CN109768270B - Carbon-coated tin-based negative electrode material, sodium ion battery and preparation method and application thereof - Google Patents
Carbon-coated tin-based negative electrode material, sodium ion battery and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon-coated tin-based negative electrode material, a sodium ion battery, and a preparation method and application thereof. The carbon-coated tin-based negative electrode material comprises sodium titanium stannate and carbon, wherein the chemical formula of the sodium titanium stannate is NaTiSnO4The carbon is coated on the surface of the sodium titanium stannate, the content of the carbon is 1-10%, and the percentage is the mass percentage of the carbon relative to the carbon-coated tin-based negative electrode material. The preparation method of the carbon-coated tin-based negative electrode material comprises the following steps: s1: mixing a sodium source, a titanium source, a tin source, a carbon source and water to obtain slurry; s2: spray drying the slurry to obtain a precursor; s3: and sintering the precursor to obtain the carbon-coated tin-based negative electrode material. The preparation method has simple process, can realize large-scale preparation, and has low cost. The carbon-coated tin-based negative electrode material has zero strain, stable structure, high charge-discharge specific capacity and good cycle performance in the sodium ion desorption/intercalation process. Can be applied to the preparation of sodium ion batteries and has great advantages as energy storage application.
Description
Technical Field
The invention relates to a carbon-coated tin-based negative electrode material, a sodium ion battery, and a preparation method and application thereof.
Background
The scale energy storage needs an energy storage system which is cheap, safe, green and environment-friendly, in the existing scale energy storage mode, the electrochemical energy storage system is widely concerned with the characteristics of high efficiency and flexibility, and is also a research hotspot at home and abroad at present, the sodium element is abundant in earth reserves, is widely distributed and simple to extract, and the sodium ion battery has the advantage of low cost and is expected to be applied as large-scale energy storage.
The sodium ion battery has obvious advantages as a large-scale energy storage application, but also has challenges, particularly the difficulty of searching for an electrode material with excellent electrochemical performance. At the present stage, the research on sodium-ion batteries is less, alternative anode and cathode materials are immature, and the corresponding preparation process is very limited, so that the performance of the sodium-ion batteries at present is far from the expected target. Therefore, it is important to find and develop high-performance sodium ion battery electrode materials. Research results show that the transition metal tin-based material has better reversible sodium insertion/removal characteristics. However, the volume expansion and contraction effect of the transition metal is obvious in the reaction process of the transition metal and sodium, and the electrode material is easy to crack after repeated charge and discharge, so that the capacity of the battery is attenuated, and the cycle performance is poor. How to more effectively alleviate the volume effect is always one of the hot points in the research of the cathode material of the sodium-ion battery.
Disclosure of Invention
The invention provides a carbon-coated tin-based negative electrode material, a sodium ion battery and a preparation method thereof, aiming at overcoming the defects of overlarge volume effect and unsatisfactory cycle stability of the tin-based negative electrode material of the sodium ion battery in the prior art. The carbon-coated tin-based negative electrode material prepared by the invention has zero strain, stable structure, high charge-discharge specific capacity and good cycle performance in the sodium ion desorption/intercalation process.
In order to achieve the above object, the present invention adopts the following technical solutions.
The invention provides a carbon-coated tin-based negative electrode material which comprises sodium titanium stannate and carbon, wherein the chemical formula of the sodium titanium stannate is NaTiSnO4The carbon is coated on the surface of the sodium titanium stannate, the content of the carbon is 1-10%, and the percentage is the mass percentage of the carbon relative to the carbon-coated tin-based negative electrode material.
In the present invention, the content of carbon is preferably 1 to 5%, for example, 2% or 3%.
In the present invention, preferably, the carbon is uniformly coated on the surface of the titanium sodium stannate.
In the invention, the carbon-coated tin-based negative electrode material can be spherical.
In the invention, the particle size of the carbon-coated tin-based negative electrode material can be 3-8 μm.
In the invention, the sodium titanium stannate can be prepared by the conventional method in the fieldThe chemical formula of the NaTiSnO is prepared by using a sodium source, a titanium source and a tin source which are conventional in the field4The product of (1).
The invention provides a preparation method of a carbon-coated tin-based negative electrode material, which comprises the following steps:
s1: mixing a sodium source, a titanium source, a tin source, a carbon source and water to obtain slurry; wherein the sodium source, the titanium source and the tin source are in a molar ratio of sodium, titanium and tin of 1: 1: 1;
s2: spray drying the slurry to obtain a precursor;
s3: sintering the precursor to obtain the carbon-coated tin-based negative electrode material;
the carbon-coated tin-based negative electrode material comprises sodium titanium stannate and carbon, wherein the chemical formula of the sodium titanium stannate is NaTiSnO4The carbon is coated on the surface of the sodium titanium stannate, the content of the carbon is 1-10%, and the percentage is the mass percentage of the carbon relative to the carbon-coated tin-based negative electrode material.
In the above preparation method, the content of carbon is preferably 1 to 5%, for example, 2% or 3%.
In the above preparation method, preferably, the carbon is uniformly coated on the surface of the sodium titanium stannate.
In the present invention, the sodium source in S1 may be a sodium salt conventionally used in the art, such as one or more of sodium carbonate, sodium hydroxide, and sodium nitrate, preferably sodium carbonate.
In the present invention, the titanium source in S1 may be a titanium source conventionally used in the art, and is preferably titanium dioxide. The titanium dioxide may be titanium dioxide conventionally used in the art, and the particle size of the titanium dioxide may be 200-500nm, for example 300nm or 400 nm.
In the present invention, the tin source in S1 may be a tin source conventionally used in the art, and is preferably tin dioxide. The tin dioxide may be tin dioxide conventionally used in the art, and the particle size of the tin dioxide may be 200-800nm, such as 400nm or 600 nm.
In the present invention, the solid content of the slurry of S1 can be conventional in the art, and is preferably 10 to 40%, for example 20%.
In the present invention, the carbon source in S1 may be a carbon source conventionally used in the art, preferably one or more of glucose, starch, and sucrose, and preferably starch. The carbon source is decomposed and carbonized in S3, and the carbon remained after the decomposition and carbonization of each carbon source is different, so the adding amount of the carbon source can be determined by the following method: the residual carbon content of the carbon source (for example, the residual carbon content of starch is 18%) is determined by a thermal analysis test, and then the adding amount of the carbon source is calculated according to the carbon content in the carbon-coated tin-based negative electrode material.
In the present invention, the mixing in S1 may be performed in a manner conventional in the art, preferably by ball milling. The ball milling time may be conventional in the art, and is preferably 1 to 5 hours, for example 3 hours. The ball milling speed may be conventional in the art, preferably 200-800rmp, such as 400rmp or 500 rmp.
In the present invention, the spray drying described in S2 may be performed in a manner conventional in the art. The inlet temperature of the spray drying is preferably 200 ℃ to 260 ℃, for example 220 ℃ or 230 ℃. The outlet temperature of the spray drying is preferably 95-120 c, for example 105 c or 110 c.
In the present invention, the precursor described in S2 is generally spherical.
In the present invention, the sintering in S3 may be performed in a manner conventional in the art. The sintering temperature is preferably 600-900 deg.C, such as 800 deg.C or 850 deg.C. The sintering time is preferably 5 to 15 hours, for example 10 hours or 12 hours. The sintering is preferably carried out under an inert atmosphere, preferably nitrogen or argon.
In the present invention, S3 preferably further includes cooling after sintering, and the cooling may be performed in a manner conventional in the art, preferably natural cooling.
The invention also provides the carbon-coated tin-based negative electrode material prepared by the preparation method. The carbon-coated tin-based negative electrode material may be spherical in shape. The particle size of the carbon-coated tin-based negative electrode material can be 3-8 mu m.
The invention also provides application of the carbon-coated tin-based negative electrode material in a sodium ion battery.
The invention also provides a sodium ion battery, and the cathode of the sodium ion battery comprises the carbon-coated tin-based cathode material.
In the invention, the sodium-ion battery is preferably a soft package sodium-ion battery.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
1. the carbon-coated tin-based negative electrode material is different from an electrode material with a laminated structure, namely NaTiSnO4The one-dimensional tunnel frame structure is adopted, sodium ions are removed/embedded in the tunnel, the stability of the whole structure is not influenced, the volume of the material is not changed, and the cycle performance of the battery is greatly improved.
2. The invention adopts spray drying to prepare the precursor, and can uniformly mix NaTiSnO4The particles are coated in the carbon microspheres, so that the ionic and electronic conductivity is obviously improved, and the charging and discharging specific capacity of the negative electrode material is favorably improved.
3. The preparation method disclosed by the invention is simple in process, can be used for large-scale preparation, reduces the manufacturing cost, can be applied to preparation of soft package sodium-ion batteries, is green, safe and cheap, and has great advantages when being used as energy storage application.
Drawings
Fig. 1 is an XRD spectrum of the carbon-coated tin-based negative electrode material prepared in example 1 of the present invention.
Fig. 2 is a scanning electron microscope image of the carbon-coated tin-based negative electrode material prepared in example 1 of the present invention.
Fig. 3 is a charge-discharge curve diagram of the carbon-coated tin-based negative electrode material prepared in example 1 of the present invention at different current densities.
FIG. 4 is a graph of the cycle curve of the carbon-coated tin-based negative electrode material prepared in example 1 of the present invention at a current density of 120 mA/g.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
Weighing 2.65g of sodium carbonate, 4g of titanium dioxide (with the particle size of 300nm), 7.53g of tin dioxide (with the particle size of 400nm) and 2.1g of starch, adding the mixture into 60mL of deionized water, uniformly mixing, placing the mixture into a ball milling tank, and carrying out ball milling for 3 hours at the ball milling speed of 500rmp to obtain slurry; spray drying and granulating the slurry to obtain a precursor, wherein the inlet temperature of the spray drying is 220 ℃, and the outlet temperature of the spray drying is 105 ℃; sintering the precursor for 12 hours at 800 ℃ in nitrogen atmosphere, and naturally cooling to room temperature to obtain the carbon-coated tin-based negative electrode material NaTiSnO4C, wherein the carbon content is 3%.
Example 2
Weighing 2.65g of sodium carbonate, 4g of titanium dioxide (with the particle size of 200nm), 7.53g of tin dioxide (with the particle size of 200nm) and 0.7g of starch, adding the mixture into 70mL of deionized water, uniformly mixing, placing the mixture into a ball milling tank, and carrying out ball milling for 1 hour at the ball milling speed of 200rmp to obtain slurry; spray drying and granulating the slurry to obtain a precursor, wherein the inlet temperature of the spray drying is 200 ℃, and the outlet temperature of the spray drying is 95 ℃; sintering the precursor for 5 hours at 600 ℃ in nitrogen atmosphere, and naturally cooling to room temperature to obtain the carbon-coated tin-based negative electrode material NaTiSnO4C, wherein the carbon content is 1%.
Example 3
Weighing 2.65g of sodium carbonate, 4g of titanium dioxide (with the particle size of 500nm), 7.53g of tin dioxide (with the particle size of 800nm) and 3.5g of starch, adding the mixture into 60mL of deionized water, uniformly mixing, placing the mixture into a ball milling tank, and carrying out ball milling for 5 hours at the ball milling speed of 800rmp to obtain slurry; spray drying and granulating the slurry to obtain a precursor, wherein the inlet temperature of the spray drying is 260 ℃, and the outlet temperature of the spray drying is 120 ℃; sintering the precursor for 15 hours at 900 ℃ in nitrogen atmosphere, and naturally cooling to room temperature to obtain the carbon-coated tin-based negative electrode material NaTiSnO4C, wherein the carbon content is 5%.
Example 4
2.65g of sodium carbonate is weighed,Adding 4g of titanium dioxide (with the particle size of 400nm), 7.53g of tin dioxide (with the particle size of 600nm) and 1.4g of cane sugar into 50mL of deionized water, and placing the mixture into a ball milling tank for ball milling for 3 hours at the ball milling speed of 400rmp to obtain slurry; spray drying and granulating the slurry to obtain a precursor, wherein the inlet temperature of the spray drying is 230 ℃, and the outlet temperature of the spray drying is 110 ℃; sintering the precursor for 10 hours at 850 ℃ in nitrogen atmosphere, and naturally cooling to room temperature to obtain the carbon-coated tin-based negative electrode material NaTiSnO4C, wherein the carbon content is 2%.
Comparative example 1
The other raw materials and their amounts and experimental conditions were the same as in example 1, without addition of starch.
Comparative example 2
The amount of starch used was 14g, and the other raw materials and their amounts and experimental conditions were the same as in example 1.
Effect example 1
The XRD pattern of the carbon-coated tin-based anode material of example 1 was measured using an X-ray diffractometer (D/max-2200/PC, Rigaku co., Ltd.), as shown in fig. 1, from which it can be seen that the peak shape is sharp and the crystallization is intact.
Effect example 2
The scanning electron microscope (Sirion 200, FEI Company) was used to measure the scanning electron micrograph of the carbon-coated tin-based negative electrode material of example 1, as shown in fig. 2. As shown in figure 2, the prepared carbon-coated tin-based negative electrode material is uniform in particle size distribution, good in sphericity and 3-8 microns in particle size.
Effect example 3
The ICP test was performed on the tin-carbon-coated tin-based negative electrode materials prepared in examples 1 to 4, and the test results are shown in table 1. As can be seen from Table 1, the ICP test result and the composition of the anode material of the invention, NaTiSnO4And (4) matching. ICP type: iCAP 6000Radial, sequier feishell technologies.
TABLE 1
Effect example 4
(1) Preparation of sodium ion battery
1.8g of the carbon-coated tin-based negative electrode material prepared in example 1 was weighed, 0.1g of carbon black and 0.1g of polyvinylidene fluoride dissolved in N, N' -methylpyrrolidone were added, and the mixture was uniformly mixed and coated on an aluminum foil to prepare an electrode sheet. In a glove box under argon atmosphere, a metallic sodium sheet is used as a counter electrode, Celgard2700 is used as a diaphragm, and 1MNaClO4(ii)/PC: EMC (1: 1) is electrolyte and is assembled into the button battery.
(2) Charge and discharge test
And carrying out charge and discharge tests on the battery within the voltage range of 0.01-2.0V. Fig. 3 is a charge-discharge test curve of the carbon-coated tin-based negative electrode material of example 1 at a current density of 12mA/g or 120mA/g, from which it can be seen that the discharge capacity of the negative electrode material is higher than 153mAh/g, and in addition, when the current density reaches 120mA/g, the discharge capacity of the carbon-coated tin-based negative electrode material prepared in example 1 reaches 121mAh/g, showing a good large-current discharge capability.
(3) Cycle performance test
Fig. 4 shows the cycle performance of the battery with the carbon-coated tin-based negative electrode material prepared in example 1 at a current density of 120mA/g, and the capacity retention rate of the battery exceeds 95% after 100 cycle cycles.
Button cells of the carbon-coated tin-based negative electrode materials prepared in examples 2 to 4 were respectively fabricated by using a sodium sheet as a counter electrode according to the method described in (1), and subjected to charge-discharge tests and cycle performance tests, with the results shown in table 2. Therefore, the carbon-coated tin-based negative electrode material prepared by the invention has higher discharge capacity and good cycle stability.
TABLE 2
Claims (16)
1. The carbon-coated tin-based negative electrode material is characterized by comprising sodium titanium stannate and carbon, wherein the chemical formula of the sodium titanium stannate is NaTiSnO4The sodium titanium stannate has a one-dimensional tunnel frame structure, the carbon is coated on the surface of the sodium titanium stannate, and the carbon containsThe amount is 1-10%, and the percentage is the mass percentage of the carbon relative to the carbon-coated tin-based negative electrode material.
2. The carbon-coated tin-based negative electrode material according to claim 1, wherein the content of carbon is 1 to 5%;
and/or the carbon is uniformly coated on the surface of the sodium titanium stannate;
and/or the shape of the carbon-coated tin-based negative electrode material is spherical;
and/or the particle size of the carbon-coated tin-based negative electrode material is 3-8 μm.
3. The carbon-coated tin-based anode material according to claim 2, wherein the content of carbon is 2% or 3%.
4. A preparation method of a carbon-coated tin-based negative electrode material is characterized by comprising the following steps:
s1: mixing a sodium source, a titanium source, a tin source, a carbon source and water to obtain slurry; wherein the sodium source, the titanium source and the tin source are in a molar ratio of sodium, titanium and tin of 1: 1: 1;
s2: spray drying the slurry to obtain a precursor;
s3: sintering the precursor to obtain the carbon-coated tin-based negative electrode material;
the carbon-coated tin-based negative electrode material comprises sodium titanium stannate and carbon, wherein the chemical formula of the sodium titanium stannate is NaTiSnO4The sodium titanium stannate has a one-dimensional tunnel frame structure, the carbon is coated on the surface of the sodium titanium stannate, the content of the carbon is 1-10%, and the percentage is the mass percentage of the carbon relative to the carbon-coated tin-based negative electrode material.
5. The method according to claim 4, wherein the sodium source in S1 is one or more of sodium carbonate, sodium hydroxide and sodium nitrate;
and/or, the titanium source in S1 is titanium dioxide;
and/or, the tin source in S1 is tin dioxide;
and/or the solid content of the slurry S1 is 10-40%;
and/or, the carbon source in S1 is one or more of glucose, starch and sucrose;
and/or, the mixing is ball milling as described in S1.
6. The method according to claim 5,
the particle size of the titanium dioxide is 200-500 nm;
and/or the particle size of the tin dioxide is 200-800 nm;
and/or, the solid content of the slurry of S1 is 20%;
and/or the ball milling time is 1-5 hours; the ball milling speed is 200 and 800 rpm.
7. The method according to claim 5,
the particle size of the titanium dioxide is 300nm or 400 nm;
and/or the particle size of the tin dioxide is 400nm or 600 nm;
and/or the ball milling time is 3 hours; the speed of the ball mill is 400rpm or 500 rpm.
8. The method of claim 4, wherein the inlet temperature of the spray drying in S2 is 200-260 ℃;
and/or the outlet temperature of the spray drying is 95-120 ℃;
and/or, the precursor in S2 is spherical.
9. The method of claim 4, wherein the inlet temperature of the spray drying in S2 is 220 ℃ or 230 ℃;
and/or the outlet temperature of the spray drying is 105 ℃ or 110 ℃.
10. The method as claimed in claim 4, wherein the sintering temperature in S3 is 600-900 ℃;
and/or, the sintering time is 5-15 hours;
and/or, the sintering is carried out under an inert atmosphere;
and/or, in S3, cooling is also included after sintering.
11. The method of claim 10, wherein the sintering temperature in S3 is 800 ℃ or 850 ℃;
and/or the sintering time is 10 hours or 12 hours;
and/or the inert atmosphere is nitrogen or argon;
and/or the cooling is natural cooling.
12. The preparation method according to claim 4, wherein the carbon content is 1 to 5% by mass of the carbon relative to the carbon-coated tin-based negative electrode material; and/or the carbon is uniformly coated on the surface of the sodium titanium stannate.
13. The method according to claim 4, wherein the carbon content is 2% or 3%.
14. The carbon-coated tin-based negative electrode material prepared by the preparation method of any one of claims 4 to 13.
15. Use of a carbon-coated tin-based negative electrode material as claimed in any one of claims 1 to 3 and 14 in a sodium ion battery.
16. A sodium ion battery whose negative electrode comprises the carbon-coated tin-based negative electrode material as recited in any one of claims 1 to 3 and 14.
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