CN114853061B - Preparation method of porous flaky sodium ion battery anode material - Google Patents
Preparation method of porous flaky sodium ion battery anode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a porous flaky sodium ion battery anode material, which takes graphene oxide as a template, takes organic or inorganic titanium as a titanium source, forms a chemical bond with a functional group on the surface of the graphene oxide under the action of an alkali catalyst, and deposits on the surface of the graphene oxide to obtain a titanium dioxide/graphene oxide/titanium dioxide sandwich structure. And (3) filtering, drying and calcining to completely remove the template, and converting the amorphous titanium dioxide into mesoporous anatase phase porous titanium dioxide nano-sheets. The particle calcining device can effectively prevent pore structures from being blocked due to insufficient gasification of the graphene oxide template in the calcining process, so that the prepared mesoporous material has larger pore volume and pore diameter, the porous structure can improve the liquid retention amount, sodium ions are facilitated to be embedded and separated, the internal stress of the material is reduced, pole piece demoulding and sodium precipitation are avoided, and the particle calcining device is suitable for high-pressure dense design and high-rate charge and discharge and can improve the energy density and the rate performance of a battery cell.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a preparation method of a porous flaky negative electrode material of a sodium ion battery.
Background
The rapid development of the lithium ion battery energy storage technology expands the application range of the lithium ion battery, and the market occupation ratio is steadily increased. However, the problems of limited lithium resource reserves on earth, immature battery recovery technology and the like cause the annual rising of the cost of lithium ion batteries. The sodium resource reserves are abundant and widely distributed, and the sodium ion energy storage principle is similar to that of a lithium ion battery, so that the lithium ion battery has higher safety. With the gradual development of high-performance sodium ion electrode materials, the sodium ion battery is expected to replace a lithium ion battery in a low-end market.
The ionic radius and the relative atomic mass of sodium ions are larger than those of lithium ions, resulting in slow transport and reaction kinetics of sodium ions. When sodium ions are embedded and extracted, the volume change of the material is large, and the structural capacity of the electrode material collapses in the circulation process. Compared with lithium ion batteries, most sodium ion battery materials have lower specific capacities and poorer capacity retention during cycling.
The anatase phase titanium dioxide has stable chemical structure, no toxicity and low price, and is widely applied to the fields of energy conversion, energy storage, catalysis and the like. Anatase serving as a lithium ion or sodium ion battery cathode material has the advantages of small change of charge and discharge volume and long cycle life. However, anatase phase titanium dioxide has low conductivity and ion diffusion rate, so that the rate capability is poor, and the anatase phase titanium dioxide is not suitable for being used as a power battery electrode material and a high-voltage compact cell design scheme, so that the application range of the material is limited.
In order to improve the electrochemical performance of titanium dioxide and expand the application field of materials, it is highly desirable to design anatase titanium dioxide with a rapid reaction kinetic structure. The common method is to construct special nano-structure materials, element doping, composite carbon materials and the like. These methods all have the effect of improving the conductivity and ion diffusivity of titanium dioxide. Patent CN112044372a designs a hollow titanium dioxide@carbon composite microsphere which has a double-shell hollow structure, adjustable particle size and carbon content, and large specific surface area, pore volume and pore diameter, and has excellent rate performance and pseudocapacitance characteristics. The patent CN113937257A designs and synthesizes a nitrogen and fluorine co-doped titanium dioxide/carbon microsphere, and the doping of nitrogen and fluorine elements shortens the band gap of titanium dioxide and carbon, thereby improving NF-TiO 2 Conductive properties of/C. And the doping of nitrogen and fluorine promotes the storage and diffusion of sodium ions, and improves the sodium storage performance of titanium dioxide. Patent CN108807923A designed and synthesized phosphorus doped titanium dioxide and oxygenThe graphene composite material is formed, the conductivity of the material is improved by compounding titanium dioxide and graphene oxide, and the sodium ion transmission capacity of the titanium dioxide surface can be improved by phosphorus doping, so that the sodium storage performance of the titanium dioxide/graphene composite electrode is improved.
In order to obtain a lamellar mesoporous material, graphene or graphene oxide is often used as a template in the prior art, titanium dioxide is firstly deposited on the surface of lamellar graphene through a sol-gel method, and then the graphene/titanium dioxide composite material is subjected to calcination operation, so that on one hand, anatase-phase titanium dioxide is formed by the titanium dioxide through high-temperature treatment, and on the other hand, the graphene template is gasified into carbon dioxide through reaction of the graphene template and oxygen through calcination under an aerobic condition, so that the template is removed, and the lamellar material with a mesoporous structure is formed. Therefore, whether the graphene or graphene oxide template can be sufficiently removed in the calcination process is important for the formation of the mesoporous structure, and if the template is too much left or insufficient to react with oxygen, the mesoporous structure is occupied or blocked by carbon, so that the pore volume and the pore diameter are greatly reduced, and the performance of the mesoporous material is seriously affected.
The existing calcination process is carried out in air by using a common calciner, the common calciner is relatively airtight in order to preserve heat, the calcination chamber is relatively airtight, the air flow circulation is relatively poor, even fresh air is continuously introduced, the fresh air can be mixed with carbon dioxide generated by the reaction in the calcination chamber, the oxygen concentration in the fresh air is reduced, and the full oxidation of graphene is affected. In addition, the fresh air is difficult to enter the inside of the calcined material, especially when the stacking thickness of the material is large, the speed of entering the inside of the calcined material by gas diffusion is extremely low, so that the graphene template of the surface material is fully oxidized, the template removal degree is higher, the pore structure is better formed, the contact oxygen of the inside material is less, the oxidation is insufficient, a large amount of carbon residues are generated, the template removal is insufficient, and the pore structure is poor.
Disclosure of Invention
The invention aims to solve the technical problems that: solves the problems existing in the preparation process of the existing anatase phase titanium dioxide lamellar mesoporous material, and prepares the lamellar mesoporous material with larger pore volume and pore diameter, which is favorable for embedding and extracting sodium ions.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the porous flaky sodium ion battery anode material comprises the following specific steps:
s1: dispersing graphene oxide in an alcohol reagent, and adding a certain amount of alkali source to enable the PH of the solution to be more than 7;
s2: adding a titanium source into the S1, continuously stirring and reacting for 12-24 hours, filtering and drying to obtain a titanium dioxide and graphene oxide composite material, and crushing to obtain particles;
s3: calcining the granule in a granule calcining device for 1-4 hours, repeatedly and uniformly introducing fresh air into the granule in the calcining process, and unidirectionally extruding the fresh air from bottom to top to replace reaction waste gas in the granule, and taking out solid powder after the calcining is finished to obtain the anatase phase porous titanium dioxide sheet.
Preferably, the mass ratio of the graphene oxide to the alcohol reagent, the alkali source and the titanium source is 1: 100-300: 1 to 3:1.5 to 2.5.
Preferably, the alcohol reagent is one or more of methanol, ethanol, isopropanol and 1, 3-butanediol; the alkali source comprises one or more of urea, ammonia water, sodium hydroxide, ethylenediamine, sodium ethoxide and triethylamine; the titanium source is one or more of titanium n-propoxide, titanium isopropoxide, tetrabutyl titanate, titanium tetrachloride, titanium citrate and titanium sulfate; the calcination temperature is 400-700 ℃.
Preferably, the granule calcining device includes the frame, the top of frame is equipped with the cylinder, the telescopic link of cylinder has the pressure box down, the top intercommunication of pressure box has the breathing pipe, the bottom intercommunication of pressure box has a plurality of cavity pestle sticks, cavity pestle stick evenly disperses the arrangement under the pressure box, through-hole one has been seted up to the bottom of cavity pestle stick, and the top of cavity pestle stick all is equipped with check valve one, check valve one all locates in the pressure box, the bottom of frame is equipped with electric heater unit, be equipped with the calcination groove on the electric heater unit, calcination inslot detachably is connected with the indent, the outer wall of indent and the inner wall sealing sliding connection of calcination groove, indent bottom intercommunication has a plurality of sleeve pipes, the sleeve pipe corresponds the below of locating cavity pestle stick, when cavity pestle stick inserts intraductally, the through-hole two has been seted up to the bottom of sleeve pipe, a plurality of ventholes have all been seted up on the bottom plate of indent, be equipped with the side opening on the lateral wall of indent, calcination groove, be equipped with the lateral opening on the blast pipe is pressed down on the lateral wall, the lateral wall and the blast pipe is equipped with the fixed slot, the lateral wall is pressed down in the fixed slot and the fixed slot.
Preferably, the top of the pressing box is also provided with a plurality of guide rods, the upper parts of the guide rods are in sliding connection with the top of the frame, and the calcining groove and the pressing groove are fixed through screws.
The application of the anatase phase porous titanium dioxide sheet in preparing button cells.
Preferably, the specific preparation method of the button cell comprises the following steps:
the anatase phase porous titanium dioxide sheet, a water-based binder and a conductive agent are mixed according to the mass ratio of 9:0.5:0.5, coating on aluminum foil, drying at 100deg.C, cutting into pole pieces, drying at 120deg.C under vacuum for 10 hr, transferring into glove box, and making into button cell with metal sodium sheet as counter electrode, 1M NaPF 6 The solution is used as electrolyte to assemble the button cell.
Preferably, the water-based binder is one or more of PAA, SBR, PAN, the conductive agent is at least one of Super P, acetylene black, graphene and carbon nano tube, and the NaPF 6 The organic solvent in the solution is a mixed solvent of EC and DEC with the volume ratio of 1:1.
The beneficial effects obtained by the invention are as follows:
according to the preparation method, graphene oxide is used as a template, organic or inorganic titanium is used as a titanium source, under the action of an alkali catalyst, the titanium source and the functional groups on the surface of the graphene oxide form chemical bonds, and the chemical bonds are deposited on the surface of the graphene oxide, so that a titanium dioxide/graphene oxide/titanium dioxide sandwich structure is obtained. And (3) filtering, drying, calcining in air, and completely removing graphene oxide, wherein amorphous titanium dioxide is converted into mesoporous anatase phase porous titanium dioxide nano sheets. The alcohol reagent after filtration and separation can be reused, and the production cost is reduced.
According to the invention, the particle calcining device can effectively prevent the pore structure from being blocked due to insufficient gasification of the graphene oxide template in the calcining process, so that the pore volume and the pore diameter of the mesoporous material are improved. The mesoporous material prepared by the method has larger pore volume and aperture, the porous structure can improve the liquid retention amount, is favorable for sodium ion embedding and releasing, reduces the internal stress of the material, avoids pole piece demoulding and sodium precipitation, is suitable for high-pressure dense design and high-rate charge and discharge, and can improve the energy density and the rate performance of the battery cell.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of the samples prepared in examples 1-3.
Fig. 2 is a Scanning Electron Microscope (SEM) picture of the sample prepared in example 1.
Fig. 3 is a Scanning Electron Microscope (SEM) picture of the sample prepared in example 1.
Fig. 4 is a Transmission Electron Microscope (TEM) image of the sample prepared in example 1.
FIG. 5 is a graph of the 1C cycle performance of the samples prepared in examples 1-3.
FIG. 6 is a graph showing the rate performance of the samples prepared in examples 1-3.
Fig. 7 is a schematic view of the overall structure of the particle calcining apparatus.
Fig. 8 is a top view of the particle calcining apparatus.
Fig. 9 is a cross-sectional view taken along A-A in fig. 8.
Fig. 10 is a sectional view taken along the direction B-B in fig. 8.
The device comprises a 1-frame, an 11-electric heating device, a 2-cylinder, a 21-guide rod, a 3-pressing box, a 31-air suction pipe, a 32-fixed lug, a 4-hollow pestle rod, a 41-one-way valve I, a 42-through hole I, a 5-pressing groove, a 51-side hole, a 52-air outlet hole, a 53-sleeve pipe, a 531-through hole II, a 6-calcining groove, a 61-exhaust pipe, a 62-one-way valve II and a 63-screw.
Detailed Description
The following description of the embodiments of the present invention is provided to facilitate a more complete, accurate and thorough understanding of the present invention's inventive concepts and technical solutions by those skilled in the art.
Example 1: preparing anatase phase titanium dioxide nano-sheets with large pore volume and pore diameter according to the following method:
s1: dispersing 1 part by weight of graphene oxide in 100 parts by weight of ethanol, and adding 1 part by weight of ammonia water to ensure that the PH of the solution is more than 7;
s2: adding 2.5 parts by weight of titanium isopropoxide into S1, stirring and reacting for 18 hours at 60 ℃, filtering and drying to obtain a titanium dioxide and graphene oxide composite material, crushing to obtain a particle material with the particle size of 1-5 mm, and crushing the titanium dioxide and graphene oxide composite material to obtain a particle material with the particle size of 1-5 mm;
s3: and calcining the granules of the titanium dioxide and graphene oxide composite material for 2 hours at 400 ℃ through a granule calcining device to obtain mesoporous anatase phase titanium dioxide.
The structure of the particle calcining apparatus used in this example as shown in fig. 7 to 10 is as follows:
the granule calcination device includes frame 1, the top of frame 1 is equipped with cylinder 2, be equipped with down the telescopic link of cylinder 2 and press box 3, press box 3's top intercommunication has breathing pipe 31, press box 3's bottom intercommunication has a plurality of cavity pestle bars 4, cavity pestle bars 4 evenly disperse the arrangement under pressing box 3, through-hole one 42 has been seted up to cavity pestle bars 4's bottom, and cavity pestle bars 4's top all is equipped with check valve one 41, check valve one 41 all locates in pressing box 3, frame 1's bottom is equipped with electric heater unit 11, be equipped with on the electric heater unit 11 and calcine groove 6, be connected with indent 5 in the indent 6, indent 5's outer wall and calcine groove 6's inner wall sealing sliding connection, indent 5 bottom intercommunication has a plurality of sleeve pipes 53, sleeve pipe 53 correspond the below of locating cavity pestle bars 4, when cavity pestle bars 4 insert sleeve pipe 53 in, cavity pestle bars 4 and sleeve pipe 53 inner wall sealing connection, two lateral hole 53 have been equipped with on the lateral hole one-way 53, indent 5 has been seted up on the lateral wall 5, indent 3 has been seted up on the lateral wall 5 and has been pressed down in the lateral wall 5, the lateral wall 3 has been pressed down on the lateral wall 5, the lateral wall has been pressed down the lateral wall 3 to be equipped with on the lateral wall 3, the lateral wall is pressed down on the lateral wall is fixed groove 3, and is pressed down on the lateral wall is fixed to be equipped with 3. The top of the pressing box 3 is also provided with a plurality of guide rods 21, the upper parts of the guide rods 21 are in sliding connection with the top of the frame 1, and the calcining groove 6 and the pressing groove 5 are fixed through screws 63. To prevent the first through hole 42 and the second through hole 531 from being blocked, a filter screen may be added.
The calcination working process of the particle calcination device is as follows: before calcination, the pressing box 3 and the pressing groove 5 are detachably nested together through bolts and fixing lugs 32, the cylinder 2 is opened to lift the pressing box 3 and the pressing groove 5 until the pressing groove 5 leaves the calcination groove 6, the titanium dioxide and graphene oxide composite material granules are put into the calcination groove 6, after the granules are vibrated and leveled, the pressing box 3 and the pressing groove 5 are lowered until the side holes 51 of the pressing groove 5 are aligned and communicated with the exhaust pipe 61, then the pressing groove 5 is fixed in the calcination groove 6 through bolts 63, the pressing groove 5 is in sealing connection with the calcination groove 6, at the moment, the sleeve 53 under the pressing groove 5 is completely inserted into the granules, at the moment, the fixing lugs 32 on the pressing groove 5 and the pressing box 3 are detached, the cylinder 2 is continuously used for controlling the pressing box 3 to repeatedly move up and down in the whole calcination process, at the same time, when the motor heating device is started to heat and calcine, as the second check valve 62 is not fed in, negative pressure is formed in the pressing groove 5 and the sleeve 53, fresh air enters the pressing groove 3 through the air suction pipe 31, then enters the hollow pestle 4 from the pressing groove 3 through the first check valve 41, enters the sleeve 53 from the first through hole 42, then enters the calcining groove 6 from the second through hole 531, fresh air extrudes and discharges gas in the calcining groove 6 upwards from the bottom, more carbon dioxide-containing gas enters the pressing groove 5 through the air outlet 52, the hollow pestle 4 is not separated from the sleeve 53 in the lifting process of the pressing groove 3, the pressing groove 5 is not separated from the pressing groove 3, fresh air is filled in the sleeve 53 and the calcining groove 6, the upper lifting of the pressing groove 3 is stopped, and the pressing of the pressing groove 3 is started. When the pressing box 3 is pressed down, the hollow pestle rod 4 is inserted into the corresponding sleeve 53 along with the downward movement, as the one-way valve I41 can only be communicated downwards, air cannot move upwards, the hollow pestle rod 4 presses fresh air in the sleeve 53 into the calcining groove 6 again through the through hole II 531, the aged air after reaction in the calcining groove 6 is further emptied upwards, the pressing box 3 is pressed down, and simultaneously the air with more carbon dioxide in the pressing groove 5 is discharged from the side hole 51 and the exhaust pipe 61 until the hollow pestle rod 4 is completely inserted into the sleeve 53, the pressing box 3 is repeatedly lifted, the operation is repeated to form airflow flowing unidirectionally in the calcining groove 6, oxygen is uniformly supplemented, the oxygen is fully contacted with the granules, the graphene oxide is fully oxidized to form carbon dioxide, and the carbon dioxide is discharged along with the unidirectional airflow, and the calcination removal of the graphene oxide template is facilitated.
In order to prevent the fresh air from entering and then reducing the temperature in the calcination tank 6, the air may be preheated and then introduced into the air intake pipe 31.
Above-mentioned granule calcination device inserts inside the material through a plurality of sleeves, can directly introduce the material deep and inside with fresh air, through the unidirectional introduction of bottom air, can effectively replace and get rid of the inside waste gas of persisting at the material after the reaction, promotes the contact of inside material and oxygen, effectively promotes the removal rate of oxidation graphite alkene template, reduces the residual of carbon material. In addition, the pressure box lifts the air suction, and the downward pressure exhaust mode can effectively reduce the residual of waste gas in the material and the calcination tank, prevent the oxygen concentration reduction caused by the mass mixing of the waste gas and fresh air, ensure that the oxygen concentration in the calcination tank is maintained at a higher level, and promote the oxidation removal of the carbon template material.
Example 2: the remainder was the same as in example 1 except that:
s1: dispersing 1 part by weight of graphene oxide in 300 parts by weight of ethanol, and adding 1 part by weight of ammonia water to ensure that the PH of the solution is more than 7;
s2: adding 2.5 parts by weight of titanium isopropoxide into S1, stirring and reacting for 24 hours at 60 ℃, filtering and drying to obtain a titanium dioxide and graphene oxide composite material, and crushing to obtain particles with the particle size of 1-5 mm;
s3: and calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 500 ℃ for 2 hours to obtain mesoporous anatase phase titanium dioxide.
Example 3: the remainder was the same as in example 1 except that:
s1: dispersing 1 part by weight of graphene oxide in 300 parts by weight of ethanol, and adding 1 part by weight of sodium hydroxide to ensure that the PH of the solution is more than 7;
s2: adding 2.5 parts by weight of titanium n-propoxide into S1, stirring and reacting for 24 hours at 60 ℃, filtering and drying to obtain a titanium dioxide and graphene oxide composite material, and crushing to obtain particles with the particle size of 1-5 mm;
s3: and calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 600 ℃ for 2 hours to obtain mesoporous anatase phase titanium dioxide.
Example 4: the remainder was the same as in example 1 except that:
s1: dispersing 1 part by weight of graphene oxide in 200 parts by weight of ethanol, and adding 3 parts by weight of urea to ensure that the PH of the solution is more than 7;
s2: adding 2 parts by weight of tetrabutyl titanate into S1, stirring and reacting for 24 hours at 60 ℃, filtering and drying to obtain a titanium dioxide and graphene oxide composite material, and crushing to obtain particles with the particle size of 1-5 mm;
s3: and calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 500 ℃ for 3 hours to obtain mesoporous anatase phase titanium dioxide.
Example 5: the remainder was the same as in example 1 except that:
s1: dispersing 1 part by weight of graphene oxide in 100 parts by weight of methanol, and adding 1 part by weight of sodium hydroxide to ensure that the PH of the solution is more than 7;
s2: adding 2 parts by weight of tetrabutyl titanate into S1, stirring and reacting for 24 hours at 60 ℃, filtering and drying to obtain a titanium dioxide and graphene oxide composite material, and crushing to obtain a 0.5-3 mm particle material;
s3: and calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 500 ℃ for 2 hours to obtain mesoporous anatase phase titanium dioxide.
Example 6: the remainder was the same as in example 1 except that:
s1: dispersing 1 part by weight of graphene oxide in 300 parts by weight of isopropanol, and adding 2 parts by weight of sodium ethoxide to ensure that the PH of the solution is more than 7;
s2: adding 1.5 parts by weight of titanium tetrachloride into S1, stirring and reacting for 24 hours at 60 ℃, filtering and drying to obtain a titanium dioxide and graphene oxide composite material, and crushing to obtain 2-4 mm granules;
s3: and calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 400 ℃ for 1 hour to obtain mesoporous anatase phase titanium dioxide.
Example 7: the remainder was the same as in example 1 except that:
s1: dispersing 1 part by weight of graphene oxide in 150 parts by weight of 1, 3-butanediol, and adding 1 part by weight of ethylenediamine to ensure that the PH of the solution is more than 7;
s2: adding 1.5 parts by weight of tetrabutyl titanate into S1, stirring and reacting for 18 hours at 60 ℃, filtering and drying to obtain a titanium dioxide and graphene oxide composite material, and crushing to obtain a 3-10 mm particle material;
s3: and calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 400 ℃ for 2 hours to obtain mesoporous anatase phase titanium dioxide.
Example 8: the remainder was the same as in example 1 except that:
s1: dispersing 1 part by weight of graphene oxide in 200 parts by weight of ethanol, and adding 2 parts by weight of ethylenediamine to ensure that the PH of the solution is more than 7;
s2: adding 2 parts by weight of titanium citrate into the S1, stirring and reacting for 18 hours at 60 ℃, filtering and drying to obtain a titanium dioxide and graphene oxide composite material, and crushing to obtain particles with the particle size of 1-5 mm;
s3: and calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 400 ℃ for 2 hours to obtain mesoporous anatase phase titanium dioxide.
Example 9: the remainder was the same as in example 1 except that:
s1: dispersing 1 part by weight of graphene oxide in 100 parts by weight of methanol, and adding 1 part by weight of triethylamine to ensure that the PH of the solution is more than 7;
s2: adding 1.5 parts by weight of titanium sulfate into the S1, stirring and reacting for 18 hours at 60 ℃, filtering and drying to obtain a titanium dioxide and graphene oxide composite material, and crushing to obtain particles with the particle size of 1-5 mm;
s3: and calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 700 ℃ for 2 hours to obtain mesoporous anatase phase titanium dioxide.
Comparative example 1: preparation of TiO by the method disclosed in example 1 of Chinese patent CN103991903A 2 Nanosheet photocatalytic material.
Comparative example 2: the rest is the same as in example 1, except that the calcination is not carried out by a particle calcination device, the conventional calcination is directly carried out in air, the calcination is carried out by a commercially available constant plastic HS-1700Q-A1 type calciner, and fresh air is continuously introduced into a calcination chamber during the calcination.
Anatase phase titanium dioxide obtained in the examples 1-3, an aqueous binder and a conductive agent according to the mass ratio of 9:0.5:0.5, mixing to form uniform slurry, coating the uniform slurry on aluminum foil, drying at 100 ℃, cutting into pole pieces, drying at 120 ℃ for 10 hours under vacuum, and transferring into a glove box for preparation. Assembled into button cell with sodium metal sheet as counter electrode, 1M NaPF 6 And the solution (wherein the organic solvent is a mixed solvent of EC and DEC with the volume ratio of 1:1) is taken as electrolyte, and the button cell is assembled to test the electrochemical performance.
The pore structure parameters of the mesoporous anatase titania prepared in examples 1 to 9 were measured and the results were as follows:
TABLE 1 pore structure parameters of mesoporous anatase phase titanium dioxide samples
| Sample of | Pore volume/cm 3 ·g -1 | Average pore size/nm | Specific surface area/m 2 ·g -1 |
| Example 1 | 0.58 | 14.2 | 229 |
| Example 2 | 0.79 | 34.4 | 338 |
| Example 3 | 0.72 | 27.8 | 314 |
| Example 4 | 0.63 | 17.1 | 261 |
| Example 5 | 0.61 | 15.2 | 246 |
| Example 6 | 0.88 | 44.6 | 369 |
| Example 7 | 0.83 | 37.3 | 355 |
| Example 8 | 0.66 | 19.5 | 278 |
| Example 9 | 0.75 | 28.7 | 323 |
| Comparative example 1 | 0.47 | 7.3 | 202 |
| Comparative example 2 | 0.49 | 5.9 | 197 |
The carbon content of different porous materials is measured, so that the carbon residue condition after calcination is known:
TABLE 2 carbon content of different porous materials
The results in tables 1 and 2 show that the comparative examples 1 and 2 have higher carbon content in the titania mesoporous material due to the calcination operation using the conventional equipment, and more carbon material remains to block the pores, resulting in significantly lower pore structure parameters than examples 1 to 9. In the embodiments 1 to 9, the particle calcining device is adopted, so that the graphene oxide template can be effectively removed, the overall pore structure parameter of the material is larger, the intercalation and deintercalation of sodium ions are facilitated, and the material has excellent electrical properties when being used for preparing the anode material.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by the above embodiments, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the present invention; the technology not related to the invention can be realized by the prior art.
Claims (5)
1. The preparation method of the porous flaky sodium ion battery anode material is characterized by comprising the following specific steps:
s1: dispersing graphene oxide in an alcohol reagent, and adding a certain amount of alkali source to enable the PH of the solution to be more than 7;
s2: adding a titanium source into the S1, continuously stirring and reacting for 12-24 hours, filtering and drying to obtain a titanium dioxide and graphene oxide composite material, and crushing to obtain particles;
s3: calcining the granule in a granule calcining device for 1-4 hours, repeatedly and uniformly introducing fresh air into the granule in the calcining process, and unidirectionally extruding the fresh air from bottom to top to replace reaction waste gas in the granule, and taking out solid powder after the calcining is finished to obtain an anatase phase porous titanium dioxide sheet;
the mass ratio of graphene oxide to alcohol reagent, alkali source and titanium source is 1: 100-300: 1 to 3:1.5 to 2.5;
the alcohol reagent is one or more of methanol, ethanol, isopropanol and 1, 3-butanediol; the alkali source comprises one or more of urea, ammonia water, sodium hydroxide, ethylenediamine, sodium ethoxide and triethylamine; the titanium source is one or more of titanium n-propoxide, titanium isopropoxide, tetrabutyl titanate, titanium tetrachloride, titanium citrate and titanium sulfate; the calcination temperature is 400-700 ℃;
the granule calcining device comprises a frame (1), cylinder (2) are arranged at the top of frame (1), press box (3) are arranged under the telescopic link of cylinder (2), press box (3)'s top intercommunication has breathing pipe (31), press box (3)'s bottom intercommunication has a plurality of cavity pestle bars (4), cavity pestle bars (4) evenly disperse and arrange under pressing box (3), through-hole one (42) have been seted up to cavity pestle bars (4)'s bottom, and cavity pestle bars (4)'s top all is equipped with check valve one (41), check valve one (41) all are located in pressing box (3), frame (1)'s bottom is equipped with electric heater unit (11), be equipped with on electric heater unit (11) and calcine groove (6), detachably is connected with pressure groove (5) in calcining groove (6), the outer wall of pressure groove (5) and the inner wall sealing sliding connection of calcining groove (6), pressure groove (5) bottom intercommunication has sleeve pipe (53), hollow pestle bars (53) correspond to each other and are located in two sleeve pipe (53) when hollow pestle bars (53) are connected with each other, hollow pestle bars (53) are sealed down, a plurality of ventholes (52) have been seted up on the bottom plate of indent (5), be equipped with side opening (51) on the lateral wall of indent (5), be equipped with blast pipe (61) on the lateral wall of calcining groove (6), be equipped with check valve two (62) on blast pipe (61), when calcining groove (6) and indent (5) are fixed, side opening (51) and blast pipe (61) align the intercommunication, all be equipped with fixed ear (32) on the outer wall of indent (5) and indent (3), indent (5) are fixed in on indent (3) through fixed ear (32), the lateral wall of indent (3) and the inside wall sealing sliding connection of indent (5).
2. The method for preparing the porous sheet-shaped sodium ion battery anode material according to claim 1, which is characterized in that: the top of pressure box (3) still is equipped with a plurality of guide bars (21), the upper portion of guide bar (21) and the top sliding connection of frame (1), calcination groove (6) are fixed through screw (63) with indent (5).
3. Use of an anatase phase porous titania sheet according to any one of claims 1 to 2 in the manufacture of a button cell.
4. The use of anatase phase porous titania flakes according to claim 3 in the preparation of button cells, wherein the specific preparation method is: the anatase phase porous titanium dioxide sheet, a water-based binder and a conductive agent are mixed according to the mass ratio of 9:0.5:0.5, coating on aluminum foil, drying at 100deg.C, cutting into pole pieces, drying at 120deg.C under vacuum for 10 hr, transferring into glove box, and making into button cell with metal sodium sheet as counter electrode, 1M NaPF 6 The solution is used as electrolyte to assemble the button cell.
5. The use of anatase phase porous titania flakes according to claim 4 in making button cell, wherein the aqueous binder is one or more of PAA, SBR, PAN, the conductive agent is at least one of SuperP, acetylene black, graphene, and carbon nanotubes, and the NaPF is 6 The organic solvent in the solution is a mixed solvent of EC and DEC with the volume ratio of 1:1.
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