CN108807907B - Method for preparing particle self-assembly spherical tin monoxide/tin dioxide sodium ion battery cathode material by one-step method - Google Patents
Method for preparing particle self-assembly spherical tin monoxide/tin dioxide sodium ion battery cathode material by one-step method Download PDFInfo
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Abstract
The invention discloses a method for preparing a granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material by a one-step method, which comprises the following steps of firstly dissolving thiourea in absolute ethyl alcohol to prepare a solution A; then adding citric acid into the solution A under the stirring action until the citric acid is completely dissolved to form a solution B; then stirring the mixture according to the element molar ratio nSn:nSWeighing SnCl (0.5-2.0): (0.9-3.0)2·2H2Dissolving O in the solution B to form a solution C; then carrying out homogeneous hydrothermal reaction on the solution C to obtain a precursor after the reaction is finished; and finally, respectively centrifugally washing the precursor for a plurality of times by deionized water and absolute ethyl alcohol, and then drying in vacuum to obtain the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material.
Description
Technical Field
The invention relates to a preparation method of a lithium ion battery cathode material, in particular to a method for preparing a particle self-assembly spherical tin monoxide/tin dioxide sodium ion battery cathode material by a one-step method.
Background
Energy and environmental problems are two major problems faced by sustainable development of human society at present, and with the increasing problems of resource scarcity and environmental pollution, the consumption of traditional fossil energy is rising year by year, and the environmental pollution caused by the combustion of the fossil energy is increasing day by day, so that the generated resource and environmental pressure forces people to accelerate the utilization and development of clean and renewable energy, and the use and development of secondary rechargeable batteries are a necessary way which is the most effective and can solve the energy and environmental crisis at present. The sodium ion battery is used as an electrochemical energy storage source and has the advantages of abundant reserves, low price, environmental friendliness, good safety and the like. Compared with the lithium ion battery, the lithium ion battery has relatively better electrochemical performance and electrochemical behavior similar to that of the lithium ion battery, so that the lithium ion battery is hopeful to replace the lithium ion battery in the field of energy storage, and has larger market competitive advantage than the lithium ion battery. However, the ionic radius (r ═ 0.113nm) of sodium ions is about 30% larger than that of lithium ions (r ═ 0.076nm), so that reversible electrochemical intercalation and deintercalation reaction is difficult to realize, and the intercalation and deintercalation process easily causes the collapse of a main body lattice structure, so that the cycle performance, rate performance and electrochemical utilization performance of the material are poor, and therefore, the search for a proper sodium-intercalated battery material has certain difficulty.
Tin oxide has two crystal structures of tetragonal system and orthorhombic system. Tetragonal tin oxide has a lattice constant of 0.3803nm (a-b), 0.4838nm (c/a), and 1.27 (c/a). Each unit cell contains 2 basic units and all oxygen atoms are equivalent. The tin oxide is of a layered structure, 1 tin atom and 4 oxygen atoms form a square pyramid structure, the tin atom is positioned at the vertex, and the bottom is provided with 4 oxygen atoms. The distance of all oxygen atoms closest to the tin atom was 0.222nm, and each oxygen ion was surrounded by four tin ions. As an important tin-based compound, the tin monoxide has an excellent layered structure, low cost and high theoretical capacity (875 mAh.g)-1) And is considered to be one of the most promising anode materials. But the large volume expansion generated in the charging and discharging cycle process causes the structure damage and electrode pulverization, and finally causes the capacity attenuation to be too fast; and low conductivity limits their application and development as electrode materials.
The particle morphology can also cause certain influence on the electrochemical performance of a sample, the smaller the particle is, the larger the specific surface area is, the better the material is contacted with the electrolyte, and Li+The migration distance is shortened, so that the rate capability of the cathode material of the sodium-ion battery is improved. At present, according to the reported literature, tin monoxide/oxides are preparedThe main methods for tin are electrospinning [ Cho J S, Kang Y C. nanofibres complexing Yolk-Shell Sn @ void @ SnO/SnO2 and Hollow SnO/SnO2 and SnO2 Nanospheres via the Kirkendall Diffusion Effect and the infrared Electrochemical Properties [ J].Small,2015,11(36):4673-4681.].Journal of Nanoengineering&Nanomanufacturing,2015,5(3):210-215.](ii) a Solid phase method [ Santhi K, Rani C, Karuppuchamy S.Synthesis and catalysis of novel SnO/SnO2 hybrid photocatalysts [ J].Journal of Alloys&Compounds,2016,662(40):102-107.]And the like. The electrostatic spinning yield is unstable, the efficiency is low, only 0.1 g/h-1 g/h can be obtained per hour, the industrialization and the scale of the electrostatic spinning are greatly hindered, the wide application of the nanofiber material is caused, the requirement of the traditional market on the dosage of the nanofiber cannot be met, the solid phase reaction method has the advantages of no need of a solvent, simple equipment, easiness in control of reaction conditions and the like, but the reaction is usually not thorough because the reaction is carried out in a solid phase, and the yield is low.
Disclosure of Invention
The invention aims to provide a method for preparing a granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material by a one-step method, so as to overcome the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material by a one-step method comprises the following steps:
the method comprises the following steps: dissolving thiourea in absolute ethyl alcohol to prepare a solution A; then adding citric acid into the solution A under the stirring action until the citric acid is completely dissolved to form a solution B;
step two: according to the element mole ratio n under the stirring actionSn:nSWeighing SnCl (0.5-2.0): (0.9-3.0)2·2H2Dissolving O in the solution B to form a solution C;
step three: carrying out homogeneous hydrothermal reaction on the solution C to obtain a precursor after the reaction is finished;
step four: and respectively centrifugally washing the precursor for several times by using deionized water and absolute ethyl alcohol, and then drying in vacuum to obtain the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material.
Further, the concentration of the solution A in the step one is 0.13-0.50 mol/L.
Further, the concentration of the citric acid in the solution B in the step one is 0.01-0.05 mol/L.
Further, the homogeneous hydrothermal reaction in the third step is specifically: and (3) putting the solution C into a homogeneous hydrothermal reaction kettle, sealing, controlling the filling ratio to be 40-60%, and putting into a homogeneous hydrothermal reaction instrument for reaction.
Further, the temperature of the homogeneous hydrothermal reaction is 160-200 ℃, and the time is 16-20 h.
And further, in the fourth step, the precursor is respectively centrifugally washed 3 times by deionized water and absolute ethyl alcohol.
Further, the temperature of vacuum drying in the fourth step is 60 ℃, and the time is 12 hours.
Compared with the prior art, the invention has the following beneficial technical effects:
the tin monoxide/tin oxide sodium ion battery cathode material prepared by the method is of a spherical structure, the average diameter size is about 500 nm-1 um, the preparation cost is low, the preparation period is short, and the appearance is relatively uniform. And moreover, the spherical tin monoxide/sodium tin oxide battery cathode material is obtained by controlling reaction parameters, and the larger specific surface area of the spherical tin monoxide/sodium tin oxide battery cathode material increases the contact chance and the reaction active sites with the electrolyte, is favorable for the migration of sodium ions, relieves the volume change in the charge and discharge process, and is favorable for improving the electrochemical performance of the material. At 100mA · g-1First discharge capacity 1433.5mAh g at current density-1Circulate 10 circles, the capacity can reach 841.5mAh g-1And the high-power-factor performance is achieved under high current density.
Compared with the preparation method, the solvothermal method has the characteristics of simple process, short preparation period and easily controlled reaction conditions, can control the reaction process, the morphology and size and the phase composition by using different temperatures, and can obtain different phase compositions and special structural morphologies at proper temperatures. The difference of phase and morphology has great influence on the performance of the material, in addition, the solvothermal method has the advantages of high reaction rate, full and thorough reaction and the like, and the defects of difficult reaction and control, high energy consumption, low yield, complex process and the like of the traditional method are overcome.
The tin dioxide adopted by the invention has two crystal structures of a rutile structure and an orthorhombic structure of a tetragonal system. Among them, the orthorhombic whisker structure (a: 0.4714nm, b: 0.5727nm, and c: 0.5210nm) is very unstable and generally exists only at high temperature. Thus, the rutile structure of the tetragonal system is most common and used. Tetragonal rutile-structured tin oxide has a lattice constant of "b" 0.4737nm, a lattice constant of "c" 0.3186nm, and a lattice constant of "c/a" 0.672. Each plane contains 2 molecules of tin oxide, wherein each Sn atom is located in the center of an approximately octahedral shape composed of 6O atoms, and each O atom is also located in the center of an equilateral triangle composed of 3 Sn atoms. Furthermore, tin dioxide has a relatively high theoretical capacity (782mAh · g)-1) And the layered structure is favorable for the intercalation and deintercalation of sodium ions. Li can be relieved by compounding tin oxide with tin dioxide+The volume expansion during the de-intercalation process improves the cycle performance of the electrode material and enhances the conductivity of the negative electrode material, thereby improving its electrochemical performance.
Drawings
FIG. 1 is an XRD pattern of a particulate self-assembled spherical tin monoxide/tin dioxide sodium ion battery anode material prepared in example 2 of the present invention;
FIG. 2 is an SEM image of the negative electrode material of the particle self-assembled spherical tin monoxide/tin dioxide sodium ion battery prepared in example 2 of the invention;
FIG. 3 is a graph showing the rate performance of the negative electrode material of the particle-assembled spherical tin monoxide/tin dioxide sodium ion battery prepared in example 2 of the present invention
Detailed Description
Embodiments of the invention are described in further detail below:
a method for preparing a granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material by a one-step method comprises the following steps:
1) dissolving Thiourea (TU) in absolute ethyl alcohol to prepare a solution A with the concentration of 0.13-0.50 mol/L, and adding citric acid into the solution A under the action of magnetic stirring until the citric acid is completely dissolved to form a solution B, so that the concentration of the citric acid in the solution B is 0.01-0.05 mol/L;
2) under the action of magnetic stirring according to the element mole ratio nSn:nSSnCl (0.5-2.0): (0.9-3.0)2·2H2Dissolving O in the solution B until the O is completely dissolved to form a solution C;
3) putting the solution C into a homogeneous hydrothermal reaction kettle, sealing, controlling the filling ratio to be 40% -60%, putting into a homogeneous hydrothermal reaction instrument, controlling the reaction temperature to be 160-200 ℃ and the reaction time to be 16-20 h;
4) and after the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by using deionized water and absolute ethyl alcohol to obtain a black precursor, and carrying out vacuum drying at the temperature of 60 ℃ for 12 hours to obtain the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material.
The present invention is described in further detail below with reference to examples:
example 1
1) Dissolving Thiourea (TU) in absolute ethyl alcohol to prepare a solution A with the concentration of 0.13mol/L, and adding citric acid into the solution A under the action of magnetic stirring until the citric acid is completely dissolved to form a solution B, so that the concentration of the citric acid in the solution B is 0.01 mol/L;
2) according to the element mole ratio nSn:nSSnCl at 0.5:0.9 ratio2·2H2Dissolving O in the solution B until the O is completely dissolved to form a solution C;
3) putting the solution C into a homogeneous hydrothermal reaction kettle, sealing, controlling the filling ratio to be 40%, putting into a homogeneous hydrothermal reaction instrument, controlling the reaction temperature to be 160 ℃ and the reaction time to be 16 h;
4) and after the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by using deionized water and absolute ethyl alcohol to obtain a black precursor, and carrying out vacuum drying at the temperature of 60 ℃ for 12 hours to obtain the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material.
Example 2
1) Dissolving Thiourea (TU) in absolute ethyl alcohol to prepare a solution A with the concentration of 0.26mol/L, and adding citric acid into the solution A under the action of magnetic stirring until the citric acid is completely dissolved to form a solution B, so that the concentration of the citric acid in the solution B is 0.03 mol/L;
2) according to the element mole ratio nSn:nSSnCl 1.0:1.62·2H2Dissolving O in the solution B until completely dissolving O into a solution C;
3) putting the solution C into a homogeneous hydrothermal reaction kettle, sealing, controlling the filling ratio to be 50%, putting into a homogeneous hydrothermal reaction instrument, controlling the reaction temperature to be 180 ℃ and the reaction time to be 18 h;
4) and after the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by using deionized water and absolute ethyl alcohol to obtain a black precursor, and carrying out vacuum drying at the temperature of 60 ℃ for 12 hours to obtain the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material.
As can be seen from FIG. 1, the prepared samples respectively correspond to standard card PDF-07-0195SnO and standard card PDF-46-1088SnO2The crystallinity and phase of the material are better as can be seen from an XRD pattern; as can be seen from FIG. 2, the prepared tin monoxide/tin oxide is a nano microsphere, and the diameter of the nano microsphere reaches 500 nm-1 um; as can be seen from FIG. 3, at 100mA · g-1First discharge capacity 1433.5mAh g at current density-1Circulate 10 circles, the capacity can reach 841.5mAh g-1The material has higher rate performance under high current density, and the negative electrode material of the particle-assembled spherical tin oxide/tin oxide sodium ion battery has better capacity retention rate under high current density.
Example 3
1) Dissolving Thiourea (TU) in absolute ethyl alcohol to prepare a solution A with the concentration of 0.50mol/L, and adding citric acid into the solution A under the action of magnetic stirring until the citric acid is completely dissolved to form a solution B, so that the concentration of the citric acid in the solution B is 0.05 mol/L;
2) according to the element mole ratio nSn:nSSnCl 2.0:3.02·2H2Dissolving O in the solution B until completely dissolving O into a solution C;
3) putting the solution C into a homogeneous hydrothermal reaction kettle, sealing, controlling the filling ratio to be 60%, putting into a homogeneous hydrothermal reaction instrument, controlling the reaction temperature to be 200 ℃ and the reaction time to be 20 h;
4) and after the reaction is finished, taking out the precursor, respectively centrifugally washing the precursor for 3 times by using deionized water and absolute ethyl alcohol to obtain a black precursor, and carrying out vacuum drying at the temperature of 60 ℃ for 12 hours to obtain the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material.
Claims (7)
1. A method for preparing a granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material by a one-step method is characterized by comprising the following steps:
the method comprises the following steps: dissolving thiourea in absolute ethyl alcohol to prepare a solution A; then adding citric acid into the solution A under the stirring action until the citric acid is completely dissolved to form a solution B;
step two: according to the element mole ratio n under the stirring actionSn:nSWeighing SnCl (0.5-2.0): (0.9-3.0)2·2H2Dissolving O in the solution B to form a solution C;
step three: carrying out homogeneous hydrothermal reaction on the solution C to obtain a precursor after the reaction is finished;
step four: and respectively centrifugally washing the precursor for several times by using deionized water and absolute ethyl alcohol, and then drying in vacuum to obtain the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery cathode material.
2. The method for preparing the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery anode material in the one-step method according to claim 1, wherein the concentration of the solution A in the first step is 0.13-0.50 mol/L.
3. The method for preparing the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery anode material in the one-step method according to claim 1, wherein the concentration of citric acid in the solution B in the first step is 0.01-0.05 mol/L.
4. The method for preparing the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery anode material by the one-step method according to claim 1, wherein the homogeneous hydrothermal reaction in the third step is specifically as follows: and (3) putting the solution C into a homogeneous hydrothermal reaction kettle, sealing, controlling the filling ratio to be 40-60%, and putting into a homogeneous hydrothermal reaction instrument for reaction.
5. The method for preparing the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery anode material through the one-step method according to claim 4, wherein the temperature of the homogeneous hydrothermal reaction is 160-200 ℃ and the time is 16-20 h.
6. The method for preparing the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery anode material according to the claim 1, wherein the precursor is centrifugally washed for 3 times by deionized water and absolute ethyl alcohol respectively in the fourth step.
7. The method for preparing the granular self-assembled spherical tin monoxide/tin dioxide sodium ion battery anode material in one step according to claim 1, wherein the temperature of vacuum drying in the fourth step is 60 ℃ and the time is 12 hours.
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| CN102602985A (en) * | 2012-04-11 | 2012-07-25 | 吉林大学 | Method for preparing nanometer stannous oxide and nanometer stannic oxide |
| CN103346299A (en) * | 2013-06-08 | 2013-10-09 | 上海大学 | In-situ etching method for preparing hollow tin-based oxide/carbon composite nano-material |
| CN105514404A (en) * | 2016-01-25 | 2016-04-20 | 陕西科技大学 | Nanoparticle assembled burr spherical SnO2 sodium-ion battery anode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102602985A (en) * | 2012-04-11 | 2012-07-25 | 吉林大学 | Method for preparing nanometer stannous oxide and nanometer stannic oxide |
| CN103346299A (en) * | 2013-06-08 | 2013-10-09 | 上海大学 | In-situ etching method for preparing hollow tin-based oxide/carbon composite nano-material |
| CN105514404A (en) * | 2016-01-25 | 2016-04-20 | 陕西科技大学 | Nanoparticle assembled burr spherical SnO2 sodium-ion battery anode material and preparation method thereof |
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