2、Na2/3Ni0.3Li0.03Mn2/3O2。
Figure 9 is an XRD pattern of a material prepared by doping different metals.
As shown in fig. 10a, the material doped with Fe and Al has a large first-turn discharge capacity and good cycle stability. Fig. 10b shows that the first-cycle discharge capacity after doping Mg element is larger than that of the undoped material. Fig. 10c shows that the first-cycle discharge capacity is not significantly increased after doping Li element, and the cycling stability is better than that of undoped material. The electrochemical properties of the materials prepared with different doping elements (Fe, Al, Ti, Li) are shown in the following tables 4-1 and 4-2.
TABLE 4-1 electrochemical Properties of materials prepared with different doping elements (Fe, Al, Ti, Li)
Figure BDA0002824954700000171
Remarking: na in the above table due to Li doping2/3Ni0.3Li0.03Mn2/3O2The cycle at 0.1C is relatively slow and only 30 cycles of testing are performed.
TABLE 4-2 electrochemical Properties of Mg-doped materials
Figure BDA0002824954700000181
Remarking: the capacitance values in the above table were measured at 1C after activation at 0.1C.
Effect example 10 Effect of different sintering temperatures
P2-type layered transition metal oxide material Na was prepared in the same manner as in example 1 except that the sintering temperatures in example 1 were set to 700, 800, 900 and 1000 ℃ respectively2/3Ni1/3Mn2/3O2。
It is shown in fig. 11 that the material prepared at 800-900 ℃ has better cycling performance effect when used in a battery. Na prepared at different sintering temperatures2/3Ni1/3Mn2/3O2The electrochemical properties of the materials are shown in table 5 below.
TABLE 5 Na prepared at different sintering temperatures2/3Ni1/3Mn2/3O2Electrochemical performance of the material
Figure BDA0002824954700000182
Effect example 11 Effect of sintering time
The sintering temperature is 1000 ℃, and the sintering time is 10 and 15 hours. The other conditions were the same as in example 1. The P2-type layered transition metal oxide material Na is prepared2/3Ni1/3Mn2/3O2。
In fig. 12, it is shown that in the case of sintering at a temperature of 1000 c, the sintering time of 15h is more effective than the cycle performance of the material produced in 10h for a battery. Na prepared by different sintering time2/3Ni1/3Mn2/3O2The electrochemical performance of the material is shown in table 6 below.
TABLE 6 Na prepared at different sintering times2/3Ni1/3Mn2/3O2Electrochemical performance of the material
Figure BDA0002824954700000191
While specific embodiments of the invention have been described above, it will be appreciated by those skilled in the art that this is by way of example only, and that the scope of the invention is defined by the appended claims. Various changes and modifications to these embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are within the scope of the invention.

Claims (24)

1. A preparation method of a transition metal oxide material is characterized by comprising the following steps:
under the condition of molten salt melting, the mixture of a sodium source and an oxygen-containing transition metal source is sintered at high temperature to prepare the transition metal oxide material NaxMeO2(ii) a The temperature of the high-temperature sintering is 800-1000 ℃, and the time of the high-temperature sintering is 10-15 h; the molten salt is sodium molybdate; the sodium source is selected from sodium carbonate or sodium hydroxide;
the crystal form of the transition metal oxide material is P2 Na2/3MeO2Or NaMeO type O32A ratio of moles of the molten salt to total moles of the oxygen-containing transition metal source of 1: (2-4);
wherein Me is a transition metal, and the transition metal is 'Ni and Mn' or 'Ni and Mn and Ti'.
2. The method for producing a transition metal oxide material according to claim 1,
the oxygen-containing transition metal source is selected from manganese oxide, manganese hydroxide, manganese carbonate, nickel oxide, nickel hydroxide, nickel carbonate or titanium dioxide;
and/or the mole number of the sodium source is 0.01-0.02 mol; the mole number of the oxygen-containing transition metal source is 0.02-0.03 mol;
and/or the raw material in the preparation method of the transition metal oxide material also comprises a doped metal element N, wherein the N is selected from one of Al, Fe, Li and Mg.
3. The method for producing a transition metal oxide material according to claim 2,
the oxygen-containing transition metal source is selected from transition metal hydroxides or transition metal carbonates;
the oxygen-containing transition metal source is selected from manganese dioxide or manganese carbonate, nickel hydroxide, nickel oxide, nickel carbonate or nano-scale titanium dioxide;
and/or the mole number of the sodium source is 0.0102-0.0153 mol;
and/or the mole number of the oxygen-containing transition metal source is 0.0205 or 0.0267 mol;
and/or the ratio of the number of moles of the molten salt to the total number of moles of the oxygen-containing transition metal source is 1: 3;
and/or the mole number of the molten salt is 0.01 mol;
and/or, the P2 type Na2/3MeO2Is Na2/3Ni1/3Mn2/3O2NaMeO type O32Is NaNi1/3Mn1/2Ti1/6O2；
And/or, when the transition metal oxide material is P2 type, the raw materials in the preparation method of the transition metal oxide material consist of sodium carbonate, manganese dioxide, nickel hydroxide and sodium molybdate;
when the transition metal oxide material is O3 type, the raw material of the preparation method of the transition metal oxide material is sodium carbonate Na2CO3Manganese dioxide, nickel hydroxide, nano titanium dioxide and sodium molybdate.
4. The method for producing a transition metal oxide material according to claim 2,
the raw material source of the doped metal element N is a nano-grade material;
and/or the mole number of the doped metal element N is 0.00167 or 0.005 mol;
and/or, when Me is selected from two transition metals and is doped with metal element N, the transition metal oxide material is prepared by using the chemical general formula Nax(TyMzN1-y-z)O2Represents; t, M is one of transition metal elements Me respectively;
wherein x is the ratio of the mole number of the sodium element to the total mole number of T, M and N, and the value range of x is as follows: x is not less than 1/3 and not more than 1;
y is the ratio of the mole number of the element T relative to the total mole number of T, M and N, and the value range of y is as follows: y is not less than 1/6 and not more than 1/3;
z is the ratio of the mole number of the M element to the total mole number of T, M and N, and the value range of z is: 1/9 is less than or equal to z is less than or equal to 2/3.
5. The method for producing a transition metal oxide material according to claim 4,
the source of the doped metal element N is nano-alumina or nano-titanium dioxide;
and/or, the Nax(TyMzN1-y-z)O2Wherein x is 1/3, 2/3 or 1, y is 1/3, 2/9 or 1/6; z is 1/3, 1/9, 2/3, 2/9 or 1/6;
and/or, the Nax(TyMzN1-y-z)O2Selected from Na2/3Ni2/9Al1/9Mn2/3O2Or Na2/3Ni1/6Ti1/6Mn2/3O2。
6. The method for producing a transition metal oxide material according to any one of claims 1 to 5, further comprising the step of compounding raw materials;
and/or the mixture of the sodium source and the oxygen-containing transition metal source is obtained by grinding and mixing;
and/or the temperature of the high-temperature sintering is 800-900 ℃;
and/or the high-temperature sintering time is 13-15 h;
and/or, the step of high-temperature sintering comprises raising the temperature from room temperature to the temperature of high-temperature sintering;
and/or after the high-temperature sintering, the method also comprises a step of cooling.
7. The method for producing a transition metal oxide material according to claim 6,
the proportioning is a step of proportioning the raw materials according to a stoichiometric ratio;
and/or the temperature of the high-temperature sintering is 840, 860 or 880 ℃;
and/or the time of high-temperature sintering is 14 and 15 hours;
and/or, the step of high-temperature sintering comprises raising the temperature from room temperature to the temperature of high-temperature sintering; wherein the rate of temperature rise is 5 ℃/min;
and/or after the high-temperature sintering, the method also comprises the step of cooling; the cooling rate is 3 ℃/min; the temperature is reduced to 300 ℃.
8. The method for producing a transition metal oxide material according to claim 7,
the step of reducing the temperature is followed by a step of washing.
9. The method for producing a transition metal oxide material according to claim 8,
the washing reagent is water;
and/or the number of washes is 2-3;
and/or, after washing with water, further washing with absolute ethyl alcohol;
and/or, the washing step is followed by the operations of removing the filtrate and drying.
10. The method for producing a transition metal oxide material according to claim 9,
the washing reagent is deionized water
And/or the operation method for removing the filtrate is centrifugation, the rotation speed of the centrifugation is 4500r/min, and the time of the centrifugation is 30 s;
and/or the drying temperature is 80 ℃, and the drying time is 1 h;
and/or, after the drying step, a heat treatment step is also included.
11. The method for preparing a transition metal oxide material as claimed in claim 10, wherein the temperature of the heat treatment is 650-800 ℃;
and/or the time of the heat treatment is 8-11 h;
and/or the heat treatment is carried out in a tube furnace in an oxygen atmosphere.
12. The method for preparing a transition metal oxide material according to claim 11, wherein the temperature of the heat treatment is 750 ℃;
and/or the time of the heat treatment is 10 h.
13. The method for preparing a transition metal oxide material according to claim 1, comprising the steps of: the high-temperature sintering temperature is 900 or 1000 ℃, and the high-temperature sintering time is 15 h.
14. The method of preparing a transition metal oxide material according to claim 13, wherein the high-temperature sintering comprises the steps of: heating to 900 ℃ from room temperature at the speed of 5 ℃/min, maintaining for 15h, then cooling to 300 ℃ at the speed of 3 ℃/min, and naturally cooling to room temperature to obtain the layered transition metal oxide material product coated by the molten salt.
15. A transition metal oxide material produced by the method for producing a transition metal oxide material according to any one of claims 1 to 14.
16. A positive electrode material for a sodium battery, comprising the transition metal oxide material according to claim 15.
17. Use of a transition metal oxide material as claimed in claim 15 in the manufacture of a sodium ion battery.
18. A sodium ion battery comprising the transition metal oxide material of claim 15.
19. A preparation method of a positive electrode material of a sodium-ion battery is characterized by comprising the following steps: the transition metal oxide material of claim 15, mixed with conductive carbon, a binder, and a solvent, and dried.
20. The method of claim 19, wherein prior to mixing the transition metal oxide material with the conductive carbon, the binder, and the solvent, further comprising sieving the transition metal oxide material;
and/or the mass ratio of the oxide material, the conductive carbon and the binder is 8: 1: 1;
and/or the solvent is 1-methyl-2-pyrrolidone;
and/or, the method also comprises a stirring step after the solvent is added, and slurry is obtained after stirring.
21. The method for preparing the positive electrode material for sodium-ion batteries according to claim 20, wherein the mesh number of the sieve is 400 meshes;
and/or the conductive carbon is Super P;
and/or the binder is polyvinylidene fluoride;
and/or, the method also comprises a stirring step after the solvent is added, wherein the stirring time is 5 minutes;
and/or, after the stirring step, uniformly coating the slurry on an aluminum foil and drying.
22. The method of claim 21, further comprising slicing the aluminum foil coated with black paste after the drying.
23. The method for preparing the positive electrode material of the sodium-ion battery as claimed in claim 22, further comprising cutting the aluminum foil coated with the black paste into circular pole pieces with a diameter of 10mm after the drying;
and/or, after the slicing, the vacuum drying of the pole piece is further included.
24. The method of claim 23, wherein the vacuum drying is performed at a temperature of 120 ℃,
and/or the vacuum drying time is 12 hours.
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