Porous silicon/carbon composite material synthesized in situ by taking porous polymer microspheres as template, preparation method and lithium ion battery
Technical Field
The invention relates to the field of preparation of lithium ion battery cathode materials, in particular to a porous silicon/carbon composite material synthesized in situ by taking porous polymer microspheres as a template, a preparation method and a lithium ion battery.
Background
With the progress of the electronic industry, electric automobiles and aerospace technologies, higher requirements are put forward on the performance of lithium ion batteries. Therefore, to realize breakthrough of lithium ion batteries in energy density and power density, a crucial "bottleneck" problem is how to design and develop new electrode materials. In the field of research of lithium ion batteries, the research focus is on negative electrode materials. At present, the graphite electrode has low theoretical lithium storage capacity (LiC)6372mAh/g) made it very difficult to make breakthrough progress any more. Therefore, research and development of novel negative electrode materials with high specific capacity, high charge-discharge efficiency, high cycle performance, good high-rate charge-discharge performance, high safety and low cost are urgent, become popular subjects in the field of lithium ion battery research, and have very important significance for development of lithium ion batteries.
Silicon-based materials are widely considered to be the most important high capacity anode materials. Besides the advantage of abundant reserves in nature, the theoretical lithium intercalation capacity is 4200mAh/g (Li)22Si59800mAh/mL), high lithium desorption and insertion platform and higher safety performance. Although siliconThe cathode material has good application prospect, but because the volume expansion of silicon is up to 420% in the charging and discharging process, under the action of stress, particles are easy to crush, and the capacity of the material is rapidly reduced. In addition, repeated volume expansion and contraction make the interface between silicon and electrolyte very unstable, leading to the continuous destruction and regrowth of SEI film on the surface of the negative electrode, and the process can consume a large amount of Li in the electrolyte+The charge and discharge efficiency is deteriorated, and an excessively thick SEI film affects Li+The transmission of (2) increases the internal resistance and polarization of the battery, further aggravating the capacity attenuation of the material.
In the prior art, in order to improve the cycle performance of a silicon material, the main strategy adopted is to design the composition and microstructure of the material so as to adapt to the volume effect of silicon and maintain an electrode conductive network, and the main approaches include nano-crystallization, composite, porous and the like. However, the effect of improving the cycle performance of the alloy material by adopting the nano material is not good; the single active doping or inert doping can partially inhibit the volume expansion of the silicon-based material, but can still not completely solve the problems of silicon dispersion and agglomeration; other methods have limited effect on improving stability and have great pollution to the environment.
Chinese patent CN103165874A discloses a porous silicon negative electrode material of a lithium ion battery, a preparation method and application thereof. The method takes silicon-based alloy powder as a raw material and reacts with inorganic acid to generate porous silicon particles; and cleaning with HF solution to remove surface silicon oxide, washing, and drying to obtain the porous silicon material. Although the capacity of the material is high, the coulombic efficiency is low for the first time (about 60%), and an HF solution is used in the preparation process, so that the environmental pollution is caused.
Chinese patent CN102157731A discloses a silicon/carbon composite negative electrode material of a lithium ion battery and a preparation method thereof. According to the method, a porous silicon substrate is prepared by magnesium thermal reduction of mesoporous silicon dioxide, and then carbon coating is carried out to obtain the silicon/carbon composite cathode material. The mesoporous silicon dioxide and magnesium powder used in the method have high cost and are not beneficial to industrial production.
Chinese patent CN102969489A discloses a silicon/carbon composite material and a preparation method thereof. The method is characterized in that silicon and metal oxide obtained by reducing silicon dioxide by using metal (such as lithium, sodium, potassium, magnesium and the like) with activity greater than that of silicon are subjected to acid corrosion and hydrothermal carbon coating to obtain the silicon/carbon composite material. The metals used in the method are all metals with strong activity, and the simple substances thereof have high cost and great danger, so the method is not beneficial to industrial production.
CN103531760 discloses a porous silicon/carbon composite microsphere with a yolk-eggshell structure and a preparation method thereof, wherein a microsphere core provided by the porous submicron silicon microsphere is a porous submicron silicon sphere with the diameter of 400-900 nm, a shell is porous carbon with the thickness of 10-60 nm and the inner diameter of a cavity of 800-1400 nm, and the preparation method is that SiO is used for preparing the porous submicron silicon microsphere2Coating the core with carbon source, and sintering to obtain porous carbon-coated SiO2Powder, treating partial SiO with alkali2Obtaining porous carbon coated SiO with yolk-eggshell structure2Powder, then reducing SiO by magnesiothermic reduction2Reducing the porous carbon particles into silicon powder, and finally treating redundant silicon dioxide through HF (hydrogen fluoride) to obtain the porous carbon-coated porous silicon/carbon composite microspheres with the yolk-eggshell structure.
Disclosure of Invention
In order to solve the problems in the prior art, the invention designs and constructs a more excellent porous structure, and provides a porous silicon/carbon composite material synthesized in situ by taking porous polymer microspheres as a template, a preparation method and a lithium ion battery, thereby improving the reversibility and the cycling stability of the porous silicon/carbon cathode material in the charge-discharge process.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
the preparation method for in-situ synthesis of the porous silicon/carbon composite negative electrode material by taking the porous polystyrene microspheres as the template comprises the following steps:
the method for in-situ synthesis of the porous silicon/carbon composite anode material by taking the porous polymer microspheres as the template comprises the following steps:
s1: adding the porous polymer microspheres into water, heating and stirring to uniformly disperse the porous polymer microspheres to obtain a suspension solution;
s2: adding a silicon source into the suspension solution obtained in the step S1, and continuously heating and stirring to obtain a mixed solution;
s3: filtering, washing with deionized water and drying the mixed solution obtained in the step S2 in sequence, adding a reducing agent, grinding and mixing to obtain an intermediate product A;
s4: treating the intermediate product A through a thermal reduction process to obtain an intermediate product B;
s5: and (4) carrying out acid washing on the intermediate product B obtained in the step (S4), washing with deionized water, filtering and drying to obtain the final product, namely the porous silicon/carbon composite negative electrode material.
Further, the porous polymer microspheres in S1 are one or a mixture of more of porous polystyrene microspheres, porous polyethylene microspheres, porous polyvinyl chloride microspheres, porous polypropylene microspheres, and porous polyurethane microspheres;
the average particle size D50 of the porous polymer microsphere is 500 nm-25 mu m, the pore distribution is uniform, and the pore size is 20-200 nm.
The average particle size of the porous polymer microspheres and the size of the gaps in the technical scheme are crucial to the realization of the final performance effect, and as the average particle size of the porous polymer microspheres is smaller, the corresponding pore size is smaller, but when the average particle size of the porous polymer microspheres is too small (D50 is less than 500 nm), the too small pore size (less than 20nm) can cause difficulty in industrial production, and is not beneficial to the performance optimization of the prepared porous silicon/carbon composite negative electrode material, so that the performance is remarkably reduced; when the average particle size D50 is too large (larger than 25 μm) and the pore size is too large (larger than 200nm), the specific capacity and the first efficiency are obviously reduced, and the capacity is not easy to maintain after multiple cycles, so that the limitation that the average particle size D50 of the porous polymer microspheres is 500 nm-25 μm and the pore size is 20-200 nm is shown in the invention, and the limitation is the core parameter limitation of the structure-activity relationship in the system.
Furthermore, the heating temperature in S1 and the heating temperature in S2 are both 40-60 ℃, the stirring time is 20-40 min, and the stirring speed is 200-2000 r/min.
Further, in S2, the silicon source is one or a mixture of more of ethyl silicate, methyl silicate, sodium silicate, methoxysilane, ethoxysilane, propoxysilane and butoxysilane, the mass ratio of the porous polymer microsphere to the silicon source is 1: 1-1: 100, and the mass ratio of the porous polymer microsphere to the silicon source is preferably 1: 10-1: 50.
Further, the drying temperature in S3 is 50-100 ℃, and the drying time is 1-3 h.
Further, in S4, the reducing agent is one or more of titanium hydride powder, lithium hydride powder, and aluminum powder;
the particle size of the reducing agent is 3-20 mu m, the mass ratio of the reducing agent to the silicon source is 5: 1-1: 5, and the mass ratio of the reducing agent to the silicon source is preferably 3: 1-1: 3.
Further, the thermal reduction process in S4 is: carrying out thermal reduction on the intermediate product A in vacuum or inert protective gas atmosphere;
the temperature in the thermal reduction process is 800-1100 ℃, the temperature rising speed is 2-20 ℃, and the heat preservation time is 1-8 h.
Further, the inert protective gas is nitrogen or argon.
Further, in S4, the thermal reduction process is performed in any one of a vacuum furnace, a box furnace, a tube furnace, a pusher kiln, a roller kiln, and a rotary furnace.
Further, hydrochloric acid or sulfuric acid with the concentration of 2.0-7.0 mol/L is adopted as a pickling solution in the pickling process of S5, and the pickling time is 0.5-3 h;
the drying process in the S5 is as follows: and drying under the condition of vacuum or inert gas (nitrogen or argon), wherein the drying temperature is 50-100 ℃, and the drying time is 1-3 h.
Compared with the prior art, the invention has the following advantages:
1) the template is one or more of porous polyethylene microspheres, porous polyvinyl chloride microspheres, porous polypropylene microspheres and porous polyurethane microspheres, and the porous silicon/carbon composite material is synthesized in situ by carbonization reaction synchronously generated in the thermal reduction process.
2) According to the invention, one or more of porous polyethylene microspheres, porous polyvinyl chloride microspheres, porous polypropylene microspheres and porous polyurethane microspheres are used as templates, and the prepared porous silicon/carbon composite material has a uniform and mutually communicated three-dimensional pore structure, so that the contact area of the porous silicon/carbon composite material and an electrolyte solution is increased, the permeation and wetting of the electrolyte solution are facilitated, the diffusion path of lithium ions is shortened, the reaction active sites are increased, the electrochemical reaction efficiency is improved, the ionic conductivity of the material is improved, and the rate capability of the material is enhanced. On the other hand, the carbon layer formed by in-situ carbonization can inhibit the volume expansion of silicon, and the specific porous structure of the carbon layer reserves an expansion space for the silicon, so that the outward absolute expansion of the material is reduced, the cycle performance of the material is improved, and the charge and discharge performance of the electrode in high-rate long-cycle is favorably improved.
3) The reducing agent is one or more of titanium hydride powder, lithium hydride powder and aluminum powder, has strong reducing capability, is relatively safe and controllable in the whole reducing process, and is a key technical element for controllable production of an intermediate product B in the invention.
The invention combines the technical advantages, skillfully combines the porous polymer microspheres and a silicon source (one or more of ethyl silicate, methyl silicate, sodium silicate, methoxysilane, ethoxysilane, propoxysilane and butoxysilane), realizes advantage complementation by utilizing the synergistic interaction of the porous polymer microspheres and the silicon source, effectively inhibits the volume change of the porous silicon/carbon composite material in the process of lithium intercalation and deintercalation by the in-situ composite carbon layer, and also solves the problem that the micro-nano structure of the existing nano silicon cathode material in the market is easy to agglomerate. Furthermore, the in-situ compounded carbon layer can better improve the electrochemical properties such as the conductivity, the cycle stability, the charge-discharge efficiency, the rate performance and the like of the silicon cathode. The unique micro-nano pores reserve a lithium-embedded expansion space for silicon, and the absolute volume change of the composite material in the charging and discharging process is reduced. Therefore, the porous silicon/carbon composite material prepared by the method has high conductivity, long cycle stability and excellent high-rate charge and discharge performance.
The porous silicon/carbon composite negative electrode material synthesized in situ by taking the porous polystyrene microspheres as the template is expected to replace graphite to become a novel lithium ion battery negative electrode material, and has high value in the application aspect of pure electric vehicles and hybrid electric vehicles.
Drawings
FIG. 1 is a process flow diagram of a porous silicon/carbon composite of the present invention;
FIG. 2 is a schematic structural diagram of a porous silicon/carbon composite anode material prepared by the present invention;
FIG. 3 is a graph showing the charge and discharge curves of the porous silicon/carbon composite obtained in example 2 at a current density of 0.1C;
fig. 4 is a graph of the cycling performance and coulombic efficiency of the porous silicon/carbon composite obtained in example 2 at a current density of 0.5C.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1:
referring to FIG. 1, 50g of porous polystyrene microspheres with particle size D50 of 500nm and pore size of about 20nm are added into a proper amount of water and heated to 40 ℃ and stirred at 200r/min for 20min to be uniformly dispersed; then, 50g of ethyl silicate is slowly added into the obtained suspension solution, and the mixture is continuously stirred for 20min at 40 ℃ at 200 r/min; and then filtering, washing with deionized water, drying at 50 ℃ for 1h, adding 250g of aluminum powder with the particle size of 3 mu m as a reducing agent, and grinding and mixing to obtain an intermediate product A.
Heating to 800 ℃ at the speed of 2 ℃/min, preserving the heat for 1h in vacuum atmosphere, and reducing the intermediate product A to obtain an intermediate product B. And (3) putting the intermediate product B into 2.0mol/L hydrochloric acid for acid washing for 0.5h, washing by deionized water, filtering, and keeping the temperature at 50 ℃ for 1h and drying to obtain the porous silicon/carbon composite material, which is shown in figure 2.
And (3) performing electrochemical performance test on the half-cell formed by the obtained porous silicon/carbon composite material and the metal lithium, wherein the test magnification is 0.1C (first) +0.5C (circulation), and the charge-discharge voltage is 0.005-2.0V, as shown in figure 3. The specific discharge capacity of the negative pole piece can reach 2195.0mAh/g, the first efficiency is 88.3%, and the capacity of 92.2% can be still maintained after 100 cycles.
Example 2:
adding 50g of porous polyvinyl chloride microspheres with the particle size D50 of 5 mu m and the pore size of about 70nm into a proper amount of water, heating to 50 ℃, stirring at 500r/min for 30min, and uniformly dispersing; then 600g of methyl silicate and 400g of sodium silicate are slowly added to the obtained suspension solution and stirring is continued at 500r/min for 40min at 50 ℃; and then filtering, washing with deionized water, drying at 70 ℃ for 2h, adding 3000g of aluminum powder with the particle size of 5 mu m as a reducing agent, and grinding and mixing to obtain an intermediate product A.
Heating to 900 ℃ at the speed of 5 ℃/min, preserving the heat for 2h under the argon atmosphere, and reducing the intermediate product A to obtain an intermediate product B. And (3) putting the intermediate product B into 3.0mol/L sulfuric acid for acid washing for 1h, washing with deionized water, filtering, and keeping the temperature at 80 ℃ for 2h and drying to obtain the porous silicon/carbon composite material.
And (3) performing electrochemical performance test on the half-cell formed by the obtained porous silicon/carbon composite material and the metal lithium, wherein the test magnification is 0.1C (first) +0.5C (circulation), and the charge-discharge voltage is 0.005-2.0V, as shown in figure 4. The specific discharge capacity of the negative pole piece can reach 2109.8mAh/g, the first efficiency is 92.3%, and after 100 cycles, the capacity of 93.3% can still be maintained.
Example 3:
20g of porous polyethylene microspheres with the particle size D50 of 15 mu m and the pore size of about 90nm and 30g of porous polyurethane microspheres with the particle size D50 of 15 mu m and the pore size of about 70nm are added into a proper amount of water and heated to 55 ℃, and the mixture is stirred at 600r/mim for 35min to be uniformly dispersed; then 700g of methoxysilane and 800g of ethoxysilane are slowly added to the suspension obtained and stirring is continued at 600r/min for 40min at 55 ℃; and then filtering, washing with deionized water, drying at 80 ℃ for 1.5h, adding 650g of uniformly mixed aluminum powder with the particle size of 8 microns and 850g of titanium hydride powder with the particle size of 10 microns as reducing agents, and grinding and mixing to obtain an intermediate product A.
Heating to 950 ℃ at the speed of 10 ℃/min, preserving the heat for 4h in the nitrogen atmosphere, and reducing the intermediate product A to obtain an intermediate product B. And (3) putting the intermediate product B into 3.0mol/L sulfuric acid for acid washing for 2h, washing with deionized water, filtering, and keeping the temperature at 90 ℃ for 2h and drying to obtain the porous silicon/carbon composite material.
And (3) performing electrochemical performance test on the half-cell formed by the porous silicon/carbon composite material and the metal lithium, wherein the test multiplying power is 0.1C (first time) +0.5C (cycle), and the charge-discharge voltage is 0.005-2.0V. The specific discharge capacity of the negative pole piece can reach 2180.5mAh/g, the first efficiency is 89.3%, and the capacity of 91.5% can be still maintained after 100 cycles.
Example 4:
taking 10g of porous polyethylene microspheres with the particle size D50 of 15 mu m and the pore size of about 90nm and 40g of porous polypropylene microspheres with the particle size D50 of 20 mu m and the pore size of about 100nm, adding a proper amount of water, heating to 55 ℃, stirring at 800r/min for 35min, and uniformly dispersing; then 1000g of propoxysilane and 1000g of butoxysilane were added slowly to the suspension obtained and stirring was continued at 55 ℃ at 800r/min for 30 min; and then filtering, washing with deionized water, drying at 80 ℃ for 1.5h, adding 500g of uniformly mixed lithium hydride powder with the particle size of 15 microns and 500g of titanium hydride powder with the particle size of 17 microns as reducing agents, and grinding and mixing to obtain an intermediate product A.
Heating to 1000 ℃ at a speed of 10 ℃/min, preserving heat for 6 hours under the argon atmosphere, and reducing the intermediate product A to obtain an intermediate product B. And (3) putting the intermediate product B into 5.0mol/L hydrochloric acid for acid washing for 2h, washing with deionized water, filtering, and keeping the temperature at 80 ℃ for 2h and drying to obtain the porous silicon/carbon composite material.
And (3) performing electrochemical performance test on the half-cell formed by the porous silicon/carbon composite material and the metal lithium, wherein the test multiplying power is 0.1C (first time) +0.5C (cycle), and the charge-discharge voltage is 0.005-2.0V. The specific discharge capacity of the negative pole piece can reach 1920.8mAh/g, the first efficiency is 90.5%, and the capacity of 90.2% can be still maintained after 100 cycles.
Example 5:
adding 50g of porous polyurethane microspheres with the particle size D50 of 18 mu m and the pore size of about 170nm into a proper amount of water, heating to 55 ℃, and stirring at 900r/min for 35min to uniformly disperse the porous polyurethane microspheres; then 3500g of ethyl silicate is slowly added into the obtained suspension solution and the mixture is continuously stirred for 20min at the temperature of 55 ℃ and at the speed of 900 r/min; and then filtering, washing with deionized water, drying at 90 ℃ for 1.5h, adding 700g of uniformly mixed lithium hydride powder with the particle size of 15 microns and 800g of titanium hydride powder with the particle size of 18 microns as reducing agents, and grinding and mixing to obtain an intermediate product A.
Heating to 1000 ℃ at a speed of 15 ℃/min, preserving heat for 8h under the argon atmosphere, and reducing the intermediate product A to obtain an intermediate product B. And (3) putting the intermediate product B into 7.0mol/L hydrochloric acid for acid washing for 3h, washing with deionized water, filtering, and keeping the temperature at 80 ℃ for 2h and drying to obtain the porous silicon/carbon composite material.
And (3) performing electrochemical performance test on the half-cell formed by the porous silicon/carbon composite material and the metal lithium, wherein the test multiplying power is 0.1C (first time) +0.5C (cycle), and the charge-discharge voltage is 0.005-2.0V. The specific discharge capacity of the negative pole piece can reach 1830.6mAh/g, the first efficiency is 89.5%, and after 100 cycles, the capacity of 93.2% can still be maintained.
Example 6:
adding 50g of porous polystyrene microspheres with the particle size D50 of 25 mu m and the pore size of about 200nm into a proper amount of water, heating to 60 ℃, stirring at 2000r/min for 40min, and uniformly dispersing; then 5000g of ethyl silicate is slowly added into the obtained suspension solution, the mixture is continuously stirred for 40min at the temperature of 60 ℃ at 2000r/min, then the mixed solution is sequentially filtered, washed by deionized water and dried for 3h at the temperature of 100 ℃, then 500g of uniformly mixed lithium hydride powder with the particle size of 20 mu m and 500g of aluminum powder with the particle size of 20 mu m are added as reducing agents, and the intermediate product A is obtained by grinding and mixing.
Heating to 1100 ℃ at the speed of 20 ℃/min, preserving the heat for 8h in vacuum atmosphere, and reducing the intermediate product A to obtain an intermediate product B. And (3) putting the intermediate product B into 7.0mol/L hydrochloric acid for acid washing for 3h, washing with deionized water, filtering, and keeping the temperature at 100 ℃ for 3h and drying to obtain the porous silicon/carbon composite material.
And (3) performing electrochemical performance test on the half-cell formed by the porous silicon/carbon composite material and the metal lithium, wherein the test multiplying power is 0.1C (first time) +0.5C (cycle), and the charge-discharge voltage is 0.005-2.0V. The specific discharge capacity of the negative pole piece can reach 1460.5mAh/g, the first efficiency is 88.3%, and the capacity of 89.6% can be still maintained after 100 cycles.
Comparative example 1:
adding silicon powder with the particle size D50 of 0.5 mu m into 1mol/L H2SO4H with the mass fraction of 2%2O2And 0.5mol/L HF, mechanically stirring for 1h at room temperature at 100r/min, removing impurities and surface silicon dioxide, and washing with deionized water and drying at 80 ℃ to obtain the nano silicon powder material.
And (3) forming the obtained nano silicon powder material and metal lithium into a half cell for electrochemical performance test, wherein the test multiplying power is 0.1C (first) +0.5C (circulation), and the charge-discharge voltage is 0.005-2.0V. The specific discharge capacity of the negative pole piece can reach 2330mAh/g, the first efficiency is 72.3%, and after 100 cycles, the capacity retention rate is only 26.2%.
Comparative example 2:
the silica powder with a particle size D50 ═ 3 μm was heat treated in a reactor at 950 ℃ for 3h to give intermediate a.
And crushing, crushing and grading the intermediate product A, and then putting the intermediate product A into a rotary furnace to perform carbon coating for 3 hours at 800 ℃ in the atmosphere of mixed gas of acetylene, ethylene and argon, wherein the gas flow rates of the acetylene, ethylene and argon are all 0.1mol/L, so as to obtain the silicon oxide/carbon composite material.
And (3) performing electrochemical performance test on the half-cell formed by the obtained silicon monoxide/carbon composite material and the metal lithium, wherein the test multiplying power is 0.1C (first time) +0.5C (circulation), and the charge-discharge voltage is 0.005-2.0V. The discharge specific capacity of the negative pole piece can reach 1430mAh/g, the first efficiency is 80.1%, and after 100 cycles, the capacity retention rate is only 56.2%.
Comparing the performance results of examples 1-6 and comparative examples 1-2, it can be seen that the in-situ composite carbon layer in the porous silicon/carbon composite material finally and successfully prepared by the technical scheme effectively inhibits the volume change of the material in the lithium intercalation and deintercalation process, also improves the problem that the micro-nano material of the material is easy to agglomerate, and further, the in-situ composite carbon layer can better improve the electrochemical properties of the silicon cathode, such as conductivity, cycle stability, charge and discharge efficiency, rate capability and the like. The unique micro-nano pores reserve a lithium-embedded expansion space for silicon, and the absolute volume change of the composite material in the charging and discharging process is reduced. Therefore, the porous silicon/carbon composite material prepared by the method has high conductivity, long cycle stability and excellent high-rate charge and discharge performance.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.