CN114853061A - Preparation method of porous sheet-shaped sodium-ion battery negative electrode material - Google Patents
Preparation method of porous sheet-shaped sodium-ion battery negative electrode material Download PDFInfo
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Abstract
The invention discloses a preparation method of a porous sheet-shaped sodium ion battery cathode material. Filtering, drying and calcining, then completely removing the template, and converting the amorphous titanium dioxide into mesoporous anatase phase porous titanium dioxide nanosheets. The particle calcining device can effectively prevent the mesoporous material prepared from the pore volume and the pore diameter because the graphene oxide template is not gasified sufficiently and blocks up the pore structure in the calcining process, the porous structure can improve the liquid retention amount, sodium ions can be embedded and separated, the internal stress of the material is reduced, the pole piece demoulding and sodium precipitation are avoided, the particle calcining device is suitable for high-pressure dense design and high-rate charging and discharging, and the energy density and the rate performance of a battery cell can be improved.
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 sodium ion battery cathode material.
Background
The rapid development of the energy storage technology of the lithium ion battery expands the application range of the lithium ion battery, and the market occupation ratio steadily increases. However, the cost of lithium ion batteries has increased year by year due to problems such as limited lithium resource reserves on the earth and immature battery recycling techniques. 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 safety is higher. With the gradual development of high-performance sodium ion electrode materials, sodium ion batteries are expected to replace lithium ion batteries in low-end markets.
The ionic radius and relative atomic mass of sodium ions are both larger than those of lithium ions, resulting in slow transport and reaction kinetics of sodium ions. When sodium ions are inserted and removed, the volume change of the material is large, and the structural capacity of the electrode material collapses in the circulating process. Compared with lithium ion batteries, most sodium ion battery materials have lower specific capacity and poorer capacity retention capacity in the circulating process.
Anatase phase titanium dioxide has a stable chemical structure, is non-toxic and low in price, and is widely applied to the fields of energy conversion, energy storage, catalysis and the like. The anatase serving as the cathode material of the lithium ion or sodium ion battery has the advantages of small charge-discharge volume change and long cycle life. However, the anatase phase titanium dioxide has low conductivity and ion diffusion rate, so that the rate performance is poor, the anatase phase titanium dioxide is not suitable for being used as a power battery electrode material and a high-voltage dense electric core design scheme, and the application range of the material is limited.
In order to improve the electrochemical performance of titanium dioxide and expand the application scenes of materials, the anatase phase titanium dioxide with a rapid reaction kinetic structure needs to be designed urgently. The general method is to adopt constructionSpecial 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 has designed a hollow titanium dioxide @ carbon composite microsphere, and this microsphere has double shell layer hollow structure, adjustable particle size and carbon content to and great specific surface area, pore volume and aperture, have excellent multiplying power performance and pseudo-capacitance characteristic. The patent CN113937257A designs and synthesizes a nitrogen and fluorine co-doped titanium dioxide/carbon micron sphere, and the doping of nitrogen and fluorine elements shortens the band gaps of titanium dioxide and carbon, thereby improving the NF-TiO 2 The conductive performance of/C. And the doping of nitrogen and fluorine elements promotes the storage and diffusion of sodium ions, and improves the sodium storage performance of titanium dioxide. Patent CN108807923A has designed and synthesized phosphorus-doped titanium dioxide and graphene oxide combined material, and titanium dioxide and graphene oxide are compound to improve material electric conductivity, and phosphorus-doping then can improve the surperficial sodium ion transmission ability of titanium dioxide, has promoted the storage sodium performance of titanium dioxide/graphene combined electrode.
In order to obtain a sheet-like mesoporous material, in the prior art, graphene or graphene oxide is often used as a template, titanium dioxide is deposited on the surface of the sheet-like graphene by a sol-gel method, and then a graphene/titanium dioxide composite material is calcined, so that on one hand, the titanium dioxide forms anatase-phase titanium dioxide by high-temperature treatment, and on the other hand, the graphene template reacts with oxygen to gasify the titanium dioxide into carbon dioxide by calcination under an aerobic condition, so that the template is removed, and the sheet-like material with a mesoporous structure is formed. Therefore, whether the graphene or graphene oxide template can be sufficiently removed in the calcining process is crucial to the formation of the mesoporous structure, and if the template is excessively remained or does not sufficiently 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 calcining process is carried out in the air by using a common calcining furnace, the common calcining furnace is used for preserving heat, a calcining chamber is relatively closed, airflow circulation is poor, and even if fresh air is continuously introduced, the fresh air can be mixed with carbon dioxide generated by reaction in the calcining chamber, so that the oxygen concentration in the fresh air is reduced, and the full oxidation of graphene is influenced. In addition, the introduced fresh air is difficult to enter the inside of the calcined material, especially when the material is stacked to a large thickness, 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 internal material is less in oxygen contact, insufficient in oxidation, a large amount of carbon residues are generated, the template removal is insufficient, and the pore structure is poor in formation.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the method solves the problems existing in the preparation process of the prior anatase phase titanium dioxide sheet mesoporous material, and prepares the sheet mesoporous material which has larger pore volume and pore diameter and is beneficial to the embedding and the separation of sodium ions.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a porous sheet-shaped sodium ion battery negative electrode 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 greater than 7;
s2: adding a titanium source into 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 a granular material;
s3: calcining the granular material in a granular calcining device for 1-4 hours, repeatedly and uniformly introducing fresh air into the granular material in the calcining process, unidirectionally extruding and replacing reaction waste gas in the granular material by the fresh air from bottom to top, 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: 1-3: 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 particle calcining device comprises a rack, a cylinder is arranged at the top of the rack, a pressure box is arranged below a telescopic rod of the cylinder, the top of the pressure box is communicated with an air suction pipe, a plurality of hollow pestle rods are communicated with the bottom of the pressure box, the hollow pestle rods are uniformly distributed and arranged below the pressure box, a first through hole is formed in the bottom of each hollow pestle rod, a first check valve is arranged at the top of each hollow pestle rod and is arranged in the pressure box, an electric heating device is arranged at the bottom of the rack, a calcining groove is formed in the electric heating device, a pressure groove is detachably connected in the calcining groove, the outer wall of the pressure groove is in sealing sliding connection with the inner wall of the calcining groove, a plurality of sleeves are communicated with the bottom of the pressure groove, the sleeves are correspondingly arranged below the hollow pestle rods, and when the hollow pestle rods are inserted into the sleeves, the hollow pestle rods are in sealing sliding connection with the inner wall of the sleeves, through-hole two has been seted up to sheathed tube bottom, a plurality of ventholes have been seted up on the bottom plate of indent, be equipped with the side opening on the lateral wall of indent, be equipped with the blast pipe on calcining the lateral wall of groove, be equipped with check valve two on the blast pipe, when calcining the groove fixed with the indent, the side opening aligns the intercommunication with the blast pipe, all be equipped with fixed ear on the indent and the outer wall of pressing the box, the indent is fixed in through fixed ear and presses on the box, the lateral wall of pressing the box and the sealed sliding connection of inside wall of indent.
Preferably, the top of the pressing box is further provided with a plurality of guide rods, the upper parts of the guide rods are slidably connected with the top of the rack, and the calcining groove and the pressing groove are fixed through screws.
The anatase phase porous titanium dioxide sheet is applied to the preparation of button cells.
Preferably, the button cell is prepared by the following specific method:
according to the mass ratio of 9: 0.5: 0.5 mixing to form uniform slurry, coating on aluminum foil, drying at 100 deg.C, cutting into pole pieces, drying at 120 deg.C for 10 hr under vacuum condition, and transferringThe glove box is prepared and assembled into a button cell, a metal sodium sheet is used as a counter electrode, and 1M NaPF 6 The solution is used as electrolyte to assemble button cell.
Preferably, the aqueous binder is one or more of PAA, SBR and PAN, the conductive agent is at least one of Super P, acetylene black, graphene and carbon nano tube, 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.
The invention has the following beneficial effects:
according to the preparation method, graphene oxide is used as a template, organic or inorganic titanium is used as a titanium source, the titanium source and a functional group on the surface of the graphene oxide form a chemical bond under the action of an alkali catalyst, and the chemical bond is deposited on the surface of the graphene oxide to obtain a titanium dioxide/graphene oxide/titanium dioxide sandwich framework. And (3) filtering, drying, calcining in air, completely removing graphene oxide, and converting amorphous titanium dioxide into mesoporous anatase phase porous titanium dioxide nanosheets. The alcohol reagent after filtration and separation can be reused, and the production cost is reduced.
According to the invention, the pore structure can be effectively prevented from being blocked due to insufficient gasification of the graphene oxide template in the calcining process through the particle calcining device, and the pore volume and the pore diameter of the mesoporous material are improved. The prepared mesoporous material has larger pore volume and pore diameter, the porous structure can improve the liquid retention amount, sodium ions can be embedded and separated, the internal stress of the material is reduced, the stripping and sodium precipitation of a pole piece are avoided, the mesoporous material is suitable for high-pressure dense design and high-rate charge and discharge, and the energy density and rate performance of a battery cell can be improved.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of samples prepared in examples 1-3.
FIG. 2 is a Scanning Electron Microscope (SEM) picture of a sample prepared in example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) picture of a sample prepared in example 1.
FIG. 4 is a Transmission Electron Microscope (TEM) picture of a 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 of rate capability of samples from 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 a particle calcining apparatus.
Fig. 9 is a sectional view taken along line a-a in fig. 8.
Fig. 10 is a sectional view taken along line B-B in fig. 8.
The device comprises a frame 1, an electric heating device 11, an air cylinder 2, a guide rod 21, a pressing box 3, an air suction pipe 31, a fixing lug 32, a hollow pestle 4, a check valve I41, a through hole I42, a pressing groove 5, a side hole 51, an air outlet hole 52, a sleeve 53, a through hole II 531, a calcining groove 6, an exhaust pipe 61, a check valve II 62 and screws 63.
Detailed Description
The following examples are included to provide further detailed description of the present invention and to provide those skilled in the art with a more complete, concise, and exact understanding of the principles and spirit of the invention.
Example 1: preparing anatase phase titanium dioxide nanosheets with large pore volume and large 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 greater 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 into a particle material with the particle size of 1-5 mm;
s3: and calcining the particle material of the titanium dioxide and graphene oxide composite material for 2 hours at 400 ℃ by using a particle calcining device to obtain the mesoporous anatase phase titanium dioxide.
The particle calcining apparatus used in this embodiment as shown in fig. 7 to 10 has the following structure:
the particle calcining device comprises a rack 1, wherein a cylinder 2 is arranged at the top of the rack 1, a pressure box 3 is arranged below a telescopic rod of the cylinder 2, the top of the pressure box 3 is communicated with an air suction pipe 31, the bottom of the pressure box 3 is communicated with a plurality of hollow pestle rods 4, the hollow pestle rods 4 are uniformly distributed and arranged below the pressure box 3, through holes 42 are formed in the bottom of the hollow pestle rods 4, check valves 41 are arranged at the top of the hollow pestle rods 4, the check valves 41 are arranged in the pressure box 3, an electric heating device 11 is arranged at the bottom of the rack 1, a calcining groove 6 is arranged on the electric heating device 11, a pressing groove 5 is detachably connected in the calcining groove 6, the outer wall of the pressing groove 5 is connected with the inner wall of the calcining groove 6 in a sealing and sliding manner, a plurality of sleeves 53 are communicated with the bottom of the pressing groove 5, the sleeves 53 are correspondingly arranged below the hollow pestle rods 4, and when the hollow pestle rods 4 are inserted into the sleeves 53, the sealed sliding connection of cavity pestle 4 and sleeve pipe 53 inner wall, two 531 through-holes have been seted up to the bottom of sleeve pipe 53, 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 two 62 check valves on the blast pipe 61, when calcining groove 6 and indent 5 are fixed, side opening 51 aligns the intercommunication with blast pipe 61, all be equipped with fixed ear 32 on indent 5 and the outer wall of pressing box 3, indent 5 is fixed in on pressing box 3 through fixed ear 32, press the sealed sliding connection of lateral wall of box 3 and the inside wall of indent 5. 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 slidably connected with the top of the frame 1, and the calcining groove 6 and the pressing groove 5 are fixed through screws 63. In order to prevent the first through hole 42 and the second through hole 531 from being blocked, a filter screen can be additionally arranged.
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 pressing box 3 and the pressing groove 5 are lifted on the air cylinder 2 until the pressing groove 5 leaves the calcination groove 6, the titanium dioxide and the particle material of the graphene oxide composite material are thrown into the calcination groove 6, the pressing box 3 and the pressing groove 5 are lowered after the particle material is vibrated to be flat, until the side hole 51 of the pressing groove 5 is aligned and communicated with the exhaust pipe 61, then the pressing groove 5 is fixed in the calcination groove 6 through a screw 63, the pressing groove 5 is hermetically connected with the calcination groove 6, the sleeve 53 below the pressing groove 5 is completely inserted into the particle material, at the moment, the fixing lugs 32 on the pressing groove 5 and the pressing box 3 are disassembled, the pressing box 3 is controlled to repeatedly move up and down by the air cylinder 2 in the whole calcination process, meanwhile, the motor thermal device is opened to start temperature rise calcination, when the pressing box 3 is lifted, the two check valves 62 only can not enter, negative pressure is formed in the pressure groove 5 and the sleeve 53, fresh air enters the pressure box 3 through the air suction pipe 31, then enters the hollow pestle rod 4 through the pressure box 3 in a descending mode through the one-way valve I41, then enters the sleeve 53 through the through hole I42, and then enters the calcining groove 6 through the through hole II 531, the fresh air extrudes and exhausts gas in the calcining groove 6 upwards from the bottom, the gas containing more carbon dioxide upwards enters the pressure groove 5 through the air outlet 52, in the lifting process of the pressure box 3, the hollow pestle rod 4 does not depart from the sleeve 53, the pressure box 3 does not depart from the pressure groove 5, at the moment, the sleeve 53 and the calcining groove 6 are filled with fresh air, the pressure box 3 stops being lifted, and the pressure box 3 starts to be pressed downwards. When the pressing box 3 is pressed downwards, the hollow pestle 4 is inserted into the corresponding sleeve 53 along with the downward movement, the air cannot go upwards because the one-way valve I41 can only be communicated downwards, the fresh air in the sleeve 53 is pressed into the calcining groove 6 through the through hole II 531 again by the hollow pestle 4, the old air after reaction in the calcining groove 6 is further emptied upwards, the gas containing more carbon dioxide in the pressing groove 5 is discharged from the side hole 51 and the exhaust pipe 61 while the pressing box 3 is pressed downwards until the hollow pestle 4 is completely inserted into the sleeve 53, then the pressing box 3 is lifted upwards repeatedly, the operation is repeated, unidirectional flowing air flow can be formed in the calcining groove 6, oxygen is supplemented uniformly, the oxygen is in full contact with the particle materials, the graphene oxide is fully oxidized to form carbon dioxide, the carbon dioxide is discharged along with the unidirectional air flow, and the calcination and removal of the graphene oxide template are facilitated.
In order to prevent the temperature in the calcining bath 6 from being lowered after the fresh air is introduced, the air may be preheated and introduced into the air suction pipe 31.
Above-mentioned granule calcining device can directly introduce material deep and inside fresh air through inside a plurality of bushing insert materials, through the one-way introduction of bottom air, can effectively replace and get rid of the reaction after and persist the waste gas in the material is inside, promotes the contact of inside material and oxygen, effectively promotes the clearance of oxidation graphite alkene template, reduces the residue of carbon material. In addition, the mode of lifting the pressure box to suck air and pressing the pressure box to exhaust air can effectively reduce the residual of the waste gas in the material and the calcining groove, prevent the oxygen concentration reduction caused by the massive mixing of the waste gas and the fresh air, maintain the oxygen concentration in the calcining groove at a higher level and promote the oxidation removal of the carbon template material.
Example 2: the rest is the same as 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 greater 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 a particle material with the particle size of 1-5 mm;
s3: calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 500 ℃ for 2 hours to obtain the mesoporous anatase phase titanium dioxide.
Example 3: the rest is the same as 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 greater 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 a particle material with the particle size of 1-5 mm;
s3: calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 600 ℃ for 2 hours to obtain the mesoporous anatase phase titanium dioxide.
Example 4: the rest is the same as 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 greater 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 granular material with the particle size of 1-5 mm;
s3: calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 500 ℃ for 3 hours to obtain the mesoporous anatase phase titanium dioxide.
Example 5: the rest is the same as 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 greater 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 particle material with the particle size of 0.5-3 mm;
s3: calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 500 ℃ for 2 hours to obtain the mesoporous anatase phase titanium dioxide.
Example 6: the rest is the same as 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 greater 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 a particle material with the particle size of 2-4 mm;
s3: calcining the titanium dioxide and graphene oxide composite material in a particle calcining device for 1 hour at 400 ℃ to obtain the mesoporous anatase phase titanium dioxide.
Example 7: the rest is the same as 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 greater 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 particle material with the particle size of 3-10 mm;
s3: calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 400 ℃ for 2 hours to obtain the mesoporous anatase phase titanium dioxide.
Example 8: the rest is the same as 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 greater than 7;
s2: adding 2 parts by weight of titanium citrate 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 granular material with the particle size of 1-5 mm;
s3: calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 400 ℃ for 2 hours to obtain the mesoporous anatase phase titanium dioxide.
Example 9: the rest is the same as 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 greater than 7;
s2: adding 1.5 parts by weight of titanium sulfate 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 granular material with the particle size of 1-5 mm;
s3: calcining the titanium dioxide and graphene oxide composite material in a particle calcining device at 700 ℃ for 2 hours to obtain the mesoporous anatase phase titanium dioxide.
Comparative example 1: TiO is prepared by adopting the method disclosed in the embodiment 1 in the Chinese patent CN103991903A 2 A nanoplatelet photocatalytic material.
Comparative example 2: the rest of the process is the same as that of example 1, except that the calcination is carried out in the absence of a particle calcination device, the conventional calcination is carried out directly in the air, the calcination is carried out by using a commercial 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 examples 1 to 3, an aqueous binder and a conductive agent were mixed in a mass ratio of 9: 0.5: 0.5, mixing to form uniform slurry, coating the uniform slurry on an aluminum foil, drying at 100 ℃, cutting into pole pieces, drying at 120 ℃ for 10 hours under a vacuum condition, and transferring the pole pieces into a glove box for preparation. Assembled into a button cell, with a metal sodium sheet as the counter electrode, 1M NaPF 6 Solution (wherein the organic solvent is in volume)EC and DEC mixed solvent in a 1:1 ratio) as an electrolyte, assembled into a button cell to test electrochemical performance.
The pore structure parameters of the mesoporous anatase phase titanium dioxide 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 (I) | Pore volume/cm 3 ·g -1 | Average pore diameter/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 after calcination is known:
TABLE 2 carbon content of different porous materials
The results in tables 1 and 2 show that, in comparative examples 1 and 2, the carbon content in the titanium dioxide mesoporous material is higher due to the calcination operation performed by the conventional equipment, and the pores are blocked by more carbon material residues, so that the pore structure parameters are obviously lower than those in examples 1 to 9. And embodiment 1 ~ 9 owing to adopted the granule calcining device, can effectively remove the oxidation graphite alkene template for the whole pore structure parameter of material is great, does benefit to the embedding of sodion, deviates from, and when being used for preparing negative electrode material with this material, has excellent electrical properties.
The above embodiments are only for illustrating the technical idea of the present invention, and the protection scope of the present invention cannot be limited thereby, and any modification made on the basis of the technical scheme according to the technical idea proposed by 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 (8)
1. A preparation method of a porous sheet-shaped sodium ion battery negative electrode 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 greater than 7;
s2: adding a titanium source into 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 a granular material;
s3: and calcining the granular material in a granular calcining device for 1-4 hours, repeatedly and uniformly introducing fresh air into the granular material in the calcining process, unidirectionally extruding and replacing reaction waste gas in the granular material by the fresh air from bottom to top, and taking out solid powder after the calcining is finished to obtain the anatase phase porous titanium dioxide sheet.
2. The preparation method of the negative electrode material of the porous sheet sodium-ion battery according to claim 1, characterized in that: the mass ratio of the graphene oxide to the alcohol reagent, the alkali source and the titanium source is 1: 100-300: 1-3: 1.5 to 2.5.
3. The preparation method of the negative electrode material of the porous sheet sodium-ion battery according to claim 1, characterized in that: 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 ℃.
4. The preparation method of the negative electrode material of the porous sheet sodium-ion battery according to claim 1, characterized in that: the particle calcining device comprises a rack (1), wherein a cylinder (2) is arranged at the top of the rack (1), a pressure box (3) is arranged below a telescopic rod of the cylinder (2), the top of the pressure box (3) is communicated with an air suction pipe (31), the bottom of the pressure box (3) is communicated with a plurality of hollow pestle rods (4), the hollow pestle rods (4) are uniformly dispersed and arranged below the pressure box (3), through holes I (42) are formed in the bottom of the hollow pestle rods (4), check valves I (41) are arranged at the top of the hollow pestle rods (4), the check valves I (41) are arranged in the pressure box (3), an electric heating device (11) is arranged at the bottom of the rack (1), a calcining groove (6) is formed in the electric heating device (11), a pressure groove (5) is detachably connected in the calcining groove (6), the outer wall of the pressure groove (5) is connected with the inner wall of the calcining groove (6) in a sealing and sliding manner, the utility model discloses a pressure tank (5) for the gas stove, including indent (5) bottom intercommunication have a plurality of sleeves (53), the below of cavity pestle stick (4) is located to sleeve pipe (53) correspondence, when cavity pestle stick (4) insert in sleeve pipe (53), cavity pestle stick (4) and the sealed sliding connection of sleeve pipe (53) inner wall, through-hole two (531) have been seted up to the bottom of sleeve pipe (53), 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 calcination groove (6), be equipped with check valve two (62) on blast pipe (61), when calcination groove (6) and indent (5) are fixed, side opening (51) and blast pipe (61) align the intercommunication, all be equipped with on the outer wall of indent (5) and pressure box (3) fixed ear (32), indent (5) are fixed in pressure box (3) through fixed ear (32), the outer side wall of the pressing box (3) is in sealing sliding connection with the inner side wall of the pressing groove (5).
5. The preparation method of the negative electrode material of the porous sheet sodium-ion battery according to claim 4, characterized in that: 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 slidably connected with the top of the rack (1), and the calcining groove (6) and the pressing groove (5) are fixed through screws (63).
6. Use of the anatase-phase porous titanium dioxide sheet according to any one of claims 1 to 5 in the production of button cells.
7. The use of the anatase phase porous titanium dioxide sheet according to claim 6 in the preparation of button cells, characterized in that the specific preparation method is:
according to the mass ratio of 9: 0.5: 0.5 to form uniform slurry, coating the slurry on an aluminum foil, drying the slurry at 100 ℃ and cutting the slurry into pole pieces, drying the pole pieces at 120 ℃ for 10 hours under a vacuum condition, transferring the pole pieces into a glove box to assemble a button cell, taking a metal sodium sheet as a counter electrode, and 1M NaPF 6 The solution is used as electrolyte to assemble the button cell.
8. Use of anatase-phase porous titanium dioxide sheet according to claim 7 in the preparation of button cellsThe aqueous binder is one or more of PAA, SBR and 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.
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