CN112018360A - Lithium ion battery cathode material, preparation method thereof and lithium ion battery - Google Patents
Lithium ion battery cathode material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a lithium ion battery cathode material, a preparation method thereof and a lithium ion battery, wherein the lithium ion battery cathode material is SnO with carbon nano particles wrapped on the surface2A nanorod, wherein the surface of the SnO is coated with carbon nano-particles2The nano rod has two horizontal mesoporous structures, and the pore sizes of the nano rod are distributed in 3.8-5nm and 18.3-24.2 nm. The lithium ion battery cathode material has larger specific surface area and excellent conductivity, thereby improving the lithium ion battery cathode materialThe electrochemical performance of (2).
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery cathode material and a preparation method thereof, and a lithium ion battery containing the lithium ion battery cathode material.
Background
The lithium ion battery is a secondary battery (rechargeable battery) which mainly depends on the movement of lithium ions between a positive electrode and a negative electrode to work, and mainly comprises the positive electrode, the negative electrode, electrolyte, a diaphragm and the like, wherein the selection of a negative electrode material is directly related to the performance of the lithium ion battery.
SnO2The material is considered to be one of lithium ion battery negative electrode materials with wide development prospect due to high theoretical specific capacity. But due to SnO2The material has large initial irreversible capacity and serious volume effect in the charge and discharge process, so that the material is prepared into a special shape with the specific capacity decaying too fast, the cycling stability is reduced, and the application of the material in the aspect of lithium ion battery cathode materials is seriously limited. SnO mainly passing through morphology at present2Nano-materials or compounding with other materials to relieve SnO2To increase SnO2The electrochemical performance of the material, but the existing composite method has certain difficulties in the synthesis aspect of the material appearance consistency and the composite mode of the material.
Disclosure of Invention
In view of the above, the present invention needs to provide a negative electrode material for a lithium ion battery, a method for preparing the same, and a lithium ion battery, wherein the negative electrode material is nano-rod-shaped SnO having two pore size levels2The @ C composite has a large specific surface area and excellent conductivity, so that the electrochemical performance of the lithium ion battery negative electrode material is improved, and the problems are solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a lithium ion battery cathode material which is SnO with carbon nano particles wrapped on the surface2Nanorods, said surface coatingSnO coated with carbon nanoparticles2The nano rod has two horizontal mesoporous structures, and the pore sizes of the nano rod are distributed in 3.8-5nm and 18.3-24.2 nm.
Further, the SnO with the surface coated with the carbon nano particles2The length of the nano rod is 1-3 μm, and the diameter is 200-300 nm.
The invention also provides a preparation method of the lithium ion battery anode material, which comprises the following steps:
respectively dissolving a tin source and a copper source in deionized water, mixing, adding a sodium hydroxide solution while mixing, and stirring for reaction to obtain a tin-copper hydroxide precursor;
and dissolving the tin-copper hydroxide precursor and polyvinylpyrrolidone in methanol, uniformly stirring, and adding a zinc source and a cobalt source to obtain a solution A.
Dissolving 2-methylimidazole in methanol to prepare a solution B;
uniformly stirring the solution A and the solution B, and performing solid-liquid separation to obtain a Zn, Co-ZIFs coated precursor material;
calcining the precursor material coated with Zn, Co-ZIFs, and etching the calcined product in hydrochloric acid solution to obtain porous carbon-coated SnO2And (4) nanorods.
Further, the tin source is SnCl4·5H2O, the copper source is Cu (NO)3)2·3H2O。
Further, the specific steps of obtaining the tin-copper hydroxide precursor after the stirring reaction are as follows: stirring for 2h, standing, and then sequentially carrying out solid-liquid separation, washing and drying to obtain the tin-copper hydroxide precursor.
Further, the zinc source is Zn (NO)3)2·6H2O, the cobalt source is Co (NO)3)2·6H2O。
Further, the solid-liquid separation comprises the following specific steps: after centrifugation, the solid was washed and dried.
Further, the calcination comprises the following specific steps: under the anaerobic condition, heating to 550-600 ℃ at the speed of 2-5 ℃/min, preserving the heat for 2-3 h, and then cooling to room temperature at the speed of 2-5 ℃/min; and then heating the product to 700-800 ℃ at the temperature of 3-4 ℃/min in the air atmosphere, preserving the heat for 3 hours, and then cooling to room temperature at the temperature of 3-4 ℃/min to obtain a calcined product.
Further, the step of placing the calcinated substance in hydrochloric acid solution for etching specifically comprises: and (3) placing the calcined substance into a hydrochloric acid solution, stirring, etching for at least 30min, carrying out solid-liquid separation, washing and drying.
The invention also provides a lithium ion battery, which comprises the lithium ion battery negative electrode material.
The lithium ion battery cathode material has two pore size levels, so that more active sites are provided for the migration of lithium ions, the transportation path of the ions is shortened, the lithium ion battery cathode material has a larger specific surface area, the migration path of the lithium ions can be shortened, the lithium storage performance of the material is improved, and the volume effect in the charge and discharge process can be buffered to a certain extent; in addition, the coating of the carbon material can improve the conductivity of the material and can further buffer the volume effect generated in the charging and discharging processes. The lithium ion battery cathode material has excellent electrochemical performance.
Drawings
Fig. 1 is an XRD characterization chart of the lithium ion battery negative electrode material prepared in example 1 of the present invention;
fig. 2 is a raman test chart of the lithium ion battery negative electrode material prepared in example 1 of the present invention;
FIG. 3 is a SEM representation of the negative electrode material of the lithium ion battery prepared in example 1 of the present invention;
FIG. 4 is a BET test chart of the lithium ion battery negative electrode material prepared in example 1 of the present invention;
fig. 5 is a graph showing the cycle performance test of a half cell made of the negative electrode material for lithium ion battery prepared in example 1.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention discloses a lithium ion battery cathode material, which is SnO with carbon nano particles wrapped on the surface2A nanorod, wherein the surface of the SnO is coated with carbon nano-particles2The nano rod has two horizontal mesoporous structures, and the pore sizes of the nano rod are distributed in 3.8-5nm and 18.3-24.2 nm.
The lithium ion battery cathode material has two levels of mesoporous structures, so that more active sites are provided for the migration of lithium ions, the transportation path of the ions is shortened, the volume expansion caused by charge and discharge can be effectively buffered, and the electrochemical performance of the cathode material is enhanced.
Further, the SnO with the surface coated with the carbon nano particles2The length of the nano rod is 1-3 μm, and the diameter is 200-300 nm. SnO with carbon nano particles wrapped on surface in invention2The nano-rod has larger specific surface area, can improve the lithium storage core of the material and buffer the volume effect in the charging and discharging process to a certain extent, and in some embodiments of the invention, the SnO with the carbon nano-particles wrapped on the surface2The nano rod is 602.58m2·g-1。
The second aspect of the present invention provides a method for preparing the negative electrode material of the lithium ion battery according to the first aspect of the present invention, comprising the following steps:
respectively dissolving a tin source and a copper source in deionized water, mixing, adding a sodium hydroxide solution while mixing, and stirring for reaction to obtain a tin-copper hydroxide precursor, wherein the copper source can participate in the later ZIFs reaction, so that tin can be mainly combined with the tin source, and the copper is replaced by zinc in the later reaction stage;
dissolving the tin-copper hydroxide precursor and polyvinylpyrrolidone in methanol, uniformly stirring, and adding a zinc source and a cobalt source to obtain a solution A;
dissolving 2-methylimidazole in methanol to prepare a solution B;
uniformly stirring the solution A and the solution B, and performing solid-liquid separation to obtain a Zn, Co-ZIFs coated precursor material;
calcining the precursor material coated with Zn, Co-ZIFs, and etching the calcined product in hydrochloric acid solution to obtain porous carbon-coated SnO2And (4) nanorods.
Firstly, preparing a nanorod-shaped tin-copper hydroxide precursor, then reacting the tin-copper hydroxide precursor and a zinc source with a cobalt source and 2-methylimidazole through the regulation and adhesion of PVP to obtain a precursor material with the surface coated with Zn and Co-ZIFs, further calcining in an inert atmosphere and an air atmosphere in two steps, and then etching by hydrochloric acid to obtain a mesoporous structure with two aperture levels.
Further, the tin source is SnCl4·5H2O, the copper source is Cu (NO)3)2·3H2And O, preferably, the mass ratio of the tin source to the copper source to the sodium hydroxide is 1: 0.52-0.69: 1.14 more preferably, the mass ratio of the tin source, the copper source and the sodium hydroxide is 1: 0.69: 1.14.
further, the specific steps of obtaining the tin-copper hydroxide precursor after the stirring reaction are as follows: stirring for 2h, standing, and then sequentially carrying out solid-liquid separation, washing and drying to obtain the tin-copper hydroxide precursor. It is understood that the purpose of standing is to perform subsequent solid-liquid separation, and therefore, the specific time thereof is not particularly limited and may be adjusted as required, and preferably, in some specific embodiments of the present invention, the standing time is 12 hours; in addition, solid-liquid separation, washing, drying and the like are all conventional operations in the field, and are not limited, preferably, in some specific embodiments of the invention, the solid-liquid separation, the washing, the drying and the like are performed by standing, centrifugal separation, washing 3 times by using deionized water and absolute ethyl alcohol alternately, and finally vacuum drying at 60 ℃.
Further, the zinc source is Zn (NO)3)2·6H2O, the cobalt source is Co (NO)3)2·6H2O, preferably, the mass ratio of the zinc source to the cobalt source to the polyvinylpyrrolidone to the tin-copper hydroxide to the 2-methylimidazole is 1.06:0.05: 1-1.5: 0.3: 2.47, more preferably, the mass ratio of the zinc source, the cobalt source, the polyvinylpyrrolidone, the tin copper hydroxide and the 2-methylimidazole is 1.06:0.05: 1: 0.3: 2.47. further, the solid-liquid separation comprises the following specific steps: after centrifugation, the solid was washed and dried. In some specific embodiments of the present invention, the specific steps are: after centrifugation, the solid was washed 3 times with methanol and dried under vacuum at 60 ℃.
Further, the calcination comprises the following specific steps: under the anaerobic condition, heating to 550-600 ℃ at the speed of 2-5 ℃/min, preserving the heat for 2-3 h, and then cooling to room temperature at the speed of 2-5 ℃/min; and then heating the product to 700-800 ℃ at the temperature of 3-4 ℃/min in the air atmosphere, preserving the heat for 3 hours, and then cooling to room temperature at the temperature of 3-4 ℃/min to obtain a calcined product. More preferably, under the anaerobic condition, the temperature is raised to 600 ℃ at the speed of 5 ℃/min, and the temperature is kept for 2h, and then the temperature is lowered to the room temperature at the speed of 5 ℃/min; then heating the product to 700 ℃ at the temperature of 4 ℃/min in the air atmosphere, preserving the heat for 3h, and then cooling to room temperature at the temperature of 4 ℃/min to obtain a calcined substance. It is understood that the anaerobic conditions herein refer to the exclusion of oxygen, which may be performed in an inert gas or nitrogen atmosphere as is conventional in the art, and that inert gases may be a conventional choice in the art, such as argon, helium, and the like.
Further, the step of placing the calcinated substance in hydrochloric acid solution for etching specifically comprises: and placing the calcined substance in a hydrochloric acid solution, stirring and etching for at least 30min, carrying out solid-liquid separation, washing and drying. Preferably, in some embodiments of the present invention, the concentration of the hydrochloric acid is 3mol/L, and the amount of the hydrochloric acid solution is not particularly limited, so as to meet the etching requirement.
In a third aspect of the invention, a lithium ion battery is disclosed, which comprises the lithium ion battery negative electrode material according to the first aspect of the invention.
The technical solution of the present invention will be more clearly and completely described below with reference to specific embodiments.
Example 1
0.35g of SnCl is weighed out4·5H2O in 100mL deionized water, 0.24g Cu (NO) was weighed3)2·3H2Dissolving O in 50mL of deionized water, mixing the two solutions, adding a sodium hydroxide solution (prepared by dissolving 0.40g of NaOH in 5mL of deionized water) while mixing, magnetically stirring the mixed solution for 2h, standing for 12h, performing centrifugal separation, alternately washing with deionized water and absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain a light blue tin-copper hydroxide precursor for later use;
dissolving 1.33g of polyvinylpyrrolidone and 0.4g of tin-copper hydroxide precursor in 120mL of methanol, stirring for 30min, fully mixing, and adding 1.416g of Zn (NO)3)2·6H2O and 0.0693g of Co (NO)3)2·6H2O, continuously stirring for 2 hours to prepare a solution A;
3.284g of 2-methylimidazole is dissolved in 120mL of methanol and stirred for 30min to prepare a solution B;
mixing the solution B and the solution A, stirring for 30min, performing centrifugal separation, washing the solid with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain a precursor material 1 coated with Zn, Co-ZIFs;
placing the precursor material 1 coated by Zn, Co-ZIFs in a tube furnace, heating to 600 ℃ at the speed of 5 ℃/min under the argon atmosphere, preserving the temperature for 2h, and then cooling to room temperature at the speed of 5 ℃/min; then the obtained product is put into a muffle furnace to be heated to 700 ℃ at the temperature of 4 ℃/min and is kept for 3h, and then the temperature is reduced to the room temperature at the same speed;
placing the obtained calcined substance in 30mL of 3mol/L hydrochloric acid solution, stirring for 30min for etching, performing centrifugal separation, washing with deionized water and anhydrous ethanol for 3 times alternately, and placingDrying in a vacuum drying oven at 60 ℃ to obtain the final SnO coated with porous carbon2And (3) a nanorod negative electrode material.
Comparative example 1
0.35g of SnCl is weighed out4·5H2O in 100mL deionized water, 0.24g Cu (NO) was weighed3)2·3H2Dissolving O in 50mL of deionized water, mixing the two solutions, adding a sodium hydroxide solution (prepared by dissolving 0.40g of NaOH in 5mL of deionized water) while mixing, magnetically stirring the mixed solution for 2h, standing for 12h, performing centrifugal separation, alternately washing with deionized water and absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain a light blue tin-copper hydroxide precursor for later use;
dissolving 1.33g of polyvinylpyrrolidone and 0.4g of tin-copper hydroxide precursor in 120mL of methanol, stirring for 30min, fully mixing, and adding 1.416g of Zn (NO)3)2·6H2O and 0.0693g of Co (NO)3)2·6H2O, continuously stirring for 2 hours to prepare a solution;
placing the solution in a centrifuge, performing centrifugal separation, washing the solid with methanol for 3 times, and then placing in a vacuum drying oven at 60 ℃ for drying to obtain a precursor material 3;
placing the Zn and Co coated precursor material 3 in a tube furnace, heating to 600 ℃ at the speed of 5 ℃/min under the argon atmosphere, preserving the heat for 2h, and then cooling to room temperature at the speed of 5 ℃/min; then the obtained product is put into a muffle furnace to be heated to 700 ℃ at the temperature of 4 ℃/min and is kept for 3h, and then the temperature is reduced to the room temperature at the same speed;
placing the obtained calcined substance in 30mL of 3mol/L hydrochloric acid solution, stirring for 30min for etching, performing centrifugal separation, washing with deionized water and anhydrous ethanol for 3 times alternately, and oven drying in a vacuum drying oven at 60 deg.C to obtain SnO2And (3) a nanorod negative electrode material.
Comparative example 2
0.35g of SnCl is weighed out4·5H2Dissolving O in 100mL deionized water, adding sodium hydroxide solution (0.40g NaOH dissolved in 5mL deionized water), magnetically stirring the mixed solution for 2h, standing for 12h, centrifuging, and alternately dissolving with deionized water and anhydrous ethanolWashing for 3 times, and drying in a vacuum drying oven at 60 deg.C to obtain precursor;
dissolving 1.33g polyvinylpyrrolidone and 0.4g precursor in 120mL methanol, stirring for 30min, adding 1.416g Zn (NO)3)2·6H2O and 0.0693g of Co (NO)3)2·6H2O, continuously stirring for 2 hours to prepare a solution A;
3.284g of 2-methylimidazole is dissolved in 120mL of methanol and stirred for 30min to prepare a solution B;
mixing the solution B and the solution A, stirring for 30min, performing centrifugal separation, washing the solid with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain a precursor material 2 coated with Zn, Co-ZIFs;
placing the precursor material 2 coated by Zn, Co-ZIFs in a tube furnace, heating to 600 ℃ at the speed of 5 ℃/min under the argon atmosphere, preserving the temperature for 2h, and then cooling to room temperature at the speed of 5 ℃/min; then the obtained product is put into a muffle furnace to be heated to 700 ℃ at the temperature of 4 ℃/min and is kept for 3h, and then the temperature is reduced to the room temperature at the same speed;
placing the obtained calcined substance in 30mL of 3mol/L hydrochloric acid solution, stirring for 30min for etching, then performing centrifugal separation, respectively washing with deionized water and absolute ethyl alcohol for 3 times alternately, and then placing in a vacuum drying oven at 60 ℃ for drying to obtain the final porous carbon coated SnO2Nanorod negative electrode material
Example 2
0.35g of SnCl is weighed out4·5H2O in 100mL DI water, 0.182g Cu (NO) was weighed3)2·3H2Dissolving O in 50mL of deionized water, mixing the two solutions, adding a sodium hydroxide solution (prepared by dissolving 0.40g of NaOH in 5mL of deionized water) while mixing, magnetically stirring the mixed solution for 2h, standing for 12h, performing centrifugal separation, alternately washing with deionized water and absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain a light blue tin-copper hydroxide precursor for later use;
dissolving 1.33g of polyvinylpyrrolidone and 0.266g of tin-copper hydroxide precursor in 120mL of methanol, stirring for 30min, fully mixing, and adding 0.940g of Zn (NO)3)2·6H2O and 0.0444g of Co (NO)3)2·6H2O, continuously stirring for 2 hours to prepare a solution A;
dissolving 2.191g of 2-methylimidazole in 120mL of methanol, and stirring for 30min to obtain a solution B;
mixing the solution B and the solution A, stirring for 30min, performing centrifugal separation, washing the solid with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain a precursor material 1 coated with Zn, Co-ZIFs;
placing the precursor material 1 coated by Zn, Co-ZIFs in a tube furnace, heating to 580 ℃ at the speed of 3 ℃/min under the argon atmosphere, preserving the temperature for 3h, and then cooling to room temperature at the speed of 3 ℃/min; then placing the obtained product in a muffle furnace, heating to 750 ℃ at the temperature of 3 ℃/min, preserving the heat for 3h, and then cooling to room temperature at the same speed;
placing the obtained calcined substance in 30mL of 3mol/L hydrochloric acid solution, stirring for 30min for etching, then performing centrifugal separation, respectively washing with deionized water and absolute ethyl alcohol for 3 times alternately, and then placing in a vacuum drying oven at 60 ℃ for drying to obtain the final porous carbon coated SnO2And (3) a nanorod negative electrode material.
Example 3
0.35g of SnCl is weighed out4·5H2O in 100mL deionized water, 0.21g Cu (NO) was weighed3)2·3H2Dissolving O in 50mL of deionized water, mixing the two solutions, adding a sodium hydroxide solution (prepared by dissolving 0.40g of NaOH in 5mL of deionized water) while mixing, magnetically stirring the mixed solution for 2h, standing for 12h, performing centrifugal separation, alternately washing with deionized water and absolute ethyl alcohol for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain a light blue tin-copper hydroxide precursor for later use;
dissolving 1.33g of polyvinylpyrrolidone and 0.3324g of tin-copper hydroxide precursor in 120mL of methanol, stirring for 30min, fully mixing, and adding 1.174g of Zn (NO)3)2·6H2O and 0.0554g of Co (NO)3)2·6H2O, continuously stirring for 2 hours to prepare a solution A;
2.737g of 2-methylimidazole is dissolved in 120mL of methanol and stirred for 30min to prepare a solution B;
mixing the solution B and the solution A, stirring for 30min, performing centrifugal separation, washing the solid with methanol for 3 times, and drying in a vacuum drying oven at 60 ℃ to obtain a precursor material 1 coated with Zn, Co-ZIFs;
placing the precursor material 1 coated by Zn, Co-ZIFs in a tube furnace, heating to 550 ℃ at the speed of 2 ℃/min under the argon atmosphere, preserving heat for 3h, and then cooling to room temperature at the speed of 2 ℃/min; then placing the obtained product in a muffle furnace, heating to 800 ℃ at the temperature of 3 ℃/min, preserving the temperature for 3h, and then cooling to room temperature at the same speed;
placing the obtained calcined substance in 30mL of 3mol/L hydrochloric acid solution, stirring for 30min for etching, then performing centrifugal separation, respectively washing with deionized water and absolute ethyl alcohol for 3 times alternately, and then placing in a vacuum drying oven at 60 ℃ for drying to obtain the final porous carbon coated SnO2And (3) a nanorod negative electrode material.
The negative electrode material prepared in example 1 was subjected to XRD characterization, and as shown in FIG. 1, the negative electrode material had a tetragonal rutile structure SnO2A diffraction peak of (a);
the anode material in example 1 was analyzed by raman spectroscopy, and as shown in fig. 2, there were characteristic raman peak D band peak and G band peak of carbon, indicating that the anode material in example 1 has a carbon material therein.
Further, the negative electrode material in example 1 is subjected to SEM characterization, and the morphology and size of the negative electrode material are observed, and it can be seen from fig. 3 that the negative electrode material in example 1 is in the shape of a nanorod, has a diameter of 1-3 μm, and is coated with carbon nanoparticles.
Further, the pore size analysis of the negative electrode material was performed using an N2 adsorption-desorption isotherm. As can be seen from FIG. 4a, the adsorption-desorption isothermal curve is type IV, which shows that the nano-rod-shaped SnO2@ C composite has a porous structure and the specific surface area is 602.58m2g-1. FIG. 4b is a pore size distribution curve diagram of nano-rod-shaped SnO2@ C, which shows that the pore sizes of the material are mainly distributed at 3.8-5nm and 18.3-24.2nm, and the material is of two horizontal mesoporous structures. The pore size analysis was performed in the same manner for the negative electrode materials of comparative example 1 and comparative example 2, and the results are shown in the following table:
| morphology of the product | Kind of pore diameter | Range of pore diameters | |
| Example 1 | |
2 | 3.8-5nm and 18.3-24.2nm |
| Comparative example 1 | Nano rod shape | 1 | 18.3-24.2nm |
| Comparative example 2 | Nano rod shape | 1 | 3.8-5nm |
Only one kind of negative electrode material with a level of pore size was obtained in both comparative example 1 and comparative example 2.
The negative electrode materials in example 1 and comparative example 1 were mixed with carbon black and a binder in the following ratio of 8: 1: 1, uniformly coating the mixture on a copper foil, drying, assembling the semi-cell with a lithium sheet in a glove box, and testing the cycle performance of the semi-cell.
As shown in FIG. 5, in a current density of0.5A·g-1The cycle performance under the conditions is shown in the figure, and the first discharge specific capacity and the charge specific capacity of the negative electrode material in the example 1 are 1101mAh g respectively-1And 650 mAh. g-1Wherein the specific discharge capacity of the negative electrode material in the embodiment 1 can be maintained to 647mAh g after 120 cycles-1The coulomb efficiency in the whole process is as high as 99.7%. The charge-discharge specific capacity of the material is obviously higher than that of the negative electrode material in the comparative example 1, the cycling stability is good, and the material shows good electrochemical performance. In addition, when the negative electrode material obtained in comparative example 1 was tested under the same conditions, the first discharge specific capacity and the charge specific capacity in comparative example 1 were 941mAh · g-1And 450 mAh.g-1. The possible reasons for the comparison result are that the carbon coating improves the conductivity of the material, the volume expansion in the charging and discharging process is relieved to a great extent, the structure with two pore diameters is favorable for the infiltration of electrolyte, and the lithium ion conductivity is higher, so that the electrochemical performance of the material is improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The lithium ion battery cathode material is characterized in that the lithium ion battery cathode material is SnO with carbon nano particles wrapped on the surface2A nanorod, wherein the surface of the SnO is coated with carbon nano-particles2The nano rod has two horizontal mesoporous structures, and the pore sizes of the nano rod are distributed in 3.8-5nm and 18.3-24.2nm。
2. The lithium ion battery negative electrode material of claim 1, wherein the SnO with the surface coated with carbon nanoparticles2The length of the nano rod is 1-3 μm, and the diameter is 200-300 nm.
3. The preparation method of the negative electrode material of the lithium ion battery as claimed in claim 1 or 2, characterized by comprising the following steps:
respectively dissolving a tin source and a copper source in deionized water, mixing, adding a sodium hydroxide solution while mixing, and stirring for reaction to obtain a tin-copper hydroxide precursor;
and dissolving the tin-copper hydroxide precursor and polyvinylpyrrolidone in methanol, uniformly stirring, and adding a zinc source and a cobalt source to obtain a solution A.
Dissolving 2-methylimidazole in methanol to prepare a solution B;
uniformly stirring the solution A and the solution B, and performing solid-liquid separation to obtain a Zn, Co-ZIFs coated precursor material;
calcining the precursor material coated with Zn, Co-ZIFs, and etching the calcined product in hydrochloric acid solution to obtain porous carbon-coated SnO2And (4) nanorods.
4. The method of claim 3, wherein the source of tin is SnCl4·5H2O, the copper source is Cu (NO)3)2·3H2O。
5. The preparation method according to claim 3, wherein the specific steps of obtaining the tin-copper hydroxide precursor after the stirring reaction are as follows: and stirring, standing, and then sequentially carrying out solid-liquid separation, washing and drying to obtain the tin-copper hydroxide precursor.
6. The method of claim 3, wherein the zinc source is Zn (NO)3)2·6H2O, the cobalt source is Co (NO)3)2·6H2O。
7. The preparation method according to claim 3, wherein the solid-liquid separation comprises the following specific steps: after centrifugation, the solid was washed and dried.
8. The preparation method according to claim 3, wherein the calcination comprises the following specific steps: under the anaerobic condition, heating to 550-600 ℃ at the speed of 2-5 ℃/min, preserving the heat for 2-3 h, and then cooling to room temperature at the speed of 2-5 ℃/min; and then heating the product to 700-800 ℃ at the temperature of 3-4 ℃/min in the air atmosphere, preserving the heat for 3 hours, and then cooling to room temperature at the temperature of 3-4 ℃/min to obtain a calcined product.
9. The preparation method according to claim 3, wherein the step of etching the calcined product in a hydrochloric acid solution comprises the following steps: and (3) placing the calcined substance into a hydrochloric acid solution, stirring, etching for at least 30min, carrying out solid-liquid separation, washing and drying.
10. A lithium ion battery comprising the lithium ion battery negative electrode material according to claim 1 or 2.
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