CN110931746B - Silicon-tin-graphene composite electrode material and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a silicon-tin-graphene composite electrode material which comprises silicon particles, tin particles and a graphene sheet layer, wherein the silicon particles and the tin particles are simultaneously loaded on the graphene sheet layer, the particle size of the silicon particles is 20-60 nm, the particle size of the tin particles is 50-100 nm, and the mass fraction of tin in silicon-tin is 5-50%. The invention also discloses a preparation method of the composite electrode material and application of the composite electrode material in a lithium ion battery cathode. Silicon-tin particles are modified on the surface of the redox graphene sheet layer, and the tin particles are close to the silicon particles, so that effective support is provided for contraction and expansion of the silicon particles in the lithium desorption and intercalation process, pulverization of the silicon particles is inhibited, and the cycle stability of the silicon-based electrode is improved. Even if the silicon particles break, the tin particles can provide electrical contact to the silicon at the surface of the silicon, improving its conductivity. The silicon-tin-graphene composite electrode material provided by the invention has the advantages of high energy density, high reversible capacity, good cycling stability and excellent conductivity.
Description
Technical Field
The invention relates to a lithium ion battery cathode material and a preparation method thereof, in particular to a silicon-tin-graphene composite electrode material and a preparation method and application thereof.
Background
With the emergence of this emerging market for Electric Vehicles (EV), there is a tremendous demand for Lithium Ion Batteries (LIBs). The current commercial negative electrode material is mainly made of carbon materials such as graphite carbon, and is widely applied due to high conductivity and strong cycling stability. However, the maximum theoretical specific capacity of the graphite carbon material is only 372mAh/g, and further requirements cannot be met. Silicon is considered to be the most promising electrode material with theoretical capacities up to 4200mAh/g (reversibly reacting with Li to form various Si-Li alloys and eventually Li)4.4Si alloy) and is abundant in resources on earth. In addition, the lithiation platform voltage of the silicon electrode is higher than that of the graphite electrode, so that the formation of dendrites can be effectively avoided, and the safety is improved. However, silicon is not highly conductive and results in a large change in the volume of the silicon electrode during charge and discharge cycles: (>300%) resulting in a silicon material structureCollapse of the battery and exfoliation, pulverization of the electrodes, decrease in conductivity, which in turn leads to sharp decrease in battery capacity.
For the volume expansion effect of a silicon-based electrode in the charging and discharging processes, people propose a silicon-carbon compounding method in recent years, and the prepared silicon-carbon negative electrode material can provide a buffer space for the volume change of silicon in the lithium intercalation/lithium deintercalation process and counteract partial internal stress. However, the cycling stability and the conductivity of the silicon-carbon negative electrode material still need to be further improved.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems, the invention provides the silicon-tin-graphene composite electrode material which has high reversible capacity and good cycling stability and can further delay electrode pulverization and cracking. The invention also aims to provide a preparation method of the composite electrode material. The invention also aims to provide application of the composite electrode material in a negative electrode of a lithium ion battery.
The technical scheme is as follows: the silicon-tin-graphene composite electrode material comprises silicon particles, tin particles and graphene sheet layers, wherein the silicon particles and the tin particles are simultaneously loaded on the graphene sheet layers, the particle size of the silicon particles is 20-60 nm, the particle size of the tin particles is 50-100 nm, and the mass fraction of tin in the silicon-tin is 5% -50%.
The method for preparing the silicon-tin-graphene composite electrode material comprises the following steps:
(1) with SnCl4After the nano silicon is impregnated by the solution, preparing a silicon-tin compound by adopting a hydrogenation reduction method;
(2) dispersing the silicon-tin compound in the step (1) in polydiallyldimethylammonium chloride-tris (hydroxymethyl) aminomethane-sodium chloride aqueous solution for adsorption, and performing centrifugal separation to obtain solid particles;
(3) and (3) adding the solid particles obtained in the step (2) into a graphene oxide solution, stirring, performing centrifugal separation to obtain a solid, freeze-drying the solid, and performing high-temperature hydrogenation reduction treatment to obtain the silicon-tin-graphene composite electrode material.
Wherein the steps(1) Middle SnCl4The concentration of the solution is 0.01-0.1 mol/L, if the concentration of the solution is too high, the content of tin in the sample is high, and the overall charge-discharge capacity can be reduced; if the concentration of the solution is too low, the content of tin is insufficient, the conductivity of the material cannot be fully improved, and the electrochemical performance is poor, so that SnCl4The concentration of the solution is further preferably 0.03-0.08 mol/L, and the dipping time is 0.5-5 h.
The hydrogenation reduction in the step (1) adopts a mixed gas of hydrogen and argon, the volume flow of the used hydrogen is 5-50 sccm, the volume flow of the used argon is 5-50 sccm, the temperature of the hydrogenation reduction is 200-1000 ℃, and the temperature rise rate is 0.5-10 ℃/min.
The preparation method of the poly (diallyldimethylammonium chloride) -tris (hydroxymethyl) aminomethane-sodium chloride aqueous solution in the step (2) comprises the following steps: adding 1-5 g of polydiallyldimethylammonium chloride solution, 0.1-0.5 g of tris (hydroxymethyl) aminomethane and 0.1-0.5 g of sodium chloride into 50-300 mL of water. The solution prepared by 2.149g of poly (diallyldimethylammonium chloride) solution, 0.363g of tris (hydroxymethyl) aminomethane, 0.173g of sodium chloride and 150mL of deionized water has the best coating performance.
The concentration of the graphene oxide solution in the step (3) is 1-4 mg/mL. The graphene oxide solution with too high concentration can increase the content of graphene in the sample and reduce the overall capacity; the low concentration of the graphene oxide solution may reduce the overall conductivity, and thus the concentration of the graphene oxide solution is most preferably 2 mg/mL.
And (4) in the step (3), the temperature is raised to 600-900 ℃ at the speed of 1-10 ℃/min for high-temperature hydrogenation reduction, and the temperature is kept for 1-6 h. Through a great deal of research, the inventor finds that the heat treatment procedure with the temperature rising of 1-5 ℃/min to 700-900 ℃ has the best effect, and can ensure that the graphene oxide is fully reduced into the redox graphene.
And (3) centrifuging at the rotating speed of 6000-10000 r/min for 2-12 min in the steps (2) and (3), but the centrifuging is not limited to this, as long as the centrifuging effect can be achieved.
The temperature of freeze drying in the step (3) is-40 to-20 ℃, and the temperature is kept for 8 to 24 hours, but the method is not limited to the temperature, as long as the effect of freeze drying can be achieved.
The invention finally provides the application of the silicon-tin-graphene composite electrode material in a lithium ion battery cathode.
The silicon-tin-graphene composite electrode material is prepared by using the advantages of high conductivity, good ductility, high lithium storage capacity (991mAh/g) and the like of metallic tin through a dipping-hydrogenation reduction method. Silicon-tin particles are modified on the surface of the redox graphene sheet layer, and the tin particles are close to the silicon particles, so that effective support is provided for contraction and expansion of the silicon particles in the lithium desorption and intercalation process, pulverization of the silicon particles is inhibited, and the cycle stability of the silicon-based electrode is improved. Even if the silicon particles break, the tin particles can provide electrical contact to the silicon at the surface of the silicon, improving its conductivity. On the other hand, the redox graphene has better conductivity, provides more conductive paths for electrons, reduces electron transfer impedance, reduces particle agglomeration, and simultaneously constructs a bridge for ion transmission among particles to accelerate the transmission of lithium ions. Therefore, the silicon-tin-graphene composite electrode material has excellent electrochemical performance.
Has the advantages that: compared with the prior art, the silicon-tin-graphene composite electrode material provided by the invention has the advantages of high energy density, high reversible capacity, good cycling stability and excellent conductivity, and can be produced in a large scale.
Drawings
FIG. 1 is a TEM image of a silicon-tin composite;
fig. 2 is a TEM image of a silicon-tin-graphene composite electrode material;
fig. 3 is an XRD pattern of a silicon-tin-graphene composite electrode material;
fig. 4 is a graph comparing electrochemical cycling stability of a silicon-tin-graphene composite electrode material;
fig. 5 is a graph comparing the ac impedance of a silicon-tin-graphene composite electrode material.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will occur to those skilled in the art upon reading the present disclosure and fall within the scope of the appended claims.
The following examples used commercial nano-silicon having a particle size of about 40nm (the particle size of the commercial nano-silicon is, but not limited to, 20 to 100nm, and further 20 to 60 nm), a commercial redox graphene solution (1.5 wt%), a commercial polydiallyldimethylammonium chloride solution (35 wt%), and tris (CAS: 77-86-1).
Examples
1. Preparation of silicon-tin-graphene (Si-Sn/rGO) composite electrode material
(1) Weighing commercial silicon nanoparticles 0.1275g, adding into SnCl with concentration of 0.015mol/L, 0.032mol/L and 0.077mol/L4In the solution, the volume of the solution is 6mL, and after ultrasonic treatment for 60min, vacuum drying is carried out for 10h at 80 ℃; putting the obtained dry sample into a tubular calcining furnace for high-temperature heat treatment, heating to 350 ℃ at the speed of 5 ℃/min, preserving the heat for 1H, and introducing 20sccm H in the whole process of hydrogenation reduction2And Ar mixed gas of 40sccm, and finally cooling to room temperature along with the furnace to obtain a silicon-tin (Si-Sn) compound;
(2) weighing 2.149g of commercial poly (diallyldimethylammonium chloride) solution, 0.363g of tris (hydroxymethyl) aminomethane and 0.173g of sodium chloride, adding the solution into 150mL of deionized water to prepare poly (diallyldimethylammonium chloride) -tris (hydroxymethyl) aminomethane-sodium chloride aqueous solution, weighing 0.1g of the silicon-tin compound obtained in the step (1), adding the silicon-tin compound into the solution, performing ultrasonic treatment for 30min, and performing centrifugal separation at the rotating speed of 10000r/min for 12min to obtain solid particles;
(3) weighing 6.67g of commercial redox graphene solution (1.5 wt%), adding the solution into 50mL of deionized water, fully stirring, adding the solid particles obtained in the step (2) into the solution, stirring for 30min, performing centrifugal separation for 12min at the rotating speed of 10000r/min to obtain a solid, and freeze-drying the solid in a freeze dryer at-20 ℃ for 12 h; putting the obtained dry sample into a tubular calcining furnace for high-temperature heat treatment, heating to 900 ℃ at the speed of 5 ℃/min, preserving heat for 3H, cooling to room temperature along with the furnace, and introducing 20sccm H in the whole process of the high-temperature heat treatment2And Ar mixed gas of 40sccm to obtain the silicon-tin-graphite oxideAn alkene (Si-Sn/rGO) composite electrode material.
SnCl with the concentration of 0.015mol/L, 0.032mol/L and 0.077mol/L respectively4Samples obtained by preparing the solution are respectively named as Si- (7.5%) Sn/rGO, Si- (15%) Sn/rGO and Si- (30%) Sn/rGO composite electrode materials, wherein 7.5% refers to the mass percentage of tin in the silicon-tin composite, and the rest contents are analogized in sequence.
2. Preparation of silicon-graphene (Si/rGO) composite electrode material
Commercial nano-silicon particles except for SnCl which does not pass through the step (1)4The preparation process other than the solution impregnation-hydrogenation reduction treatment is the same as in the above steps (2) and (3).
3. Structure detection
(1) TEM analysis
The silicon-tin (Si- (15%) Sn) composite and the silicon-tin-graphene (Si- (15%) Sn/rGO) composite electrode materials were observed under a Transmission Electron Microscope (TEM), respectively. As shown in fig. 1, the silicon-tin composite contains silicon particles and tin particles. As shown in figure 2, the Si- (15%) Sn/rGO composite electrode material simultaneously contains silicon particles, tin particles and graphene sheet layers, wherein the particle size of the silicon particles is mainly 20-60 nm, the particle size of the tin particles is mainly 50-100 nm, and the tin particles are close to the silicon particles and simultaneously loaded on the graphene sheet layers.
(2) XRD analysis
The prepared Si/rGO, Si- (15%) Sn and Si- (15%) Sn/rGO composite electrode material is subjected to X-ray diffraction (XRD) test, and the test result is shown in figure 3. It can be seen from the figure that neither of the samples of Si- (15%) Sn and Si- (15%) Sn/rGO composite electrode materials have SnCl present4Indicating that Sn has been completely reduced. The peaks at 28.4 °, 47.3 °, 56.1 °, 69.1 °, 76.4 ° correspond to the (111), (220), (311), (400), (331) crystal planes of a silicon crystal, respectively; the peaks at 30.6 °, 32.0 °, 43.8 °, 44.9 ° correspond to the (220), (101), (220), (211) crystal planes of the tin crystal, respectively.
4. Performance detection
And taking out the obtained silicon-tin-graphene powder, conductive carbon black super P and sodium alginate serving as a binder, mixing according to a mass ratio of 6:2:2, adding a proper amount of deionized water to prepare uniform slurry, and coating the uniform slurry (with the thickness of about 5 microns) on a current collector copper foil. The copper foil coated with the sample was placed in a vacuum drying oven and dried at 80 ℃ for 10 hours. And taking out the dried sample, and charging an electrode plate with the diameter of 12 mm. The electrode sheet was used for the following cycle stability test and electrochemical impedance test.
(1) Analysis of cycling stability
The electrochemical test is carried out in a 2032 type button cell system, and the electrolyte is 1mol/LLIPF6Dissolved in an EC/DEC (ethylene carbonate/diethyl carbonate, 1:1 by volume) solution with 2% VC (vinylene carbonate) added, the counter electrode was a lithium metal plate. First, the discharge is carried out at a current density of 500mA/g until the cut-off potential is 0.01V (vs. Li/Li)+) After standing for 2min, the mixture was charged to a cut-off potential of 2V (vs. Li/Li) at a current density of 500mA/g+) A cyclic capacity map is obtained (fig. 4).
The silicon-tin-graphene composite electrode material with the yolk core-shell structure, which is prepared by the embodiment, is Si- (15%) Sn/rGO composite electrode material, shows the most excellent performance, and the specific discharge capacity after 60 cycles is 1881 mAh/g. The specific discharge capacity of the Si- (15%) Sn, Si/rGO, Si- (7.5%) Sn/rGO and Si- (30%) Sn/rGO composite electrode material after 60 cycles is 1019, 1181, 1129 and 1067mAh/g respectively.
(2) Electrochemical impedance analysis
The electrochemical impedance spectrum of the sample was measured by an electrochemical comprehensive tester model CHI604E of Chen Hua instruments, Shanghai, at a frequency of 100kHz to 0.1Hz, to obtain an AC impedance spectrum (see FIG. 5). The charge transfer resistance values of the Si- (15%) Sn/rGO composite electrode material are 193 omega, the charge transfer resistance values of the Si- (15%) Sn, Si/rGO, Si- (7.5%) Sn/rGO and Si- (30%) Sn/rGO composite electrode materials are 258, 292, 408 and 243 omega respectively. Therefore, the Si- (15%) Sn/rGO composite electrode material has lower charge transfer resistance, so that the electrochemical performance is more excellent.
Claims (8)
1. The silicon-tin-graphene composite electrode material is characterized by comprising silicon particles, tin particles and graphene sheet layers, wherein the silicon particles and the tin particles are simultaneously loaded on the graphene sheet layers, the particle size of the silicon particles is 20-60 nm, the particle size of the tin particles is 50-100 nm, and the mass fraction of tin in the silicon-tin is 5% -50%;
the preparation method of the silicon-tin-graphene composite electrode material comprises the following steps:
(1) with SnCl4After the nano silicon is impregnated by the solution, preparing a silicon-tin compound by adopting a hydrogenation reduction method;
(2) dispersing the silicon-tin compound in the step (1) in polydiallyldimethylammonium chloride-tris (hydroxymethyl) aminomethane-sodium chloride aqueous solution for adsorption, and performing centrifugal separation to obtain solid particles;
(3) adding the solid particles obtained in the step (2) into a graphene oxide solution, stirring, performing centrifugal separation to obtain a solid, freeze-drying the solid, and performing high-temperature hydrogenation reduction treatment to obtain a silicon-tin-graphene composite electrode material;
the preparation method of the poly (diallyldimethylammonium chloride) -tris (hydroxymethyl) aminomethane-sodium chloride aqueous solution in the step (2) comprises the following steps: adding 1-5 g of polydiallyldimethylammonium chloride solution, 0.1-0.5 g of tris (hydroxymethyl) aminomethane and 0.1-0.5 g of sodium chloride into 50-300 mL of water.
2. The silicon-tin-graphene composite electrode material according to claim 1, wherein the SnCl in the step (1)4The concentration of the solution is 0.01-0.1 mol/L, and the dipping time is 0.5-5 h.
3. The silicon-tin-graphene composite electrode material according to claim 2, wherein the SnCl in the step (1)4The concentration of the solution is 0.03-0.08 mol/L.
4. The silicon-tin-graphene composite electrode material as claimed in claim 1, wherein a mixed gas of hydrogen and argon is used for the hydrogenation reduction in the step (1), a volume flow of the hydrogen is 5-50 sccm, a volume flow of the argon is 5-50 sccm, a temperature of the hydrogenation reduction is 200-1000 ℃, and a temperature rise rate is 0.5-10 ℃/min.
5. The method for preparing the silicon-tin-graphene composite electrode material according to claim 1, wherein the concentration of the graphene oxide solution in the step (3) is 1-4 mg/mL.
6. The silicon-tin-graphene composite electrode material as claimed in claim 1, wherein the temperature of the high-temperature hydrogenation reduction in the step (3) is raised to 600-900 ℃ at a rate of 1-10 ℃/min, and the temperature is maintained for 1-6 h.
7. The silicon-tin-graphene composite electrode material as claimed in claim 6, wherein the temperature of the high-temperature hydrogenation reduction in the step (3) is raised to 700-900 ℃ at a rate of 1-5 ℃/min.
8. The use of the silicon-tin-graphene composite electrode material of claim 1 in a lithium ion battery negative electrode.
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| CN103050661A (en) * | 2012-12-12 | 2013-04-17 | 清华大学深圳研究生院 | Lithium ion battery cathode material compounded with graphene and preparation method thereof |
| CN107959013A (en) * | 2017-11-20 | 2018-04-24 | 清华大学 | The carbon-silicon composite material of graphene coated silicon grain and its preparation and application |
| CN108493421A (en) * | 2018-04-08 | 2018-09-04 | 深圳新恒业电池科技有限公司 | A kind of preparation method of lithium ion battery tin-silicon substrate graphene ball negative material |
| CN109585834A (en) * | 2018-12-10 | 2019-04-05 | 包头市石墨烯材料研究院有限责任公司 | A kind of mesoporous silicon-tin composite electrode material and its preparation method and application |
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| CN103050661A (en) * | 2012-12-12 | 2013-04-17 | 清华大学深圳研究生院 | Lithium ion battery cathode material compounded with graphene and preparation method thereof |
| CN107959013A (en) * | 2017-11-20 | 2018-04-24 | 清华大学 | The carbon-silicon composite material of graphene coated silicon grain and its preparation and application |
| CN108493421A (en) * | 2018-04-08 | 2018-09-04 | 深圳新恒业电池科技有限公司 | A kind of preparation method of lithium ion battery tin-silicon substrate graphene ball negative material |
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