CN112952071B - Porous conductive ceramic composite silicon negative electrode material and preparation method thereof - Google Patents
Porous conductive ceramic composite silicon negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a porous conductive ceramic composite silicon negative electrode material which comprises the following raw materials in parts by weight: 50-80 parts of nano silicon powder coated with organic template and TiO210-20 parts of nano fiber powder, 0.5-2 parts of nitriding accelerant, 300 parts of deionized water and 500 parts of non-ionic surfactant and 1-3 parts of non-ionic surfactant; the nano silicon powder coating the organic template comprises the following raw materials in parts by weight: 20-30 parts of nano silicon powder, 4-10 parts of fatty acid and 10-20 parts of organic solvent; the fatty acid is a straight chain or branched chain fatty acid containing 12-18 carbon atoms. The invention also provides a preparation method of the porous conductive ceramic composite silicon negative electrode material. According to the porous conductive ceramic composite silicon negative electrode material provided by the invention, the porous coating layer effectively buffers the volume expansion of nano silicon and keeps the high conductive property of the silicon material, the mobility of lithium ions is improved, the direct contact between the silicon negative electrode and an electrolyte is effectively avoided, a firm SEI film can be formed on the surface of the composite silicon negative electrode, and the cycle performance of the silicon material is greatly improved.
Description
Technical Field
The invention relates to the technical field of preparation of electrode materials, in particular to a porous conductive ceramic composite silicon negative electrode material and a preparation method thereof.
Background
The common negative electrode materials of the lithium ion battery in the current market are mainly graphite materials, such as natural graphite, artificial graphite, hard carbon, mesocarbon microbeads and the like, but the theoretical capacity of the carbon negative electrode material is only 372 mAh/g; moreover, the lithium intercalation potential of the material is mainly concentrated in the range of 0-0.1V, which is very close to the deposition potential of metallic lithium, and is not beneficial to the safety of the battery, while the lithium titanate negative electrode material has the biggest problem that the theoretical capacity is low, the flatulence is easy to generate, and the lithium titanate negative electrode material does not accord with the development trend of power batteries.
Silicon is considered as one of novel negative electrode materials most likely to replace graphite, because the theoretical specific capacity of the silicon is 4200mAh/g, which is much higher than that of the graphite material, and the voltage platform of the silicon is slightly higher than that of the graphite, which does not cause surface lithium precipitation during charging, has better safety performance, and in addition, the silicon has wide sources and abundant storage, for example, patent CN111115638A discloses a preparation method of a silicon-based negative electrode material. However, the silicon cathode also faces serious problems, firstly, the conductivity of silicon is low, and the silicon cannot be directly used as a cathode material; secondly, the volume change of the silicon material is large (about 300%) in the using process, so that the material is easy to gradually pulverize, the structure is collapsed, and finally, the electrode active substance is separated from a current collector and loses electric contact, and the cycle performance of the battery is greatly reduced; with the destruction of the electrode structure, new SEI films are continuously formed on the exposed silicon surface, which aggravates silicon corrosion and capacity fade.
Disclosure of Invention
The invention aims to solve the technical problems that a silicon negative electrode material in a lithium battery is low in conductivity and prone to volume expansion failure.
The invention solves the technical problems through the following technical means:
a porous conductive ceramic composite silicon negative electrode material comprises the following raw materials in parts by weight: 50-80 parts of nano silicon powder coated with organic template and TiO210-20 parts of nano fiber powder, 0.5-2 parts of nitriding accelerant, 500 parts of deionized water and 1-3 parts of nonionic surfactant;
the nano silicon powder coated on the organic template comprises the following raw materials in parts by weight: 20-30 parts of nano silicon powder, 4-10 parts of fatty acid and 10-20 parts of organic solvent;
the fatty acid is a straight chain or branched chain fatty acid containing 12-18 carbon atoms.
According to the porous conductive ceramic composite silicon negative electrode material provided by the invention, the porous coating layer effectively buffers the volume expansion of nano silicon and keeps the high conductive property of the silicon material, the mobility of lithium ions is improved, the direct contact between the silicon negative electrode and an electrolyte is effectively avoided, a firm SEI film can be formed on the surface of the composite silicon negative electrode, and the cycle performance of the silicon material is greatly improved.
Preferably, the organic solvent is an ester or ketone solvent.
A preparation method of a porous conductive ceramic composite silicon negative electrode material comprises the following steps:
(1) uniformly mixing nano silicon powder, fatty acid and an organic solvent by weight, heating and refluxing at 50-80 ℃, cooling, filtering out solids, evaporating the organic solvent at 25-50 ℃ under reduced pressure for 0.5-2h to obtain nano silicon powder coated with the organic template;
(2) uniformly mixing a titanate solution and a polyvinylpyrrolidone solution according to a mass ratio of 2:1-5:1 to obtain an electrostatic spinning stock solution, controlling the extrusion of the electrostatic spinning stock solution by a micro-injection device, connecting a nozzle of the micro-injection device with a cathode of a power supply, connecting a metal plate covered with an aluminum foil layer and connected with an anode of the power supply with a spinning receiving device, and carrying out electrostatic spinning to obtain TiO2A nanofiber; after the reaction is finished, the obtained TiO2Calcining the nano-fiber at the temperature of 400-500 ℃ for 3-8h to obtain anatase TiO2A nanofiber;
(3) coating the nano silicon powder and TiO of the organic template by weight2Uniformly mixing the nano-fiber powder, the nitriding accelerant and deionized water, carrying out ball milling at the ball milling rotation speed of 500-1500 r/min for 2-8h, adding the nonionic surfactant, dispersing at the high speed of 1000-1500r/min for 1-4h, and then carrying out reduced pressure drying at 80-90 ℃ to obtain porous precursor powder;
(4) and (4) placing the porous precursor powder prepared in the step (3) into an ammonia gas atmosphere furnace, introducing ammonia gas at the flow rate of 50-2000mL/min, heating to 900-1200 ℃ at the speed of 4-10 ℃/min, keeping for 2-8h, and cooling to room temperature in the nitrogen or argon atmosphere to obtain the porous conductive ceramic composite silicon cathode material.
Further, the preparation method of the titanate solution comprises the following steps: the preparation method is characterized in that a mixed solution of ethanol and acetic acid is used as a solvent, and titanate is added to obtain the product.
Further, the titanate is selected from at least one of ethyl titanate, isopropyl titanate and butyl titanate.
Furthermore, in the mixed solution of ethanol and acetic acid, the volume ratio of ethanol to acetic acid is 1: 1.
Further, the preparation method of the polyvinylpyrrolidone solution comprises the following steps: the preparation method is characterized by taking ethanol as a solvent and adding polyvinylpyrrolidone to prepare the compound.
Further, the polyvinylpyrrolidone has a number average molecular weight of 1,300,000.
Further, the flow rate of the electrostatic spinning solution is 4-20 mL/h; the voltage of the power supply is 2-4 ten thousand volts, and the distance from the nozzle of the micro-injection device to the metal plate covered with the aluminum foil layer is 15-30 cm.
Further, the nitriding accelerant comprises one or more of nano titanium nitride powder, metal titanium powder or titanium hydride powder; the particle size of the nitriding promoter is less than 100 nm.
The invention has the following beneficial effects:
1. according to the porous conductive ceramic composite silicon negative electrode material provided by the invention, the porous coating layer effectively buffers the volume expansion of nano silicon and keeps the high conductive property of the silicon material, the mobility of lithium ions is improved, the direct contact between the silicon negative electrode and an electrolyte is effectively avoided, a firm SEI film can be formed on the surface of the composite silicon negative electrode, and the cycle performance of the silicon material is greatly improved.
2. The porous conductive ceramic coating layer of the porous conductive ceramic composite silicon negative electrode material prepared by the invention has the advantages of high porosity, uniform pore size distribution, controllable structure, excellent mechanical property, good conductivity, and stronger electrochemical stability and corrosion resistance.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
A porous conductive ceramic composite silicon negative electrode material comprises the following steps:
(1) uniformly mixing 20 parts of nano silicon powder, 4 parts of fatty acid and 10 parts of ethyl acetate by weight, heating and refluxing at 60 ℃, cooling, filtering out solids, and evaporating an organic solvent at 50 ℃ under reduced pressure for 1h to obtain nano silicon powder coated with an organic template;
(2) adding 1.5g of n-isopropyl titanate into a mixed solution of 3mL of ethanol and 3mL of acetic acid, fully stirring, then adding into 7.5mL of ethanol dissolved with 0.45g of polyvinylpyrrolidone (PVP number average molecular weight is 1,300,000), magnetically stirring for 15min, sucking the obtained solution into a plastic syringe, controlling the flow rate to be 4mL/h, connecting a stainless steel needle head with an anode of a high-voltage power supply, setting the voltage to be 3 kilovolts, and setting the distance from the needle head to a receiving plate to be 25 cm; after the reaction is finished, calcining the obtained TiO2 nano-fiber for 4 hours at 500 ℃ to obtain anatase TiO2 nano-fiber;
(3) uniformly mixing 50 parts by weight of nano silicon powder coated with an organic template, 10 parts by weight of TiO2 nano fiber powder, 0.5 part by weight of nano titanium nitride powder and 300 parts by weight of deionized water, carrying out ball milling at the ball milling rotating speed of 1000 r/min for 5h, adding 1 part by weight of nonionic surfactant, dispersing at the high speed of 1200r/min for 2h, and drying at 90 ℃ under reduced pressure to obtain porous precursor powder;
(4) and (4) placing the porous precursor powder prepared in the step (3) into an ammonia gas atmosphere furnace, introducing ammonia gas at the flow rate of 150mL/min, heating to 900 ℃ at the speed of 4 ℃/min, keeping for 8h, and cooling to room temperature in the nitrogen atmosphere to obtain the porous conductive ceramic composite silicon negative electrode material.
Example 2
A porous conductive ceramic composite silicon negative electrode material comprises the following steps:
(1) uniformly mixing 30 parts of nano silicon powder, 10 parts of stearic acid and 20 parts of ethyl acetate by weight, heating and refluxing at 60 ℃, cooling, filtering out solids, and distilling out an organic solvent at 50 ℃ under reduced pressure for 1h to obtain nano silicon powder coated with an organic template;
(2) adding 1.5g of ethyl orthotitanate into a mixed solution of 5mL of ethanol and 5mL of acetic acid, fully stirring, then adding into 9mL of ethanol dissolved with 0.78g of polyvinylpyrrolidone (PVP number average molecular weight is 1,300,000), magnetically stirring for 25min, sucking the obtained solution into a plastic syringe, controlling the flow rate to be 6mL/h, connecting a stainless steel needle with an anode of a high-voltage power supply, setting the voltage to be 2.5 ten thousand volts, and setting the distance from the needle to a receiving plate to be 18 cm; after the reaction is finished, calcining the obtained TiO2 nano-fiber for 4 hours at 500 ℃ to obtain anatase TiO2 nano-fiber;
(3) uniformly mixing 70 parts of nano silicon powder coated with an organic template, 20 parts of TiO2 nano fiber powder, 1 part of metal titanium powder and 500 parts of deionized water by weight, carrying out ball milling at the ball milling rotating speed of 1000 r/min for 5h, adding 2 parts of nonionic surfactant, dispersing at the high speed of 1200r/min for 2h, and drying at 90 ℃ under reduced pressure to obtain porous precursor powder;
(4) and (4) placing the porous precursor powder prepared in the step (3) into an ammonia gas atmosphere furnace, introducing ammonia gas at the flow rate of 500mL/min, heating to 1000 ℃ at the speed of 8 ℃/min, keeping for 2h, and then cooling to room temperature under the argon atmosphere to obtain the porous conductive ceramic composite silicon cathode material.
Example 3
A porous conductive ceramic composite silicon negative electrode material comprises the following steps:
(1) uniformly mixing 25 parts by weight of nano silicon powder, 5 parts by weight of stearic acid and 15 parts by weight of acetone, heating and refluxing at 60 ℃, cooling, filtering out solids, and evaporating an organic solvent at 50 ℃ under reduced pressure for 1h to obtain nano silicon powder coated with an organic template;
(2) 2.5g of n-butyl titanate was added to a mixed solution of 7mL of ethanol and 7mL of acetic acid, sufficiently stirred, then added to 12mL of ethanol in which 0.85g of polyvinylpyrrolidone (PVP number average molecular weight 1,300,000) was dissolved, magnetically stirred for 50min, the resulting solution was taken into a plastic syringe with a flow rate of 5mL/h, a stainless steel needle was connected to the anode of a high voltage power supply, the voltage was set to 3.5 ten thousand volts, and the distance from the needle to the receiving plate was 25 cm. After the reaction is finished, calcining the obtained TiO2 nano-fiber for 4 hours at 500 ℃ to obtain anatase TiO2 nano-fiber;
(3) 80 parts of nano silicon powder coated with an organic template and TiO by weight2Uniformly mixing 15 parts of nano fiber powder, 2 parts of titanium hydride powder and 400 parts of deionized water, carrying out ball milling at the ball milling rotation speed of 1000 r/min for 5h, adding 3 parts of nonionic surfactant, dispersing at the high speed of 1200r/min for 2h, and carrying out reduced pressure drying at 80 ℃ to obtain porous precursor powder;
(4) and (4) placing the porous precursor powder prepared in the step (3) into an ammonia gas atmosphere furnace, introducing ammonia gas at the flow rate of 2000mL/min, heating to 1200 ℃ at the speed of 10 ℃/min, keeping for 5h, and then cooling to room temperature under the argon atmosphere to obtain the porous conductive ceramic composite silicon cathode material.
Example 4
A porous conductive ceramic composite silicon negative electrode material comprises the following steps:
(1) uniformly mixing 20 parts of nano silicon powder, 8 parts of stearic acid and 15 parts of ethyl acetate by weight, heating and refluxing at 60 ℃, cooling, filtering out solids, and distilling out an organic solvent at 50 ℃ under reduced pressure for 1h to obtain nano silicon powder coated with an organic template;
(2) adding 1.0g of n-isopropyl titanate into a mixed solution of 5mL of ethanol and 5mL of acetic acid, stirring the mixture sufficiently, then adding the mixture into 8mL of ethanol dissolved with 0.25g of polyvinylpyrrolidone (PVP number average molecular weight is 1,300,000), stirring the mixture magnetically for 30min, sucking the obtained solution into a plastic syringe, controlling the flow rate to be 4mL/h, connecting a stainless steel needle with an anode of a high-voltage power supply, setting the voltage to be 2 ten thousand volts, and setting the distance from the needle to a receiving plate to be 15 cm. After the reaction is finished, calcining the obtained TiO2 nano-fiber at 400 ℃ for 5 hours to obtain anatase TiO2 nano-fiber;
(3) uniformly mixing 60 parts of nano silicon powder coated with an organic template, 15 parts of TiO2 nano fiber powder, 1 part of titanium nitride powder and 400 parts of deionized water by weight, carrying out ball milling at the ball milling rotating speed of 1000 r/min for 5h, adding 2 parts of nonionic surfactant, dispersing at the high speed of 1200r/min for 2h, and drying at 80 ℃ under reduced pressure to obtain porous precursor powder;
(4) and (4) placing the porous precursor powder prepared in the step (3) into an ammonia gas atmosphere furnace, introducing ammonia gas at the flow rate of 1000mL/min, heating to 1100 ℃ at the speed of 6 ℃/min, keeping for 6h, and then cooling to room temperature under the nitrogen atmosphere to obtain the porous conductive ceramic composite silicon cathode material.
Example 5
The electrochemical performance of the cathode material is researched by adopting a button cell, deionized water is adopted as a solvent for the cathode, and the ratio of active substances: SP: CMC: preparing slurry with the solid content of 45% from the mixture of 85:5:5:5, uniformly coating the slurry on a copper foil, putting the copper foil into an oven, carrying out vacuum drying at 80 ℃ for 12h, taking out the copper foil, carrying out slicing and rolling, and carrying out vacuum drying at 80 ℃ for 12h to obtain a pole piece for the experimental battery; a metal lithium sheet is used as a counter electrode, an electrolyte is a solution of EC and DMC (volume ratio of 1:1) of 1.0mol/LLIPF6, a diaphragm is a celgard2000 film, and the CR2016 type button cell is assembled in a glove box filled with argon atmosphere.
And (3) carrying out charge-discharge cycle test on the button cell: the cut-off voltage of charge and discharge is 0.01-2.0V, the charge and discharge multiplying power is 0.1C, and the specific charge and discharge data are shown in Table 1.
Table 1 shows the results of electrochemical properties of the porous conductive ceramic composite silicon negative electrode materials prepared in examples 1 to 4
In conclusion, the porous coating layer of the porous conductive ceramic composite silicon negative electrode material provided by the invention effectively buffers the volume expansion of nano silicon, keeps the silicon material with high conductive property, improves the mobility of lithium ions, effectively avoids the direct contact of the silicon negative electrode and electrolyte, can form a firm SEI film on the surface of the composite silicon negative electrode, and greatly improves the cycle performance of the silicon material.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. The porous conductive ceramic composite silicon anode material is characterized by comprising the following raw materials in parts by weight: 50-80 parts of nano silicon powder coated with organic template and TiO210-20 parts of nano fiber powder, 0.5-2 parts of nitriding accelerant, 500 parts of deionized water and 1-3 parts of nonionic surfactant;
the nano silicon powder coated on the organic template comprises the following raw materials in parts by weight: 20-30 parts of nano silicon powder, 4-10 parts of fatty acid and 10-20 parts of organic solvent;
the fatty acid is a straight chain or branched chain fatty acid containing 12-18 carbon atoms;
the nitriding accelerant comprises one or more of nano titanium nitride powder, metal titanium powder or titanium hydride powder;
the preparation method of the porous conductive ceramic composite silicon negative electrode material comprises the following steps:
(1) uniformly mixing nano silicon powder, fatty acid and an organic solvent by weight, heating and refluxing at 50-80 ℃, cooling, filtering out solids, and distilling the organic solvent under reduced pressure at 25-50 ℃ for 0.5-2h to obtain nano silicon powder coated with the organic template;
(2) uniformly mixing titanate solution and polyvinylpyrrolidone solution according to the mass ratio of 2:1-5:1 to obtain electrostatic spinning stock solution, controlling the extrusion of the electrostatic spinning stock solution by a micro-injection device, connecting a nozzle of the micro-injection device with a cathode of a power supply, and connecting a cover connected with an anode of the power supplyUsing a metal plate with an aluminum foil layer as a spinning receiving device to carry out electrostatic spinning to obtain TiO2A nanofiber; after the reaction is finished, the obtained TiO2Calcining the nano-fiber at the temperature of 400-500 ℃ for 3-8h to obtain anatase TiO2A nanofiber;
(3) coating the nano silicon powder and TiO of the organic template by weight2Uniformly mixing the nano-fiber powder, the nitriding accelerant and deionized water, carrying out ball milling at the ball milling rotation speed of 500-1500 r/min for 2-8h, adding the nonionic surfactant, dispersing at the high speed of 1000-1500r/min for 1-4h, and then carrying out reduced pressure drying at 80-90 ℃ to obtain porous precursor powder;
(4) and (4) placing the porous precursor powder prepared in the step (3) into an ammonia gas atmosphere furnace, introducing ammonia gas at the flow rate of 50-2000mL/min, heating to 900-1200 ℃ at the speed of 4-10 ℃/min, keeping for 2-8h, and cooling to room temperature in the nitrogen or argon atmosphere to obtain the porous conductive ceramic composite silicon cathode material.
2. The porous conductive ceramic composite silicon anode material as claimed in claim 1, wherein: the organic solvent is an ester or ketone solvent.
3. The preparation method of the porous conductive ceramic composite silicon anode material as claimed in claim 1, wherein the preparation method of the titanate solution comprises the following steps: the preparation method is characterized in that a mixed solution of ethanol and acetic acid is used as a solvent, and titanate is added to obtain the product.
4. The preparation method of the porous conductive ceramic composite silicon negative electrode material according to claim 3, characterized in that: the titanate is at least one selected from ethyl titanate, isopropyl titanate and butyl titanate.
5. The preparation method of the porous conductive ceramic composite silicon negative electrode material according to claim 3, characterized in that: in the mixed solution of the ethanol and the acetic acid, the volume ratio of the ethanol to the acetic acid is 1: 1.
6. The preparation method of the porous conductive ceramic composite silicon anode material as claimed in claim 1, wherein the preparation method of the polyvinylpyrrolidone solution comprises the following steps: the preparation method is characterized by taking ethanol as a solvent and adding polyvinylpyrrolidone to prepare the compound.
7. The preparation method of the porous conductive ceramic composite silicon negative electrode material according to claim 6, characterized in that: the polyvinylpyrrolidone has a number average molecular weight of 1,300,000.
8. The preparation method of the porous conductive ceramic composite silicon negative electrode material according to claim 1, characterized in that: the flow rate of the electrostatic spinning solution is 4-20 mL/h; the voltage of the power supply is 2-4 ten thousand volts, and the distance from the nozzle of the micro-injection device to the metal plate covered with the aluminum foil layer is 15-30 cm.
9. The preparation method of the porous conductive ceramic composite silicon negative electrode material according to claim 1, characterized in that: the particle size of the nitriding promoter is less than 100 nm.
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| CN110350161A (en) * | 2019-06-18 | 2019-10-18 | 长沙矿冶研究院有限责任公司 | A kind of preparation method of silicon-carbon cathode presoma |
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