CN109694075B - Low-temperature ball-milling nano silicon powder, preparation method and application - Google Patents
Low-temperature ball-milling nano silicon powder, preparation method and application Download PDFInfo
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- C01B33/00—Silicon; Compounds thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses low-temperature ball-milling nano silicon powder, which comprises a silicon source, light metal powder and an accelerator, wherein the silicon source is any one of white carbon black, quartz powder and kaolin, the light metal powder is magnesium powder or aluminum powder, the mass ratio of the silicon source to the light metal powder to the accelerator is 1: 2.5-3.0, the molar ratio of silicon dioxide in the silicon source to the aluminum powder is 1: 1.45-1.6, the molar ratio of the silicon dioxide in the silicon source to the magnesium powder is 1: 2.1-2.4, and the reaction accelerator is ternary chloride salt; the preparation method of the low-temperature ball-milling nano silicon powder comprises the following steps: weighing a silicon source, aluminum powder or magnesium powder and a reaction promoter, putting the silicon source, the aluminum powder or magnesium powder and the reaction promoter into a mortar, grinding and uniformly mixing to obtain mixed powder; transferring the mixed powder into a grinding tank, and performing ball milling to obtain a nano silicon powder prefabricated product; processing the nano silicon powder prefabricated product to obtain nano silicon powder; the nano silicon powder is brown yellow powder, the yield is 90.1-94.7%, and the grain size of the pure cubic system silicon is 30-100 nm.
Description
Technical Field
The invention belongs to the technical field of preparation of nano silicon, and particularly relates to low-temperature ball-milled nano silicon powder, a preparation method and application.
Background
Theoretically, the specific capacity of the silicon material is 3579 milliampere hour/gram (mAh/g), which is much higher than that of the current graphite cathode material, and the silicon element is rich in storage capacity in the earth crust and low in price, so that the silicon material is a lithium ion battery cathode material with a great application prospect and is widely concerned by people. However, the volume expansion of the silicon negative electrode material is severe in the charging and discharging process, and under the state of complete lithium intercalation, the volume expansion rate of silicon is as high as 300%, and the severe volume expansion causes the silicon particles to be crushed, thereby causing the separation of silicon active substances from a conductive agent, a binder or a current collector, and further causing the rapid attenuation of reversible specific capacity. Research shows that the nano-size of the silicon particles can effectively reduce the stress generated by the volume change of the silicon particles, thereby obviously inhibiting the crushing of the silicon active material and improving the electrochemical performance of the silicon negative electrode material.
Currently, a common method for preparing nano-sized silicon powder is aluminothermic reduction of SiO2The reaction temperature of the method is required to be more than 700 ℃, and Al as a byproduct2O3Isolating Al powder and SiO2The contact between the two components hinders the continuous progress of the reduction reaction, and the product yield is low; the subject group of professor Lixing China of Beijing university adopts nano Mg powder and nano SiO2The nanometer silicon powder is prepared by room temperature reaction ball milling method as raw material with the yield of 89 percent, but the method relies on nanometer Mg powder and nanometer SiO2The raw material is limited in application range, and the raw material cost is high; in addition, the nano-Mg powder has high activity and has safety risks in transportation, storage and production, so that the production process is complex and the production cost is high.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the reaction temperature of the prior art for preparing the nano silicon powder is higher, the product yield is lower and depends on nano raw materials, and the low-temperature ball-milling nano silicon powder, the preparation method and the application are provided.
The invention solves the technical problems through the following technical scheme, and the invention comprises the following steps:
the low-temperature ball-milling nanometer silicon powder comprises a silicon source, light metal powder and an accelerator, wherein the silicon source is any one of white carbon black, quartz powder and kaolin, the light metal powder is aluminum powder or magnesium powder, the mass ratio of the silicon source to the light metal powder to the accelerator is 1: 2.5-3.0, the molar ratio of silicon dioxide in the silicon source to the aluminum powder is 1: 1.45-1.6, and the molar ratio of the silicon dioxide in the silicon source to the magnesium powder is 1: 2.1-2.4.
The particle size of the silicon source is 10-5000 meshes, and the particle sizes of the aluminum powder and the magnesium powder are both 50-300 meshes.
The reaction promoter is ternary chloride salt, and the ternary chloride salt comprises 17.0-20.5 mol% of NaCl, 9.5-11.6 mol% of KCl and 68.7-71.5 mol% of AlCl3。
The nano silicon powder is pure cubic system silicon, and the particle size is 30-100 nm.
The preparation method of the low-temperature ball-milling nano silicon powder is characterized by comprising the following steps of:
(1) weighing a silicon source, aluminum powder or magnesium powder and a reaction promoter, putting the silicon source, the aluminum powder or magnesium powder and the reaction promoter into a mortar, grinding and uniformly mixing to obtain mixed powder;
(2) transferring the mixed powder into a grinding tank, adding grinding balls into the grinding tank, filling argon gas into the grinding tank, sealing the grinding tank, and carrying out batch reaction on the mixed powder for 6-8 hours at 95-160 ℃ on ball milling equipment to obtain a nano silicon powder prefabricated product;
(3) spraying deionized water fog drops on the nano silicon powder prefabricated product to further reduce the residual silicon source by the excessive high-activity aluminum powder or magnesium powder to obtain a suspension;
(4) transferring the suspension into a container, adding hydrochloric acid, continuously stirring for 3-5 hours at 50-60 ℃ to obtain a khaki suspension, and performing centrifugal separation to obtain brown yellow slurry;
(5) adding hydrofluoric acid into the brown yellow slurry, stirring and reacting for 5-20 min at room temperature, reacting, performing centrifugal separation and washing on a reaction product, and performing vacuum drying for 10-12 h at 50-65 ℃ to obtain nano silicon powder;
in the step (2), the weight ratio of the materials to the grinding balls is 1: 8-10, wherein the ball milling equipment is a planetary ball mill, the ball milling speed is 450-600 rpm, and the grinding balls are wear-resistant steel grinding balls.
In the step (2), the outer layer of the grinding tank is sleeved with a heat insulation sleeve, a temperature sensor is arranged to control the temperature of the outer layer of the tank body, ball milling is stopped when the temperature of the outer layer of the grinding tank reaches 160 ℃, the temperature is naturally reduced, the ball milling is started when the temperature is reduced to 95 ℃, and the batch reaction is completed in this way in a circulating manner.
And (3) spraying deionized water fog drops into the tank body when the temperature of the tank body is reduced to 85-100 ℃, wherein the flow rate of the deionized water fog drops is 10-20 ml/min.
The concentration of the hydrochloric acid in the step (4) is 5-10 wt%, and the concentration of the hydrofluoric acid in the step (5) is 4-10 wt%.
An application of low-temperature ball-milled nano silicon powder in a lithium ion battery cathode material.
As a negative electrode material of a lithium ion battery, the reversible specific capacity of the lithium ion battery at the current density of 0.3A/g is 2843.4-2916.9 mAh/g, and the specific capacity of the lithium ion battery after 1000 cycles of 3.0A/g circulation is 863.5-905.6 mAh/g.
In the invention, the silicon source and the aluminum powder or the magnesium powder are subjected to chemical reaction, and the reaction formula is SiO2+Al/Mg→Si+Al2O3MgO, in which NaCl, KCl and AlCl are introduced in specific molar ratio3The melting point of the ternary chloride salt is 95-160 ℃, Al or Mg powder can be activated at the temperature, the activation energy of the reaction of the Al or Mg powder and a silicon source is reduced, the reaction can be carried out at the temperature of 95-160 ℃, the reaction temperature is reduced, meanwhile, the ternary chloride salt has the functions of a grinding aid and a dispersing agent, the Al or Mg powder and the silicon source are uniformly dispersed and fully contacted, and the yield of the nano silicon powder is improved.
In the ball milling process, the ball milling tank body is subjected to heat insulation treatment, the reaction of a silicon source and Al powder or Mg powder is promoted from the aspects of thermodynamics and kinetics, and the inherent defects of high temperature and low yield in the prior art are overcome;
the method uses the Al powder or Mg powder with larger grain diameter and the silicon source, does not need to be operated in a glove box, simplifies the preparation process and reduces the cost of raw materials.
Compared with the prior art, the invention has the following advantages: compared with the prior art, the preparation method has the advantages of low reaction temperature, high product yield, no dependence on nano-grade raw materials, simple preparation process, low cost, no need of complex equipment, environmental friendliness and capability of being directly used for industrial production, and the yield of the nano-silicon can reach 90.1-94.7%.
Drawings
FIG. 1 is an XRD spectrum of a silica nanopowder of example 1;
FIG. 2 is a FESEM photograph of the nano silicon powder of example 1;
FIG. 3 is an XRD spectrum of the silica nanopowder of example 2;
FIG. 4 is a FESEM photograph of the silica nanopowder of example 2;
FIG. 5 is a constant current charge/discharge curve at 0.3A/g for a simulated battery sample assembled with the nano-silicon powder as the negative electrode material in example 1;
FIG. 6 is a cycle performance curve at 3.0A/g for a simulated battery sample assembled with the nano-silica powder of example 1 as the negative electrode material;
FIG. 7 is a constant current charge/discharge curve at 0.3A/g for a simulated battery sample assembled with the nano-silica powder as the negative electrode material in example 2;
FIG. 8 is a cycle performance curve at 3.0A/g for a simulated battery sample assembled with the nano-silica powder of example 2 as the negative electrode material.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Taking 2.6320g as an example for producing the product of the invention, the raw materials and the mixture ratio are as follows:
white carbon black: 6.0060g, SiO299.0 percent of the total content and 5000 meshes of particle size;
aluminum powder: 3.9592g, the particle size is 200-300 meshes;
NaCl：2.6180g；
KCl：1.9031g；
AlCl3：23.1540g；
firstly, white carbon black, aluminum powder, NaCl, KCl and AlCl3The method comprises the following steps of placing ternary chloride salt into a mortar for grinding and uniformly mixing to obtain mixed powder, transferring the mixed powder into a grinding tank, adding a wear-resistant steel grinding ball into the tank, wherein the weight ratio of a material to the grinding ball is 1: 8, filling argon gas, sealing, and carrying out ball milling on a planet ball mill at the ball milling speed of 450 rpm; the outer layer of the grinding tank is sleeved with a heat insulation sleeve, and a temperature sensor is arranged to control the outer layer temperature of the tank bodyStopping ball milling and naturally cooling when the outer layer temperature of the milling tank reaches 160 ℃, starting ball milling when the temperature is reduced to 95 ℃, and performing the circular batch reaction for 6 hours to obtain a nano silicon powder prefabricated product;
when the temperature of the tank body is reduced to 85 ℃, deionized water fog drops with the flow rate of 10ml/min are sprayed on the nano silicon powder prefabricated product to obtain suspension;
transferring the suspension into a container, adding 5 wt% hydrochloric acid, continuously stirring at 50 ℃ for 3h to obtain a khaki suspension, and performing centrifugal separation to obtain brown yellow slurry;
and adding 4 wt% of hydrofluoric acid into the brown yellow slurry, stirring and reacting for 5min at room temperature, performing centrifugal separation and washing on a reaction product, and drying for 10h in vacuum at 50 ℃ to obtain the nano silicon powder.
The nano silicon powder is brown yellow powder;
as shown in the XRD spectrum of fig. 1 and the FESEM photograph of fig. 2, the nano-silicon powder prepared in this example is pure cubic silicon (jcpdsno.27-1402), and has high crystallinity, uniform particle size, and primary particle size of 30-80 nm;
the mass of the obtained nano silicon powder is 2.6320g, so that the calculated yield of the nano silicon of the example is equal to 94.7%;
the nano-silicon yield was 2.6320 ÷ (6.0060 × 0.990 ÷ 60.083 × 28.085) × 100% ═ 94.7%.
Example 2
Taking 2.5480g as an example for producing the product of the invention, the raw materials and the mixture ratio are as follows:
quartz powder: 6.0606g, SiO2The content of the active carbon is 99.0 percent, and the particle size is 3000 meshes;
magnesium powder: 5.3471g, the particle size is 50-100 meshes;
NaCl：2.6739g；
KCl：2.2414g；
AlCl3：24.7447g；
firstly, white carbon black, aluminum powder, NaCl, KCl and AlCl3The method comprises the following steps of placing ternary chloride salt into a mortar for grinding and uniformly mixing to obtain mixed powder, transferring the mixed powder into a grinding tank, adding a wear-resistant steel grinding ball into the tank, wherein the weight ratio of a material to the grinding ball is 1: 9, filling argon andsealing, and carrying out ball milling on a planetary ball mill at the ball milling speed of 500 rpm; sleeving a heat insulation sleeve on the outer layer of the grinding tank, arranging a temperature sensor to control the temperature of the outer layer of the tank body, stopping ball milling when the temperature of the outer layer of the grinding tank reaches 160 ℃, naturally cooling, starting ball milling when the temperature is reduced to 95 ℃, and performing a circular intermittent reaction for 7 hours to obtain a nano silicon powder prefabricated product;
when the temperature of the tank body is reduced to 95 ℃, spraying deionized water fog drops with the flow rate of 15ml/min on the nano silicon powder prefabricated product to obtain a suspension;
transferring the suspension into a container, adding 8 wt% hydrochloric acid, continuously stirring at 55 ℃ for 4h to obtain a khaki suspension, and performing centrifugal separation to obtain brown yellow slurry;
and adding 7 wt% of hydrofluoric acid into the brown yellow slurry, stirring and reacting for 10min at room temperature, reacting, performing centrifugal separation and washing on a reaction product, and drying for 11h in vacuum at 60 ℃ to obtain the nano silicon powder.
The nano silicon powder is brown yellow powder;
as shown in an XRD pattern of FIG. 3, the nano silicon powder prepared in the example is pure cubic silicon (JCPDS No.27-1402), and is well crystallized; as shown in the FESEM photograph of FIG. 4, the nano-silicon powder is characterized by aggregates, and the particle size of the primary particles is 50-100 nm;
the mass of the prepared silicon powder is 2.5480g, and the yield of the nano silicon powder prepared by the embodiment is calculated to be equal to 90.9%; the nano-silicon yield was 2.5480 ÷ (6.0606 × 0.99 ÷ 60.083 × 28.085) × 100% ═ 90.9%.
Example 3
Taking 2.5256g as an example for producing the product of the invention, the raw materials and the mixture ratio are as follows:
kaolin: 12.9032g, SiO2The content is 46.5%, and the particle size is 20-100 meshes;
aluminum powder: 4.3170g, the particle size is 100-200 meshes;
NaCl：4.3528g；
KCl：3.6417g；
AlCl3：41.0831g；
firstly, white carbon black, aluminum powder, NaCl, KCl and AlCl3Grinding and mixing the ternary chloride salt in a mortarClose evenly, obtain the mixed powder, transfer the mixed powder to grinding jar in, to adding wear-resisting steel ball mill in the jar, the weight ratio of material and ball mill is 1: 10, filling argon gas, sealing, and carrying out ball milling on a planet ball mill at the ball milling speed of 600 rpm; sleeving a heat insulation sleeve on the outer layer of the grinding tank, arranging a temperature sensor to control the temperature of the outer layer of the tank body, stopping ball milling when the temperature of the outer layer of the grinding tank reaches 160 ℃, naturally cooling, starting ball milling when the temperature is reduced to 95 ℃, and performing a cyclic intermittent reaction for 8 hours to obtain a nano silicon powder prefabricated product;
when the temperature of the tank body is reduced to 100 ℃, spraying deionized water fog drops with the flow rate of 20ml/min on the nano silicon powder prefabricated product to obtain a suspension;
transferring the suspension into a container, adding 10wt% hydrochloric acid, continuously stirring at 60 ℃ for 5h to obtain a khaki suspension, and performing centrifugal separation to obtain brown yellow slurry;
and adding 10wt% of hydrofluoric acid into the brown yellow slurry, stirring and reacting for 20min at room temperature, performing centrifugal separation and washing on a reaction product, and drying for 12h in vacuum at 65 ℃ to obtain the nano silicon powder.
The nano silicon powder is brown yellow powder;
the nano silicon powder prepared by the embodiment is pure cubic system silicon, the crystallinity is high, and the particle size of primary particles is 40-80 nm.
The mass of the prepared nano silicon powder is 2.5256g, so that the yield of the nano silicon prepared by the embodiment is calculated to be equal to 90.1%;
the nano-silicon yield was 2.5256 ÷ (12.9032 × 0.465 ÷ 60.083 × 28.085) × 100% ═ 90.1%.
Example 4
A simulation battery is assembled by taking the nano silicon powder as a negative electrode material in example 1, and a simulation battery sample is prepared by uniformly mixing the active substance of the nano silicon powder, conductive carbon black and sodium alginate (the mass ratio is 60:25:15) to prepare slurry, coating the slurry on copper foil to prepare a working electrode plate, assembling a CR2025 button battery by taking lithium foil as a counter electrode and a reference electrode plate and taking Celgard 2400 polypropylene porous membrane as a diaphragm, wherein 1mol/L LiPF is used as electrolyte6EC + DEC (EC and DEC in a 1:1 volume ratio).
As shown in the constant-current charge-discharge curve of FIG. 5 and the cycle performance curve of FIG. 6, when the nano-silicon powder prepared in this example is used as the negative electrode material, the reversible specific capacity at the current density of 0.3A/g is 2843.4mAh/g, and after 1000 cycles of charge-discharge cycle at 3A/g, the reversible specific capacity is 863.5 mAh/g.
Example 5
The method for manufacturing the simulated battery sample is the same as that in example 4 by using the nano silicon powder in example 2 as the negative electrode material to assemble the simulated battery.
As shown in the constant-current charge-discharge curve of FIG. 7 and the cycle performance curve of FIG. 8, the reversible specific capacity of the nano-silicon powder prepared in this example is 2846.6mAh/g at a current density of 0.3A/g, and 896.9mAh/g after 1000 cycles of charge-discharge cycle at 3A/g.
Example 6
The method for manufacturing the simulated battery sample is the same as that in example 4 by using the nano silicon powder in example 3 as the negative electrode material to assemble the simulated battery.
The nano silicon powder prepared in the embodiment is used as a negative electrode material, the reversible specific capacity of the nano silicon powder is 2916.9mAh/g when the current density is 0.3A/g, and the reversible specific capacity of the nano silicon powder is 905.5mAh/g after the nano silicon powder is subjected to charge-discharge cycling for 1000 circles at the current density of 3A/g.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. The low-temperature ball-milling nanometer silicon powder is characterized by comprising a silicon source, light metal powder and an accelerator, wherein the silicon source is any one of white carbon black, quartz powder and kaolin, the light metal powder is magnesium powder or aluminum powder, the mass ratio of the silicon source to the light metal powder to the accelerator is 1: 2.5-3.0, the molar ratio of silicon dioxide in the silicon source to the aluminum powder is 1: 1.45-1.6, and the molar ratio of the silicon dioxide in the silicon source to the magnesium powder is 1: 2.1-2.4; the accelerant is ternary chloride salt, which comprises 17.0 to 20.5 mole percent of NaCl and 9.5 to E-11.6 percent of KCl and 68.7 to 71.5 percent of AlCl3The nano silicon powder is pure cubic system silicon, and the particle size is 30-100 nm;
the preparation method of the low-temperature ball-milling nano silicon powder comprises the following steps:
(1) weighing a silicon source, aluminum powder or magnesium powder and a reaction promoter, putting the silicon source, the aluminum powder or magnesium powder and the reaction promoter into a mortar, grinding and uniformly mixing to obtain mixed powder;
(2) transferring the mixed powder into a grinding tank, adding grinding balls into the grinding tank, filling argon gas into the grinding tank, sealing the grinding tank, and performing intermittent reaction on ball milling equipment at 95-160 ℃ for 6-8 hours to obtain a nano silicon powder prefabricated product, wherein a heat insulation sleeve is sleeved on the outer layer of the grinding tank, a temperature sensor is arranged to control the temperature of the outer layer of the grinding tank, the ball milling is stopped when the temperature of the outer layer of the grinding tank reaches 160 ℃, the temperature is naturally reduced, the ball milling is started when the temperature is reduced to 95 ℃, and the intermittent reaction is completed in a circulating manner;
(3) spraying deionized water fog drops on the nano silicon powder prefabricated product to further reduce the residual silicon source by the excessive high-activity aluminum powder or magnesium powder to obtain a suspension;
(4) transferring the suspension into a container, adding hydrochloric acid, continuously stirring for 3-5 hours at 50-60 ℃ to obtain a khaki suspension, and performing centrifugal separation to obtain brown yellow slurry;
(5) and adding hydrofluoric acid into the brown yellow slurry, stirring and reacting for 5-20 min at room temperature, performing centrifugal separation and washing on a reaction product, and performing vacuum drying for 10-12 h at 50-65 ℃ to obtain the nano silicon powder.
2. The low-temperature ball-milling nanometer silicon powder as claimed in claim 1, wherein the silicon source has a particle size of 10-5000 meshes, and the aluminum powder and the magnesium powder have particle sizes of 50-300 meshes.
3. The low-temperature ball-milling nanometer silicon powder as claimed in claim 1, wherein in the step (2), the weight ratio of the material to the grinding balls is 1: 8-10, wherein the ball milling equipment is a planetary ball mill, the ball milling speed is 450-600 rpm, and the grinding balls are wear-resistant steel grinding balls.
4. The low-temperature ball-milling nanometer silicon powder as claimed in claim 1, wherein in the step (3), when the temperature of the tank body is reduced to 85-100 ℃, deionized water mist drops are sprayed into the tank body, and the flow rate of the deionized water mist drops is 10-20 ml/min.
5. The low-temperature ball-milled nano silicon powder as claimed in claim 1, wherein the concentration of hydrochloric acid in step (4) is 5-10 wt%, and the concentration of hydrofluoric acid in step (5) is 4-10 wt%.
6. The application of the low-temperature ball-milled nano silicon powder as defined in any one of claims 1-2 in a negative electrode material of a lithium ion battery.
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| CN110386604A (en) * | 2019-08-09 | 2019-10-29 | 北方奥钛纳米技术有限公司 | The preparation method of nano-silicon, silicon based anode material and preparation method thereof |
| CN110371982A (en) * | 2019-08-29 | 2019-10-25 | 贵州大学 | A kind of method of fused salt magnesium reduction process reduced nano silica |
| CN110943211A (en) * | 2019-12-16 | 2020-03-31 | 安徽工业大学 | Preparation method of high-performance Si/C negative electrode material |
| CN115485085A (en) * | 2020-04-30 | 2022-12-16 | 基纳泰克有限公司 | Low temperature reduction of metal oxides |
| CN114142016A (en) * | 2021-11-30 | 2022-03-04 | 陕西榆能集团能源化工研究院有限公司 | Micron-scale sheet layered Si/SiO2Composite material, preparation method and application thereof |
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