CN114068897A - Tin triphosphate electrode material for potassium ion battery, preparation method and application thereof - Google Patents
Tin triphosphate electrode material for potassium ion battery, preparation method and application thereof Download PDFInfo
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- XCWCJGRYIMDVQP-UHFFFAOYSA-A [O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[Sn+4].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[Sn+4].[Sn+4].[Sn+4].[Sn+4] Chemical compound [O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[Sn+4].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[O-]P([O-])(=O)OP(=O)([O-])OP(=O)([O-])[O-].[Sn+4].[Sn+4].[Sn+4].[Sn+4] XCWCJGRYIMDVQP-UHFFFAOYSA-A 0.000 title claims abstract description 129
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 39
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000007772 electrode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000002245 particle Substances 0.000 claims abstract description 69
- 238000000498 ball milling Methods 0.000 claims abstract description 65
- 239000002131 composite material Substances 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 52
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006229 carbon black Substances 0.000 claims description 60
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 59
- 239000002041 carbon nanotube Substances 0.000 claims description 59
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 40
- 238000005303 weighing Methods 0.000 claims description 11
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- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 150000004770 chalcogenides Chemical class 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
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- 229910021392 nanocarbon Inorganic materials 0.000 description 10
- -1 tin triphosphite Chemical compound 0.000 description 8
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- 238000001878 scanning electron micrograph Methods 0.000 description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5805—Phosphides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a tin triphosphate electrode material for a potassium ion battery, a preparation method and application thereof. The method comprises the steps of S1, preparing tin triphosphate powder from tin powder and red phosphorus by a mechanical ball milling method; and S2, preparing the tin triphosphate composite material by the tin triphosphate powder and the carbon carrier through a secondary ball milling method. According to the tin triphosphate composite material disclosed by the invention, the carbon particles are coated on the surfaces of the tin triphosphate particles and filled between the tin triphosphate particles with adjacent coating structures, so that an effective conductive network and a protective barrier are constructed, and a new way is provided for the efficient preparation of other metal phosphide, chalcogenide, oxide and carbon composite structures.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a tin triphosphate electrode material for a potassium ion battery, a preparation method and application thereof.
Background
The potassium ion battery has the advantages of rich resources, low cost and the like, and has an energy storage mechanism and performance similar to those of a lithium ion battery, so that the potassium ion battery has the potential to become a future alternative energy storage device. However, the development of potassium ion batteries also faces some challenges. For example, potassium ions have a large ionic radius
Not only can lead to slower diffusion kinetics in a solid electrode, but also can easily cause larger volume change of an electrode material in the charging and discharging process, and seriously restricts the rate capability and the cycling stability of the potassium ion battery. Therefore, the development of high-performance electrode materials has become a focus of research in the field of potassium ion batteries in recent years.
In recent years, tin triphosphate has been receiving increasing attention as a negative electrode material for potassium ion batteries. The material has two potassium storage mechanisms of conversion and alloying, shows higher specific capacity than a carbon material, and is a very potential negative electrode material for constructing a high-energy-density potassium ion battery. However, its poor conductivity increases polarization during the reaction, resulting in poor rate performance and capacity fade during cycling; the large volume change during charge and discharge can cause the continuous rupture and formation of the solid electrolyte interface during the circulation process, which causes serious side reaction and electrolyte consumption. The novel carbon materials such as the carbon nanotube and the carbon black are used as good conductive media, so that the conductivity of the electrode material can be improved, and the good electrochemical stability of the electrode material is also beneficial to improving the cycling stability of the electrode material. The compounding of the high specific capacity tin triphosphate with the carbon nanotube with good conductivity/stability, carbon black and other novel carbon materials is one of the important approaches for preparing the potassium ion battery with high energy density and good cycling stability.
Disclosure of Invention
The invention aims to overcome the defects, and provides a tin triphosphate electrode material for a potassium ion battery, a preparation method of the tin triphosphate electrode material and application of the tin triphosphate electrode material to the potassium ion battery.
The technical scheme adopted by the invention is as follows:
the tin triphosphate electrode material for the potassium ion battery comprises tin triphosphate particles, carbon particles coated on the tin triphosphate particles and filled between adjacent tin triphosphate particles in a microstructure, wherein the carbon particles are flaky or spherical.
Specifically, the carbon particles are carbon nano tube grinding particles, and the mass ratio of the carbon particles to the tin triphosphate particles is 1:9-3: 7.
As another specific embodiment, the carbon particles are carbon black abrasive particles, and the mass ratio of the carbon particles to the tin triphosphate particles is from 1:9 to 3: 7.
As another specific embodiment, the carbon particles are double-carbon mixed grinding particles of carbon nanotubes and carbon black, the mass ratio of the carbon particles to the tin triphosphate particles is 1:9-3:7, and the mass ratio of the carbon nanotubes to the carbon black is 1:2-2: 1.
The invention also provides a preparation method of the tin triphosphate electrode material for the potassium ion battery, which comprises the following steps:
s1, preparing tin triphosphate powder by using a mechanical ball milling method for tin powder and red phosphorus:
and S2, preparing the tin triphosphate composite material by the tin triphosphate powder and the carbon carrier through a secondary ball milling method.
In step S1, weighing tin powder and red phosphorus in a glove box according to set amounts, putting the tin powder and red phosphorus into a zirconia ball milling tank, adding zirconia balls, sealing the ball milling tank, and putting the ball milling tank into a ball mill for ball milling to obtain pure-phase tin triphosphate powder;
in step S2, the tin triphosphate powder ground in step S1 is weighed and placed into a zirconia ball milling pot, then the carbon carrier is weighed and placed into the ball milling pot, the zirconia balls are placed, the ball milling pot is sealed, and then the ball milling pot is placed into a ball mill for ball milling.
As a further optimization of the method of the present invention, in step S1 of the present invention, the molar ratio of tin powder to red phosphorus is 1: 3.
As a further optimization of the method, in the step S1 of the invention, in the preparation process of the tin triphosphate powder, the rotation speed of the ball mill is 400-600rpm, and the ball milling time is 20-40h, and in the step S2, in the preparation process of the tin triphosphate composite material, the rotation speed of the ball mill is 400-600rpm, and the ball milling time is 20-40 h.
As a further optimization of the method of the present invention, the carbon support of the present invention is carbon nanotube or carbon black or a mixture of carbon nanotube and carbon black, in step S2, the mass ratio of the carbon support to the tin triphosphate is 1:9-3:7, and when the carbon support is a mixture of carbon nanotube and carbon black, the mass ratio of the carbon nanotube to the carbon black is 1:2-2: 1.
The invention also provides an application of the tin triphosphate electrode material for the potassium ion battery, and the tin triphosphate electrode material is used for preparing a negative electrode material of the potassium ion battery.
The invention has the following advantages:
1. according to the tin triphosphate composite material disclosed by the invention, the carbon particles are coated on the surfaces of the tin triphosphate particles and filled between the tin triphosphate particles with adjacent coating structures, so that an effective conductive network and a protective barrier are constructed, and a new way is provided for the efficient preparation of other metal phosphide, chalcogenide, oxide and carbon composite structures.
2. According to the tin triphosphate composite material, the carbon nano tubes and the carbon black have a double-carbon combined structure, the particles of the carbon nano tubes are of a sheet structure, good wrapping performance can be formed on the tin triphosphate particles, the carbon black particles are spherical particles, the gap filling performance is good, a conductive network and a protective barrier constructed by the carbon nano tubes are better, and the structural superiority is better;
3. the processing method of the tin triphosphate composite material adopts a mechanical ball milling method, so that the processing mode is simpler, and the manufacturing cost is lower;
4. the tin triphosphate composite material can be used in the production process of the negative electrode material of the potassium ion battery, has good energy density and cycle stability, and has wide application prospect.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a schematic synthesis of example III;
FIG. 2 is a comparative XRD pattern of three tin triphosphate composites of examples one, two and three;
FIG. 3 is an SEM image of a tin triphosphate/carbon nanotube composite of the first embodiment;
FIG. 4 is a TEM image of the tin triphosphate/carbon nanotube composite of example one;
FIG. 5 is an SEM image of a tin triphosphite/carbon black composite of example two;
FIG. 6 is a TEM image of a tin triphosphite/carbon black composite of example two;
FIG. 7 is an SEM image of a tin triphosphate/dual carbon composite of example III;
FIG. 8 is a TEM image of a tin triphosphite/dual carbon composite of example III;
FIG. 9 is a graph of constant current charge-discharge cycles of three tin triphosphate composites of examples one, two and three;
FIG. 10 is a graph of rate capability of three tin triphosphate composites of examples one, two and three;
FIG. 11 is an electrochemical impedance plot of three tin triphosphate composites of examples one, two and three;
fig. 12 is a graph comparing the reversible specific capacity and cycling stability of potassium ion half cells assembled with tin triphosphate composites of example three with other literature data.
Detailed Description
The present invention is further described in the following with reference to the drawings and the specific embodiments so that those skilled in the art can better understand the present invention and can implement the present invention, but the embodiments are not to be construed as limiting the present invention, and the embodiments and the technical features of the embodiments can be combined with each other without conflict.
It is to be understood that the terms first, second, and the like in the description of the embodiments of the invention are used for distinguishing between the descriptions and not necessarily for describing a sequential or chronological order. The "plurality" in the embodiment of the present invention means two or more.
The term "and/or" in the embodiment of the present invention is only an association relationship describing an associated object, and indicates that three relationships may exist, for example, a and/or B may indicate: a exists alone, B exists alone, and A and B exist at the same time. In addition, the character "/" herein generally indicates that the former and latter associated objects are in an "or" relationship.
Example one
The embodiment provides a tin triphosphate electrode material for a potassium ion battery, which comprises tin triphosphate particles and carbon particles coated on the tin triphosphate particles in a microstructure, wherein the carbon particles are formed by grinding carbon nano tubes.
The embodiment also provides a preparation method for preparing the tin triphosphate electrode material for the potassium ion battery, which comprises the following steps:
s1, preparing tin triphosphate powder: respectively weighing 1g of tin powder and 0.78g of red phosphorus in a glove box according to the set amount, putting the tin powder and the red phosphorus into a zirconia ball milling tank, adding zirconia balls, sealing the ball milling tank, putting the ball milling tank into a ball mill for ball milling, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 30 hours, so as to obtain pure-phase tin triphosphate powder;
s2, preparing the tin triphosphite/carbon nano tube composite material: weighing 2g of the tin triphosphate powder ground in the step S1, putting the tin triphosphate powder into a zirconia ball milling tank, weighing 0.5g of carbon nanotubes, putting the carbon nanotubes into the ball milling tank, putting zirconia balls, sealing the ball milling tank, and putting the ball milling tank into a ball mill for ball milling, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 8 hours, so that the tin triphosphate/carbon nanotube composite material is obtained.
Example two
The embodiment provides a tin triphosphate electrode material for a potassium ion battery, which comprises tin triphosphate particles and carbon particles coated on the tin triphosphate particles in a microstructure, wherein the carbon particles are formed by grinding carbon black.
The embodiment also provides a preparation method for preparing the tin triphosphate electrode material for the potassium ion battery, which comprises the following steps:
s1, preparing tin triphosphate powder: respectively weighing 1g of tin powder and 0.78g of red phosphorus in a glove box according to the set amount, putting the tin powder and the red phosphorus into a zirconia ball milling tank, adding zirconia balls, sealing the ball milling tank, putting the ball milling tank into a ball mill for ball milling, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 30 hours, so as to obtain pure-phase tin triphosphate powder;
s2, preparing the tin triphosphide/carbon black composite material: weighing 2g of the tin triphosphate powder ground in the step S1, putting the tin triphosphate powder into a zirconia ball milling tank, weighing 0.5g of carbon black, putting the carbon black into the ball milling tank, putting zirconia balls, sealing the ball milling tank, and putting the ball milling tank into a ball mill for ball milling, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 8 hours, so that the tin triphosphate/carbon black composite material is obtained.
EXAMPLE III
The embodiment provides a tin triphosphate electrode material for a potassium ion battery, which comprises tin triphosphate particles and carbon particles coated on the tin triphosphate particles in a microstructure, wherein the carbon particles are formed by mixing and grinding carbon nanotubes and carbon black, and the carbon nanotubes are in a sheet structure after grinding, and the carbon black is in a spherical particle after grinding, so that the microstructure of the tin triphosphate electrode material is shown in fig. 1, the carbon nanotube particles in the sheet structure are coated on the surfaces of the tin triphosphate particles, and the carbon black in a particle state is filled between the adjacent coated tin triphosphate particles.
The embodiment also provides a preparation method for preparing the tin triphosphate electrode material for the potassium ion battery, which comprises the following steps:
s1, preparing tin triphosphate powder: respectively weighing 1g of tin powder and 0.78g of red phosphorus in a glove box according to the set amount, putting the tin powder and the red phosphorus into a zirconia ball milling tank, adding zirconia balls, sealing the ball milling tank, putting the ball milling tank into a ball mill for ball milling, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 30 hours, so as to obtain pure-phase tin triphosphate powder;
s2, preparing a tin triphosphite/double carbon (mixture of carbon nano tube and carbon black) composite material: weighing 2g of the tin triphosphate powder ground in the step S1, putting the tin triphosphate powder into a zirconia ball milling tank, then respectively weighing 0.25g of carbon nanotubes and 0.25g of carbon black, putting the carbon nanotubes and the carbon black into the ball milling tank, putting zirconia balls, sealing the ball milling tank, and putting the ball milling tank into a ball mill for ball milling, wherein the rotating speed of the ball mill is 500rpm, and the ball milling time is 8 hours, so that the tin triphosphate/dual-carbon composite material is obtained.
And (4) analyzing results:
crystal structure change of tin triphosphate:
fig. 2 is XRD patterns of three tin triphosphores of the tin triphosphores/carbon nanotubes composite provided in example one, the tin triphosphores/carbon black composite provided in example two, and the tin triphosphores/nanocarbon (combination of carbon nanotubes and carbon black) composite provided in example three, and the main purpose of XRD analysis is to analyze the crystal change of tin triphosphores after ball milling, and from the XRD pattern analysis in fig. 2, the angles of diffraction peaks appearing in the three XRD pattern lines are the same, and it can be seen that the original crystal structure of tin triphosphores is not significantly changed after secondary ball milling with different carbon materials.
The microstructure of the tin triphosphate composite material is as follows:
fig. 3 is an SEM image of the tin triphosphate/carbon nanotube composite material provided in the first embodiment, fig. 4 is a TEM high resolution image of the tin triphosphate/carbon nanotube, and it can be seen from fig. 3 and 4 that after the carbon nanotube is added, the tin triphosphate is tightly wrapped by the carbon nanotube, and the individual particles are changed into a carbon-coated structure, and the particle size of the tin triphosphate is changed to about 10 nm due to the ball milling effect.
Fig. 5 is an SEM image of the tin triphosphate/carbon black composite material provided in example two, and fig. 6 is a TEM high resolution image of the tin triphosphate/carbon black composite material, and it can be seen from fig. 5 and fig. 6 that after the carbon black is added, the tin triphosphate is tightly wrapped by the carbon layer to be a carbon-coated structure, the particle size is about 10 nm, and a severe agglomeration phenomenon occurs between particles, thereby showing that the carbon black has a gap filling effect.
Fig. 7 is an SEM image of the tin triphosphate/nanocarbon (combination of carbon nanotubes and carbon black) composite provided in example three, and fig. 8 is a TEM high resolution image of the tin triphosphate/nanocarbon (combination of carbon nanotubes and carbon black) composite, and it can be seen from fig. 1 and 8 that, after the carbon nanotubes and the carbon black are added, the tin triphosphate is tightly wrapped by the carbon layer to form a carbon-coated structure, the particle size is about 10 nanometers, and a slight agglomeration phenomenon occurs between particles.
Thirdly, the performance of the potassium ion battery assembled by the prepared tin triphosphate composite material is as follows:
in the battery manufacturing industry, the negative pole piece of the battery is prepared by coating electrode slurry on a copper sheet and drying the electrode slurry. Based on the above manufacturing process, the tin triphosphate/carbon nanotube composite obtained in example one, the tin triphosphate/carbon black composite obtained in example two, and the tin triphosphate/carbon black composite obtained in example three (a combination of carbon nanotubes and carbon black) were used as three experimental samples, each experimental sample was mixed with conductive carbon black and sodium carboxymethyl cellulose at a ratio of 5:3:2, and ground for 0.5h, the mixed composite material was uniformly coated on a copper foil, and dried in vacuum at 60 ℃ for 12h, and 1M KFSI-EC/DEC was used as an electrolyte solution. A2032 type button cell is assembled by taking a potassium sheet as a counter electrode and a reference electrode, and then electrochemical performance tests are carried out to obtain an experimental result of a constant current charge-discharge cycle curve chart shown in figure 9, an experimental result of a rate performance chart shown in figure 10 and an experimental result of an electrochemical impedance chart shown in figure 11.
As can be seen from the experimental results of the constant current charge-discharge cycle profile shown in FIG. 9, at 1000mA g-1The tin triphosphide/nanocarbon (combination of carbon nanotubes and carbon black) composites exhibited a reversible capacity that was significantly higher than that of the tin triphosphide/carbon black composites and the tin triphosphide/carbon nanotube composites, as a result of which, in the three examples described above,
as can be seen from the results of the rate capability graph experiment shown in FIG. 10, at 50mA g-1At lower current densities, the tin triphosphite/nanocarbon (combination of carbon nanotubes and carbon black) composite can exhibit greater than 400mAh g-1High reversible capacity of (2), even at 1000mA g-1The tin triphosphate/carbon composite material still can show more than 200mAh g under larger current density-1The reversible capacity of the composite material indicates that the tin triphosphate/carbon bicide (combination of the carbon nano tube and the carbon black) composite material has good rate performance as a potassium ion battery cathode material, and is obviously superior to the rate performance of the tin triphosphate/carbon black composite material and the rate performance of the tin triphosphate/carbon nano tube composite material.
As can be seen from the experimental results of the electrochemical impedance diagram shown in fig. 11, the prepared tin triphosphide/nanocarbon (combination of carbon nanotubes and carbon black) composite material has a lower charge transfer impedance, and the tin triphosphide/nanocarbon composite material has more excellent electrical conductivity than the charge transfer impedance of the tin triphosphide/carbon black composite material and the charge transfer impedance of the tin triphosphide/carbon nanotube composite material.
The results obtained by performing performance tests on the potassium ion battery assembled by the tin triphosphate composite materials of the three examples show that the relevant physical parameter performance of the tin triphosphate/dicarbon (combination of carbon nano tube and carbon black) composite material is obviously superior to that of the tin triphosphate/carbon black composite material and that of the tin triphosphate/carbon nano tube, and the structural superiority of the tin triphosphate/dicarbon (combination of carbon nano tube and carbon black) composite material provided by the third example is proved.
In the tin triphosphate/dicarbon (combination of carbon nanotubes and carbon black) composite material provided in example three, since the carbon nanotubes have a sheet-like structure after being ground, and the carbon black has spherical particles after being ground, the microstructure of the tin triphosphate motor material is as shown in fig. 1, the carbon nanotube particles having a sheet-like structure are coated on the surface of the tin triphosphate particles, and the carbon black in a particle state is filled between adjacent coated tin triphosphate particles, so that the electrical properties are more advantageous in structural analysis. In the following, we compare the performance of the composite material of tin triphosphate/dicarbon (combination of carbon nanotube and carbon black) provided in example three with that of the existing battery anode material, and the expression of the composite material of tin triphosphate/dicarbon (combination of carbon nanotube and carbon black) is SnP3@ DC, the current production battery negative electrode materials compared are all from the prior published material literature:
1、Sn4P3/C——W.Zhang,J.Mao,S.Li,Z.Chen and Z.Guo,J.Am.Chem.Soc.,2017,139,3316-3319；
2、Sn4P3@carbon fiber——W.Zhang,W.K.Pang,V.Sencadas and Z.Guo,Joule,2018,2,1534-1547；
3、Sn4P3/RGO——W.Yang,J.Zhang,D.Huo,S.Sun,S.Tao,Z.Wang,J.Wang,D.Wu and B.Qian,Ionics,2019,25,4795-4803；
4、Sn4P3@C——D.Li,Y.Zhang,Q.Sun,S.Zhang,Z.Wang,Z.Liang,P.Si and L.Ci,Energy Storage Mater.,2019,23,367-374；
5、SnP0.94@GO——X.Zhao,W.Wang,Z.Hou,G.Wei,Y.Yu,J.Zhang and Z.Quan,Chem.Eng.J.,2019,370,677-683；
6、SnP3/C——R.Verma,P.N.Didwal,H.-S.Ki,G.Cao and C.-J.Park,ACS Appl.Mater.Interfaces,2019,11,26976-26984；
7、r-SnP/C——B.Li,S.Shang,J.Zhao,D.M.Itkis,X.Jiao,C.Zhang,Z.-K.Liu and J.Song,Carbon,2020,168,468-474；
by comparing the specific capacity and the cycling stability of the assembled potassium ion half-cell of the tin triphosphite/nanocarbon (combination of carbon nanotubes and carbon black) composite material provided in the third comparative example with those of the negative electrode material for potassium ion cell in the prior art, a data comparison graph as shown in fig. 12 is obtained, thereby illustrating that the tin triphosphite/nanocarbon (combination of carbon nanotubes and carbon black) composite material in the present example has higher reversible specific capacity and better cycling stability due to the effective protective barrier and conductive network formed by the nanocarbon compared with the prior art.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. A tin triphosphate electrode material for a potassium ion battery is characterized in that: in the microstructure, the electrode material comprises tin triphosphate particles and carbon particles which are coated on the tin triphosphate particles and filled between the adjacent tin triphosphate particles, wherein the carbon particles are in a sheet shape or a spherical shape.
2. The tin triphosphate electrode material for a potassium ion battery according to claim 1, characterized in that: the carbon particles are carbon nano tube grinding particles, and the mass ratio of the carbon particles to the tin triphosphate particles is 1:9-3: 7.
3. The tin triphosphate electrode material for a potassium ion battery according to claim 1, characterized in that: the carbon particles are carbon black grinding particles, and the mass ratio of the carbon particles to the tin triphosphate particles is 1:9-3: 7.
4. The tin triphosphate electrode material for a potassium ion battery according to claim 1, characterized in that: the carbon particles are double-carbon mixed grinding particles of carbon nanotubes and carbon black, the mass ratio of the carbon particles to the tin triphosphate particles is 1:9-3:7, and the mass ratio of the carbon nanotubes to the carbon black is 1:2-2: 1.
5. A preparation method of a tin triphosphate electrode material for a potassium ion battery is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing tin triphosphate powder from the tin powder and red phosphorus by a mechanical ball milling method;
and S2, preparing the tin triphosphate composite material by the tin triphosphate powder and the carbon carrier through a secondary ball milling method.
6. The method of claim 5, wherein:
step S1, weighing tin powder and red phosphorus with set amounts in a glove box, putting the tin powder and the red phosphorus into a zirconia ball milling tank, adding zirconia balls, sealing the ball milling tank, and putting the ball milling tank into a ball mill for ball milling to obtain pure-phase tin triphosphate powder;
in step S2, the tin triphosphate powder ground in step S1 is weighed and placed into a zirconia ball milling pot, then the carbon carrier is weighed and placed into the ball milling pot, the zirconia balls are placed, the ball milling pot is sealed, and then the ball milling pot is placed into a ball mill for ball milling.
7. The method of claim 6, wherein: in step S1, the molar ratio of tin powder to red phosphorus is 1: 3.
8. The method of claim 6, wherein: in the step S1, in the preparation process of the tin triphosphate powder, the rotation speed of the ball mill is 400-600rpm, and the ball milling time is 20-40h, and in the step S2, in the preparation process of the tin triphosphate composite material, the rotation speed of the ball mill is 400-600rpm, and the ball milling time is 20-40 h.
9. The method of claim 6, wherein: the carbon carrier is carbon nano tubes or carbon black or a mixture of the carbon nano tubes and the carbon black, in the step S2, the adding mass ratio of the carbon carrier to the tin triphosphate is 1:9-3:7, and when the carbon carrier is the mixture of the carbon nano tubes and the carbon black, the mass ratio of the carbon nano tubes to the carbon black is 1:2-2: 1.
10. The application of the tin triphosphate electrode material for the potassium ion battery is characterized in that: the use of a tin triphosphide electrode material according to any of claims 1 to 4 for the preparation of a negative electrode material for a potassium ion battery.
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