CN110556517A - Negative electrode material, negative electrode and preparation method of negative electrode - Google Patents
Negative electrode material, negative electrode and preparation method of negative electrode Download PDFInfo
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Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a negative electrode material, a negative electrode and a preparation method of the negative electrode. The tin dioxide is attached to the porous carbon, so that the porous carbon can provide a three-dimensional support carrier for the tin dioxide nanoparticles, the volume expansion of the tin dioxide in the charging and discharging processes is relieved, and the cycle stability of the lithium ion battery is improved; meanwhile, the surface of the negative electrode material is provided with the nitrogen-doped carbon coating layer, so that the side reaction between tin dioxide and electrolyte is inhibited, the integral conductivity of the electrode is improved, and the specific capacity of the lithium ion battery is improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a negative electrode material, a negative electrode and a preparation method of the negative electrode.
Background
the lithium ion battery, as a secondary battery, mainly depends on lithium ions moving between a positive electrode and a negative electrode to work, and is widely applied to the fields of energy storage power systems, electric tools, portable electrical appliances, military equipment, aerospace and the like due to the advantages of high energy, long service life, low cost, strong adaptability, environmental protection and the like.
The negative electrode of the lithium ion battery is used as an important component of the lithium ion battery, and the structure and the performance of the negative electrode directly influence the capacity and the cycle performance of the lithium ion battery. At present, graphite materials are generally adopted by the conventional lithium ion battery as a negative electrode, but the theoretical specific capacity of the graphite materials is only 372mAh/g, so that the development requirement of the high-specific-energy lithium ion battery is difficult to meet, and therefore, a new high-specific-capacity lithium ion battery negative electrode material is urgently needed to be developed.
The theoretical specific capacity of the tin dioxide (SnO 2) is up to 1494mAh/g, the tin dioxide has wide sources, low cost and good safety, so the tin dioxide has obvious advantages when being used as the lithium ion battery cathode material, however, the tin dioxide is accompanied with huge volume expansion (the volume expansion is more than 300 percent) in the circulation process, so that electrode pulverization and shedding are easily caused, and the lithium ion battery has lower actual capacity and poorer circulation stability.
Disclosure of Invention
The invention aims to provide a negative electrode material, a negative electrode and a preparation method of the negative electrode, which are used for solving the technical problems of low specific capacity and poor cycle stability of the conventional lithium ion battery, so that the specific capacity and the cycle stability of the lithium ion battery are improved.
In order to solve the technical problem, the invention provides a negative electrode material which comprises a nitrogen-doped carbon coating layer, porous carbon and tin dioxide, wherein the tin dioxide is attached to the porous carbon, and the nitrogen-doped carbon coating layer wraps the tin dioxide and the porous carbon.
Preferably, the thickness of the nitrogen-doped carbon coating layer is 1-5 nm.
Preferably, the particle size of the tin dioxide is 2-6 nm.
Preferably, the nitrogen-doped carbon coating layer is formed by carbonizing polyacrylonitrile.
In order to solve the same technical problem, the invention also provides a negative electrode, which comprises a copper foil and the negative electrode material, wherein the negative electrode material is attached to the copper foil.
When the cathode material provided by the invention is used as a lithium ion battery cathode, the porous carbon matrix can provide a three-dimensional support carrier for the tin dioxide nanoparticles, so that the volume expansion of tin dioxide in the charging and discharging processes is relieved, and the cycle stability of the lithium ion battery is further improved; meanwhile, the surface of the negative electrode material is provided with the nitrogen-doped carbon coating layer, so that the side reaction between tin dioxide and electrolyte is inhibited, the integral conductivity of the electrode is improved, and the specific capacity of the lithium ion battery is improved.
In order to solve the same technical problem, the invention also provides a preparation method of the cathode, which comprises the following steps:
carrying out hydrolysis reaction on the porous carbon and stanniferous chloride salt to obtain stannic oxide/porous carbon composite powder;
Mixing the tin dioxide/porous carbon composite powder with polyacrylonitrile to obtain slurry;
Coating the slurry on a copper foil to obtain a pole piece;
Drying the pole piece;
and in an inert gas atmosphere, carrying out carbonization heat treatment on the dried pole piece under a preset carbonization heat treatment condition to obtain the nitrogen-doped carbon/tin dioxide/porous carbon composite cathode, and finishing the preparation of the cathode.
As a preferred scheme, the hydrolysis reaction of the porous carbon and the stanniferous chloride salt is carried out to obtain the tin dioxide/porous carbon composite powder, and the method comprises the following steps:
dispersing porous carbon powder in a mixed solution of an organic solvent and water to obtain a dispersion liquid of the porous carbon powder;
stirring and mixing the dispersion liquid of the porous carbon powder and concentrated hydrochloric acid;
Carrying out hydrolysis reaction on the dispersion liquid of the porous carbon powder after stirring and mixing, concentrated hydrochloric acid and stanniferous chloride under preset reaction conditions to obtain a tin dioxide/porous carbon solution;
And carrying out suction filtration, washing and drying treatment on the tin dioxide/porous carbon solution to obtain the tin dioxide/porous carbon composite powder.
Preferably, the volume ratio of the organic solvent to the water is 1: 3-3: 1.
Preferably, the organic solvent is any one of absolute ethyl alcohol, ethylene glycol, methanol and propanol.
preferably, the mass ratio of the porous carbon to the stanniferous chloride is 1:10 to 1: 20.
Preferably, the stanniferous chloride salt is stannous chloride monohydrate.
As a preferred scheme, the preset reaction conditions specifically include: the reaction temperature is 70-90 ℃, and the reaction time is 0.5-2 h.
As a preferred scheme, the tin dioxide/porous carbon composite powder is mixed with polyacrylonitrile to obtain slurry, and the method specifically comprises the following steps:
And stirring and mixing the tin dioxide/porous carbon composite powder and polyacrylonitrile powder with a dimethylformamide solvent to obtain the slurry.
According to a preferable scheme, the mass ratio of the tin dioxide/porous carbon composite powder to the polyacrylonitrile is 4: 1-9: 1.
Preferably, the inert gas is nitrogen or argon.
preferably, the preset carbonization heat treatment conditions specifically include: the heating rate is 2-10 ℃/min, the heat treatment temperature is 200-500 ℃, and the heat preservation time is 0.5-1 h.
the invention provides a preparation method of a cathode, which comprises the steps of carrying out hydrolysis reaction on porous carbon and stanniferous chloride salt to enable the stanniferous chloride salt to generate uniformly distributed stannic oxide nano particles on a porous carbon substrate in situ to obtain stannic oxide/porous carbon composite powder, so that organic combination of stannic oxide and porous carbon is realized, the generated nano stannic oxide is favorable for exerting electrochemical activity, the porous carbon has a unique multi-stage pore structure, a buffer space is provided for volume expansion of stannic oxide in a circulation process, and circulation stability is improved; then mixing the obtained tin dioxide/porous carbon composite powder with polyacrylonitrile to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; finally, in an inert gas atmosphere, carrying out carbonization heat treatment on the dried pole piece under a preset carbonization heat treatment condition to obtain a nitrogen-doped carbon/tin dioxide/porous carbon composite cathode, and completing preparation of the cathode; through to the drying after the pole piece carries out the carbonization heat treatment for polyacrylonitrile carbonization forms nitrogen-doped carbon coating, nitrogen-doped carbon coating has restrained the side reaction between tin dioxide and electrolyte on the tin dioxide surface formation protective layer, and because nitrogen-doped carbon coating self has high conductivity, has accelerated the quick transmission of electron, thereby has improved the electric conductivity of negative pole effectively, consequently when the negative pole that will adopt above-mentioned method to prepare is as lithium ion battery's negative pole, can improve lithium ion battery's specific capacity and cyclical stability. In addition, in the process of preparing the negative electrode, the preparation of the negative electrode is combined with the preparation of the composite material, so that the polyacrylonitrile is used as an organic carbon source of the nitrogen-doped carbon coating layer and is also used as a binder, and therefore, the preparation process of the negative electrode is simplified.
Drawings
fig. 1 is a transmission electron microscope photograph of a negative electrode material in an example of the invention;
Fig. 2 is a flowchart of a method of manufacturing a negative electrode in an embodiment of the invention;
FIG. 3 is a flow chart of a method for preparing a tin dioxide/porous carbon composite powder according to an embodiment of the present invention;
fig. 4 is an X-ray diffraction pattern of the nitrogen-doped carbon/tin dioxide/porous carbon composite powder in example 1 of the present invention;
Fig. 5 is a graph of the cycling performance of the nitrogen-doped carbon/tin dioxide/porous carbon composite anode of example 1 of the present invention at different current densities;
Fig. 6 is a graph of the cycle performance of the nitrogen-doped carbon/tin dioxide/porous carbon composite anode at a current density of 1A/g in example 1 of the present invention;
Fig. 7 is a graph of cycle performance of the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrodes in example 1 and comparative examples 7 to 9 of the present invention at a current density of 0.1A/g.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
As shown in fig. 1, a negative electrode material according to a preferred embodiment of the present invention includes a nitrogen-doped carbon coating layer, porous carbon, and tin dioxide, wherein the tin dioxide is attached to the porous carbon, and the nitrogen-doped carbon coating layer covers the tin dioxide and the porous carbon. Wherein, the nitrogen-doped carbon coating layer is formed by carbonizing polyacrylonitrile.
in the embodiment of the invention, the thickness of the nitrogen-doped carbon coating layer is 1-5 nm; the particle size of the tin dioxide is 2-6 nm. As known to those skilled in the art, "particle size" can be used to characterize the size of a particle.
In the embodiment of the invention, the porous carbon material comprises micropores, mesopores and macropores, wherein the pore diameter of the micropores is 1-2 nm, the pore diameter of the mesopores is 2-5 nm, the pore diameter of the macropores is 20-100 nm, the specific surface area of the porous carbon is 820m 2/g, and the pore volume is 0.75cm 3/g.
In the embodiment of the invention, when the cathode material is used as a cathode of a lithium ion battery, the porous carbon matrix can provide a three-dimensional support carrier for the tin dioxide nanoparticles, so that the volume expansion of tin dioxide in the charging and discharging processes is relieved, and the cycle stability of the lithium ion battery is further improved; meanwhile, the surface of the negative electrode material is provided with the nitrogen-doped carbon coating layer, so that the side reaction between tin dioxide and electrolyte is inhibited, the integral conductivity of the electrode is improved, and the specific capacity of the lithium ion battery is improved.
In order to solve the same technical problem, the invention also provides a negative electrode, which comprises a copper foil and the negative electrode material, wherein the negative electrode material is attached to the copper foil.
in an embodiment of the present invention, the above-described negative electrode may be prepared according to the preparation method shown in fig. 2, including the steps of:
S1, carrying out hydrolysis reaction on the porous carbon and stanniferous chloride to obtain stannic oxide/porous carbon composite powder;
S2, mixing the tin dioxide/porous carbon composite powder with polyacrylonitrile to obtain slurry;
S3, coating the slurry on a copper foil to obtain a pole piece;
S4, drying the pole piece;
And S5, performing carbonization heat treatment on the dried pole piece under a preset carbonization heat treatment condition in an inert gas atmosphere to obtain the nitrogen-doped carbon/tin dioxide/porous carbon composite cathode, and completing the preparation of the cathode.
As shown in fig. 3, in step S1, the step of performing hydrolysis reaction on the porous carbon and the tin-containing chloride salt to obtain the tin dioxide/porous carbon composite powder includes the steps of:
s11, dispersing the porous carbon powder in a mixed solution of an organic solvent and water to obtain a dispersion liquid of the porous carbon powder;
S12, stirring and mixing the dispersion liquid of the porous carbon powder and concentrated hydrochloric acid;
s13, carrying out hydrolysis reaction on the stirred and mixed dispersion liquid of the porous carbon powder, concentrated hydrochloric acid and stanniferous chloride under preset reaction conditions to obtain a tin dioxide/porous carbon solution;
And S14, carrying out suction filtration, washing and drying treatment on the tin dioxide/porous carbon solution to obtain the tin dioxide/porous carbon composite powder.
in step S11, the porous carbon powder is dispersed in a mixed solution of an organic solvent and water by an ultrasonic action; wherein the mixed solution of the organic solvent and water is 300-500 ml; the used organic solvent can be any one of absolute ethyl alcohol, ethylene glycol, methanol and propanol, and the volume ratio of the organic solvent to water is 1: 3-3: 1.
In step S12, 1 to 2ml of concentrated hydrochloric acid is added to the dispersion of the porous carbon powder obtained in step S11, and the mixture is stirred and mixed.
in step S13, under the condition of vigorously stirring the dispersion of the porous carbon powder and concentrated hydrochloric acid, adding a tin-containing chloride salt, and performing a hydrolysis reaction under a preset reaction condition to obtain a tin dioxide/porous carbon solution; wherein the violent stirring is to make the porous carbon in the dispersion liquid of the porous carbon powder fully contact with the stanniferous chloride salt, so that the stannic oxide is favorably and uniformly attached to the porous carbon; the mass ratio of the porous carbon powder to the stanniferous chloride salt is 1: 10-1: 20, and the stanniferous chloride salt is stannous chloride monohydrate; the preset reaction conditions comprise: the reaction temperature is 70-90 ℃, and the reaction time is 0.5-2 h.
In step S14, after the temperature of the tin dioxide/porous carbon solution obtained in step S13 is reduced to room temperature, the tin dioxide/porous carbon solution is subjected to suction filtration, sufficiently washed with deionized water, and dried to obtain the tin dioxide/porous carbon composite powder.
In the embodiment of the invention, the porous carbon and the stannic chloride salt are subjected to hydrolysis reaction, so that the stannic chloride salt generates tin dioxide nanoparticles with uniform distribution in situ on the porous carbon substrate, and thus the stannic dioxide/porous carbon composite powder is obtained, and compared with the traditional two-phase physical mixing (such as stirring or ball milling), the in-situ chemical method adopted in the embodiment of the invention is more favorable for realizing the organic combination of the stannic dioxide and the porous carbon, so as to ensure that the stannic dioxide can be uniformly attached to the porous carbon; in addition, the hydrolysis reaction process does not involve harsh reaction conditions such as high temperature and high pressure, so that the operation is simpler and more convenient, and the method is easy to popularize.
in step S2, the tin dioxide/porous carbon composite powder is mixed with polyacrylonitrile to obtain a slurry, specifically: and stirring and mixing the tin dioxide/porous carbon composite powder and polyacrylonitrile powder with a dimethylformamide solvent to obtain slurry. The mass ratio of the tin dioxide/porous carbon composite powder to the polyacrylonitrile is 4: 1-9: 1.
In step S3, the slurry is coated on a copper foil to obtain a pole piece, which specifically includes: and coating the slurry on the copper foil in a tape casting manner to form a uniform thin layer, thereby obtaining the pole piece.
In step S4, the pole piece is dried at 60-100 ℃.
In step S5, the dried pole piece is cut into a small disc with a diameter of 12mm, and the small disc is placed in a tube furnace, and subjected to carbonization heat treatment under a preset carbonization heat treatment condition in an inert gas atmosphere to obtain a nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode, thereby completing the preparation of the negative electrode. Wherein the inert gas atmosphere is any one of nitrogen or argon; the preset carbonization heat treatment conditions comprise: the heating rate is 2-10 ℃/min, the heat treatment temperature is 200-500 ℃, and the heat preservation time is 0.5-1 h. Preferably, the heat treatment temperature is 300-400 ℃. In the embodiment of the invention, because the valence state of the tin element is changeable, a tin simple substance, a plurality of tin-containing oxides, tin-copper alloy and other substances can be formed in the carbonization heat treatment process, and the heat treatment temperature is controlled within the range of 200-500 ℃, so that the crystallinity of tin dioxide subjected to carbonization heat treatment is properly improved, and the electrochemical performance of the tin dioxide is favorably exerted; however, when the heat treatment temperature is further increased, the obtained negative electrode has impurity phases, and the mass change of tin dioxide of the negative electrode pole piece before and after the carbonization heat treatment is large, so that the obtained pole piece has a loose structure, active substances are easy to fall off from the copper foil, and the electrochemical performance is reduced.
In the embodiment of the invention, the preparation method of the porous carbon powder specifically comprises the following steps:
S101, adding 50g of pretreated ion exchange resin into 200ml of cobalt chloride aqueous solution, stirring for 2 hours, putting into a water bath at 80 ℃, stirring, evaporating to dryness, and drying at 80 ℃ for 12 hours to obtain a first mixture; crushing the first mixture to obtain a resin for adsorbing cobalt ions; wherein the concentration of the cobalt chloride aqueous solution is 0.2 mol/L.
S102, dissolving 100g of potassium hydroxide in 400ml of absolute ethanol to obtain a potassium hydroxide/ethanol solution; adding the resin adsorbing cobalt ions obtained in the step S101 into the potassium hydroxide/ethanol solution, stirring and mixing, and putting the resin adsorbing cobalt ions and the potassium hydroxide/ethanol solution which are stirred and mixed into an oil bath at 80 ℃ for stirring and evaporation to obtain paste-like slurry; drying the slurry at 80 ℃, and then crushing again;
S103, in a nitrogen atmosphere, heating the product obtained in the step S102 to 800 ℃ at the speed of 2 ℃/min, preserving the heat for 2 hours, and then naturally cooling to room temperature;
s104, soaking the product obtained in the step S103 in 1mol/L hydrochloric acid solution for 36 hours, filtering, drying at 60 ℃ for 36 hours, and then continuously drying at 150 ℃ for 8 hours to obtain a porous carbon material, wherein the obtained porous carbon material presents a porous structure, and a BET test result shows that the obtained porous carbon material comprises micropores, mesopores and macropores, wherein the pore diameter of the micropores is 1-2 nm, the pore diameter of the mesopores is 2-5 nm, the pore diameter of the macropores is 20-100 nm, the specific surface area of the porous carbon is 820m 2/g, and the pore volume is 0.75cm 3/g.
in the embodiment of the invention, the preparation method of the cathode comprises the steps of carrying out hydrolysis reaction on porous carbon and stanniferous chloride salt to enable the stanniferous chloride salt to generate uniformly distributed stannic oxide nanoparticles in situ on a porous carbon substrate to obtain stannic oxide/porous carbon composite powder, so that organic combination of stannic oxide and porous carbon is realized, the generated nanoscale stannic oxide is favorable for exerting electrochemical activity, the porous carbon has a unique hierarchical pore structure, a buffer space is provided for volume expansion of stannic oxide in a circulation process, and circulation stability is improved; then mixing the obtained tin dioxide/porous carbon composite powder with polyacrylonitrile to obtain slurry; coating the slurry on a copper foil to obtain a pole piece; finally, in an inert gas atmosphere, carrying out carbonization heat treatment on the dried pole piece under a preset carbonization heat treatment condition to obtain a nitrogen-doped carbon/tin dioxide/porous carbon composite cathode, and completing preparation of the cathode; through to the drying after the pole piece carries out the carbonization heat treatment for polyacrylonitrile carbonization forms nitrogen-doped carbon coating, nitrogen-doped carbon coating has restrained the side reaction between tin dioxide and electrolyte on the tin dioxide surface formation protective layer, and because nitrogen-doped carbon coating self has high conductivity, has accelerated the quick transmission of electron, thereby has improved the electric conductivity of negative pole effectively, consequently when the negative pole that will adopt above-mentioned method to prepare is as lithium ion battery's negative pole, can improve lithium ion battery's specific capacity and cyclical stability. In addition, in the process of preparing the negative electrode, the preparation of the negative electrode is combined with the preparation of the composite material, so that the polyacrylonitrile is used as an organic carbon source of the nitrogen-doped carbon coating layer and is also used as a binder, and therefore, the preparation process of the negative electrode is simplified.
The following examples are provided to illustrate the preparation of the negative electrode, specifically as follows:
example 1
dispersing 100mg of porous carbon powder in a mixed solution of 200ml of absolute ethyl alcohol and 200ml of water through an ultrasonic effect to obtain a dispersion liquid of the porous carbon powder; then adding 1.5ml of concentrated hydrochloric acid into the dispersion liquid of the porous carbon powder and uniformly stirring; then under vigorous stirring, adding 1.2g of tin dichloride monohydrate into the dispersion liquid of the porous carbon powder and concentrated hydrochloric acid, heating to 80 ℃, and carrying out hydrolysis reaction for 1 hour to obtain a tin dioxide/porous carbon solution after the reaction is finished; after the temperature of the tin dioxide/porous carbon solution is reduced to room temperature, carrying out suction filtration on the tin dioxide/porous carbon solution, fully washing the tin dioxide/porous carbon solution with deionized water, and drying the tin dioxide/porous carbon solution to obtain tin dioxide/porous carbon composite powder; weighing the tin dioxide/porous carbon composite powder and the polyacrylonitrile powder according to the mass ratio of 90:10, adding the tin dioxide/porous carbon composite powder and the polyacrylonitrile powder into a dimethylformamide solvent, stirring and mixing to prepare slurry with good fluidity; coating the slurry on the copper foil in a tape casting manner to form a uniform thin layer with the thickness of 100 mu m, thereby obtaining a pole piece; drying the pole piece at 70 ℃; and then, carrying out carbonization heat treatment on the dried pole piece: cutting the dried pole piece into a small wafer with the diameter of 12mm, putting the small wafer into a tube furnace, heating to 400 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, and preserving heat for 1 hour to obtain the nitrogen-doped carbon/tin dioxide/porous carbon composite cathode, thereby completing the preparation of the cathode.
In the embodiment of the present invention, in order to analyze the structure and the morphology of the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode in example 1, the slurry obtained in example 1 is coated on a glass plate and is dried to obtain polyacrylonitrile/tin dioxide/porous carbon composite powder, and the polyacrylonitrile/tin dioxide/porous carbon composite powder is subjected to the same carbonization heat treatment process as in example 1 to obtain nitrogen-doped carbon/tin dioxide/porous carbon composite powder, and the result is shown in fig. 1 and 4, wherein fig. 4 is an X-ray diffraction pattern of the nitrogen-doped carbon/tin dioxide/porous carbon composite powder in example 1, and as can be seen from the X-ray diffraction pattern, the nitrogen-doped carbon/tin dioxide/porous carbon composite powder contains XRD peaks (X-ray diffraction ) of SnO 2 crystals (tin dioxide crystals), and the size of the XRD peaks is relatively wide, thus it is illustrated that the grain size of 2 is relatively small, fig. 1 is a photograph of the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode material in the embodiment of the present invention, and the external surface layer of the polyacrylonitrile/tin dioxide is characterized by the XRD peaks (X-ray diffraction) of carbon-doped carbon dioxide, and the carbon/tin dioxide powder is further illustrated by the high-doped carbon composite carbon powder adhesion state that the carbon-doped carbon dioxide thin-carbon composite powder is formed by the XPS, and the carbon-carbon composite powder is further illustrated by the carbon-carbon composite thin carbon-carbon composite powder.
as shown in fig. 5 to 7, the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode prepared in example 1 is applied to a lithium ion battery, and shows excellent electrochemical performance. Fig. 5 is a cycle performance diagram of the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode in example 1 of the present invention at different current densities, and it can be seen from fig. 5 that, when the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode is cycled at different current densities, higher specific capacity can be provided, and the stable test can still be performed after the large current charge and discharge; fig. 6 is a graph of the cycle performance of the nitrogen-doped carbon/tin dioxide/porous carbon composite anode in example 1 of the present invention at a current density of 1A/g, and it can be seen from fig. 6 that the nitrogen-doped carbon/tin dioxide/porous carbon composite anode has a specific capacity of 767mAh/g after 500 cycles, and the coulombic efficiency is close to 100% during the whole cycle except for the first few cycles, thus showing excellent cycle stability. Fig. 7 is a cycle performance diagram of the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrodes in example 1 and comparative examples 7 to 9 of the present invention at a current density of 0.1A/g, and as can be seen from fig. 7, the specific capacities of the first discharge and the second discharge of the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode obtained in example 1 at a current density of 0.1A/g are 1439mAh/g and 1067mAh/g, respectively, and after 100 cycles, the specific capacity is stabilized at 1117 mAh/g. Therefore, when the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode obtained in the embodiment is applied to a lithium ion battery, the specific capacity and the cycling stability of the lithium ion battery can be improved.
Example 2
this example is different from example 1 in that in the mixed solution of anhydrous ethanol and water, the anhydrous ethanol is 100ml, and the water is 300 ml; 1ml of concentrated hydrochloric acid is added into the dispersion liquid of the porous carbon powder; adding 2g of tin dichloride monohydrate into the dispersion liquid of the porous carbon powder and concentrated hydrochloric acid, and heating to 90 ℃ for hydrolysis reaction; in the carbonization heat treatment process, the temperature is raised to 400 ℃ at the heating rate of 10 ℃/min under the argon atmosphere, and the temperature is kept for 1 hour. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
example 3
This example is different from example 1 in that in the mixed solution of anhydrous ethanol and water, the anhydrous ethanol is 200ml, and the water is 300 ml; 2ml of concentrated hydrochloric acid is added into the dispersion liquid of the porous carbon powder; 1g of tin dichloride monohydrate added into the dispersion liquid of the porous carbon powder and concentrated hydrochloric acid; weighing the mass ratio of the tin dioxide/porous carbon composite powder to the polyacrylonitrile powder is 80: 20; in the carbonization heat treatment process, the temperature is raised to 400 ℃ at the heating rate of 3 ℃/min under the nitrogen atmosphere, and the temperature is kept for 0.5 hour. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
Example 4
This example differs from example 1 in that the heat treatment temperature during the carbonization heat treatment was 200 ℃. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
example 5
This example differs from example 1 in that the heat treatment temperature during the carbonization heat treatment was 300 ℃. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
example 6
This example differs from example 1 in that the heat treatment temperature during the carbonization heat treatment was 500 ℃. Other processes and steps of this embodiment are the same as those of embodiment 1, and will not be further described herein.
in the process of preparing the negative electrode, carbonization heat treatment and hydrolysis reaction are critical to the preparation method of the negative electrode, and therefore the following comparative examples 7 to 9 are carried out.
Comparative example 7
The difference between this comparative example and example 1 is that the pole piece after drying treatment was not carbonized, i.e. the final negative electrode obtained was the pole piece after drying. Other processes and steps of this comparative example are the same as those of example 1, and are not further described herein.
characterizing the obtained cathode; the X-ray diffraction pattern revealed that the diffraction peak of tin dioxide was weak, indicating that tin dioxide had poor crystallinity. The amorphous carbon coating on the tin dioxide surface, which is not characterized by high graphitization, is observed by transmission electron micrographs, thus indicating poor conductivity. The cycle performance of the obtained final negative electrode under the current density of 0.1A/g is shown in figure 7, and as can be seen from figure 7, the specific capacity attenuation amplitude of the negative electrode is large after 100 cycles of charge and discharge; the reason for this is that the tin dioxide particles have poor crystallinity, resulting in poor electrochemical activity, and the carbon coating layer on the surface of the tin dioxide has poor conductivity, so that electron transfer cannot be effectively accelerated during charging and discharging, resulting in a large specific capacity attenuation range.
comparative example 8
This comparative example is different from example 1 in that the heat treatment temperature was 600 c during the carbonization heat treatment. Other processes and steps of this comparative example are the same as those of example 1, and are not further described herein.
Characterizing the obtained nitrogen-doped carbon/tin dioxide/porous carbon composite cathode; the diffraction peak of tin dioxide is high and strong as seen from the X-ray diffraction spectrum, thereby indicating that the crystal grain size of tin dioxide is larger, and in addition, some mixed peaks which are attributed to the copper-tin alloy appear. The cycle performance of the obtained nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode under the current density of 0.1A/g is shown in fig. 7, and as can be seen from fig. 7, the initial discharge specific capacity of the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode is far lower than that of the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode prepared in example 1; the reason for this is that, increasing the heat treatment temperature causes formation of inactive copper-tin alloy impurity phases, which makes the structure of the negative electrode loose, resulting in easy detachment of the active material from the copper foil; in addition, the tin dioxide has larger particle size, which aggravates the volume expansion of the tin dioxide in the charging and discharging process, thereby causing lower specific capacity.
Comparative example 9
This comparative example differs from example 1 in that it employs a simple mechanical agitation method instead of an in-situ chemical method to mix the porous carbon and tin dioxide. Other processes and steps of this comparative example are the same as those of example 1, and are not further described herein.
This comparative example adopts simple mechanical stirring method to mix porous carbon and tin dioxide, specifically is: weighing the nanoscale tin dioxide powder, the porous carbon powder and the polyacrylonitrile powder according to the mass ratio of the nanoscale tin dioxide powder to the porous carbon powder to the polyacrylonitrile powder of 60:30:10, and mixing the porous carbon and the tin dioxide by adopting a mechanical stirring mode. The other process steps of this comparative example were the same as example 1.
the cycle performance of the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode of the comparative example under the current density of 0.1A/g is shown in fig. 7, and as can be seen from fig. 7, the initial discharge specific capacity of the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode is higher, but the attenuation of the specific capacity along with the increase of the cycle times is very obvious; the reason for this is that, with a simple mechanical mixing method, it is difficult to uniformly attach tin dioxide particles to the surface of the porous carbon substrate, so that the tin dioxide particles are easily stacked and agglomerated as the number of cycles increases, and it is difficult to sufficiently exert the buffer effect of the structure of the porous carbon on the volume expansion of tin dioxide, thereby causing the specific capacity of the nitrogen-doped carbon/tin dioxide/porous carbon composite negative electrode to be increasingly attenuated as the number of cycles increases.
the nitrogen-doped carbon/tin dioxide/porous carbon composite cathodes prepared in examples 2 to 6 and comparative examples 7 to 9 of the invention were applied to the lithium ion battery under the same process conditions as in example 1, and the cycle performance of the lithium ion battery at a current density of 0.1A/g was tested, and the test results are shown in table 1. Table 1 shows the cycle performance of the composite negative electrodes prepared in examples 1 to 6 and comparative examples 7 to 9 at a current density of 0.1A/g.
TABLE 1
As can be seen from table 1, compared with comparative examples 7 to 9, the nitrogen-doped carbon/tin dioxide/porous carbon composite cathodes prepared in examples 1 to 6 of the present invention all achieve high specific capacity and good cycling stability, which is inseparable from their unique composite structures. Specifically, the porous carbon matrix of the cathode obtained by the preparation method can provide a three-dimensional support carrier for the tin dioxide nanoparticles, so that the volume expansion of tin dioxide in the charging and discharging processes is relieved, and the cycle performance of the lithium ion battery is improved; and because the surface of the negative electrode material is adhered with the nitrogen-doped carbon coating thin layer, the side reaction between the tin dioxide and the electrolyte can be inhibited, so that the integral conductivity of the electrode is improved, and the specific capacity of the lithium ion battery is improved. In addition, by controlling the proper heat treatment temperature, the tin dioxide in the negative electrode material is small in particle size and is a single crystal phase in the negative electrode material, so that the prepared negative electrode can play a high role.
In summary, when the negative electrode material is used as a negative electrode of a lithium ion battery, the porous carbon matrix can provide a three-dimensional support carrier for the tin dioxide nanoparticles, so that volume expansion of tin dioxide in the charging and discharging processes is relieved, and the cycle stability of the lithium ion battery is improved; meanwhile, the surface of the negative electrode material is provided with the nitrogen-doped carbon coating layer, so that the side reaction between tin dioxide and electrolyte is inhibited, the integral conductivity of the electrode is improved, and the specific capacity of the lithium ion battery is improved.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and substitutions can be made without departing from the technical principle of the present invention, and these modifications and substitutions should also be regarded as the protection scope of the present invention.
Claims (16)
1. the negative electrode material is characterized by comprising a nitrogen-doped carbon coating layer, porous carbon and tin dioxide, wherein the tin dioxide is attached to the porous carbon, and the nitrogen-doped carbon coating layer wraps the tin dioxide and the porous carbon.
2. The negative electrode material of claim 1, wherein the nitrogen-doped carbon coating layer has a thickness of 1 to 5 nm.
3. The negative electrode material according to claim 1, wherein the tin dioxide has a particle size of 2 to 6 nm.
4. The negative electrode material of claim 1, wherein the nitrogen-doped carbon cladding layer is formed by carbonizing polyacrylonitrile.
5. a negative electrode comprising a copper foil and the negative electrode material according to any one of claims 1 to 4, wherein the negative electrode material is attached to the copper foil.
6. a method for producing a negative electrode, characterized by comprising the steps of:
Carrying out hydrolysis reaction on the porous carbon and stanniferous chloride salt to obtain stannic oxide/porous carbon composite powder;
Mixing the tin dioxide/porous carbon composite powder with polyacrylonitrile to obtain slurry;
Coating the slurry on a copper foil to obtain a pole piece;
Drying the pole piece;
And in an inert gas atmosphere, carrying out carbonization heat treatment on the dried pole piece under a preset carbonization heat treatment condition to obtain the nitrogen-doped carbon/tin dioxide/porous carbon composite cathode, and finishing the preparation of the cathode.
7. The preparation method of the negative electrode according to claim 6, wherein the hydrolysis reaction of the porous carbon and the stanniferous chloride salt is carried out to obtain the tin dioxide/porous carbon composite powder, and the method comprises the following steps:
Dispersing porous carbon powder in a mixed solution formed by an organic solvent and water to obtain a dispersion liquid of the porous carbon powder;
Stirring and mixing the dispersion liquid of the porous carbon powder and concentrated hydrochloric acid;
Carrying out hydrolysis reaction on the dispersion liquid of the porous carbon powder after stirring and mixing, concentrated hydrochloric acid and stanniferous chloride under preset reaction conditions to obtain a tin dioxide/porous carbon solution;
And carrying out suction filtration, washing and drying treatment on the tin dioxide/porous carbon solution to obtain the tin dioxide/porous carbon composite powder.
8. the method for manufacturing the negative electrode according to claim 7, wherein the volume ratio of the organic solvent to the water is 1:3 to 3: 1.
9. The method for manufacturing the negative electrode according to claim 7, wherein the organic solvent is any one of absolute ethanol, ethylene glycol, methanol, and propanol.
10. The method for producing the anode according to claim 6 or 7, wherein a mass ratio of the porous carbon to the tin-containing chloride salt is 1:10 to 1: 20.
11. The method for producing an anode according to claim 6 or 7, wherein the tin-containing chlorine salt is tin dichloride monohydrate.
12. The method of preparing the anode of claim 7, wherein the predetermined reaction conditions include: the reaction temperature is 70-90 ℃, and the reaction time is 0.5-2 h.
13. The method for preparing the negative electrode according to claim 6, wherein the tin dioxide/porous carbon composite powder is mixed with polyacrylonitrile to obtain slurry, and the slurry specifically comprises:
And stirring and mixing the tin dioxide/porous carbon composite powder and polyacrylonitrile powder with a dimethylformamide solvent to obtain the slurry.
14. The method for preparing the negative electrode according to claim 6 or 13, wherein the mass ratio of the tin dioxide/porous carbon composite powder to the polyacrylonitrile is 4: 1-9: 1.
15. The method for manufacturing an anode according to claim 6, wherein the inert gas is nitrogen or argon.
16. the method of preparing the anode according to claim 6, wherein the preset carbonization heat treatment conditions include: the heating rate is 2-10 ℃/min, the heat treatment temperature is 200-500 ℃, and the heat preservation time is 0.5-1 h.
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