CN114335490A - Preparation method of C @ Cu @ Si composite porous negative electrode material of lithium ion battery - Google Patents
Preparation method of C @ Cu @ Si composite porous negative electrode material of lithium ion battery Download PDFInfo
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- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- -1 polypropylene Polymers 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
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- 239000004743 Polypropylene Substances 0.000 claims description 6
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- 229920001155 polypropylene Polymers 0.000 claims description 6
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- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
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- 229910021338 magnesium silicide Inorganic materials 0.000 description 1
- YTHCQFKNFVSQBC-UHFFFAOYSA-N magnesium silicide Chemical compound [Mg]=[Si]=[Mg] YTHCQFKNFVSQBC-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a C @ Cu @ Si composite porous negative electrode material of a lithium ion battery, which comprises the steps of grinding and compounding silicon powder and copper powder to obtain copper-silicon composite powder; magnetically stirring asphalt powder, deionized water and tetrahydrofuran to obtain a uniform mixed solution; establishing a cold spraying system, taking copper foil as a substrate, configuring a pressure balancing device outside a powder feeder, and connecting the output end of an atomizer to the Laval nozzle expansion section; introducing copper-silicon composite powder into a powder feeder by adopting a double powder feeding mode, filling the mixed solution into an atomizer through an injection pump, carrying the copper-silicon composite powder into a spray pipe through high-temperature and high-pressure airflow, colliding with and wrapping liquid drops atomized by the atomizer, and colliding with the surface of a substrate at a high speed to realize deposition to obtain a composite coating; the composite coating is carbonized after being dried to obtain the lithium ion battery C @ Cu @ Si composite porous cathode material, and the double-layer coating structure of the carbon, the copper and the silicon can effectively relieve the problem of volume expansion of a silicon-based cathode.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to a preparation method of a C @ Cu @ Si composite porous negative electrode material of a lithium ion battery.
Background
Lithium ion battery is used in convenient intelligent product fields such as cell-phone, unmanned aerial vehicle because of its specific capacity height, long cycle life's advantage such as is used in a large number, and is along with portable energy storage equipment's appearance and popularization equally, lithium ion battery's commercial demand is bigger and bigger.
Because the theoretical capacity is too small, the conventional graphite cathode cannot meet the commercial requirements of the existing lithium ion battery. Silicon materials have gained attention in a number of alternative materials due to their own high specific capacity (3580 mAh/g).
The technology for extracting the simple substance silicon is mature in industry, however, the silicon is used as the negative electrode of the lithium ion battery, the battery has huge volume change in the working process, namely the process of lithium ion insertion and extraction, the violent volume expansion can cause larger stress to be generated in the negative electrode, and finally, part of electrode materials are pulverized to cause the failure of the battery; in addition, the constant volume expansion of silicon in each cycle process can prevent the stable and uniform SEI film from being formed in the electrode, then the electrode can crack, and new SEI films are continuously generated until the electrolyte is completely consumed, so that the battery is also failed.
Researchers at home and abroad make a great deal of research on the defects of the lithium ion silicon-based negative electrode, such as modes of nano-sizing particles, coating carbon, compounding with carbon materials or non-metal materials and the like aiming at the materials; in addition to materials, novel adhesives are developed, electrolyte compositions are improved, and current collectors are coated.
The high-energy ball milling method is different from the traditional composite process, has the advantages of low reaction temperature, uniform powder particle size, suitability for batch production and the like, and can be used for preparing superfine composite powder which cannot be prepared by a chemical method or a high-temperature method.
The cold gas dynamic spraying (cold spraying) technology is a surface deposition technology developed in recent years, spraying powder is sent into a Laval nozzle by a powder feeder, is accelerated by supersonic airflow and then impacts on a substrate at high speed to generate severe plastic deformation, and is deposited on the substrate to form a coating.
Atomization is a technique of dispersing a liquid into numerous tiny droplets by a special device. The liquid is sprayed in a mist form through a high-speed air flow or a pressure nozzle.
The currently adopted preparation schemes of silicon-carbon compounding, silicon-copper compounding and the like have the defects of high production cost, low efficiency, low bonding strength, complex process, difficulty in large-scale production and the like.
The invention discloses a preparation method of a porous silicon-carbon composite material, as in the Chinese patent with the application number of CN201610164963.4, which comprises the following steps: placing magnesium silicide powder in a CO2/Ar mixed atmosphere, carrying out heat treatment at 700-900 ℃, and carrying out acid pickling and post-treatment to obtain the porous silicon-carbon composite material; in the CO2/Ar mixed atmosphere, the volume fraction of CO2 is 10-90%. The heat treatment time of the scheme is about 10-20 hours, hydrochloric acid with the concentration of 0.5-5 mol/L is adopted for acid washing, the treatment time is 2-10 hours, and the method further comprises the processes of water washing, product centrifugation, vacuum drying and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a lithium ion battery C @ Cu @ Si composite porous negative electrode material. A series of physical methods are adopted to construct a porous structure, so that a containable space is provided for the volume expansion of the silicon-based negative electrode of the lithium ion battery, and the conductivity is enhanced.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a lithium ion battery C @ Cu @ Si composite porous negative electrode material comprises the following steps:
(1) mixing silicon powder and copper powder in proportion, and grinding and compounding by adopting a high-energy ball milling method to obtain copper-silicon composite powder;
(2) mixing asphalt powder, deionized water and tetrahydrofuran in proportion, and magnetically stirring to obtain a uniform mixed solution;
(3) establishing a cold spraying system, taking a pre-cleaned copper foil as a substrate, configuring a pressure balancing device outside a powder feeder to realize gravity powder feeding, driving the fed powder through high-temperature and high-pressure airflow, introducing the powder into a Laval nozzle, and connecting the output end of an atomizer to an expansion section of the Laval nozzle;
(4) introducing the copper-silicon composite powder into a powder feeder by adopting a double powder feeding mode, filling the mixed solution into an atomizer through an injection pump, carrying the copper-silicon composite powder sent out by gravity into a Laval nozzle through high-temperature and high-pressure airflow in the spraying process, passing through a throat part to reach a nozzle expansion section, colliding with and being wrapped by liquid drops atomized by the atomizer, and colliding with the surface of a substrate at high speed to realize deposition to obtain a composite coating;
(5) and drying the composite coating and then carbonizing to obtain the carbon-copper-silicon composite porous cathode of the lithium ion battery.
Furthermore, the volume ratio of the copper powder to the silicon powder in the step (1) is 1 (1-2).
Further, in the step (1), the average grain diameter of the silicon powder is 500nm-50 μm, and the average grain diameter of the copper powder is 500nm-30 μm.
Further, the rotation speed range of the ball mill in the step (1) is 200-600rpm, the ball-material ratio is 10:1, and the ball milling time is 4-24 h.
Further, in the step (2), the asphalt powder, the deionized water and the tetrahydrofuran are mixed at room temperature and are magnetically stirred.
Further, the volume ratio of the asphalt powder, the deionized water and the tetrahydrofuran in the step (2) is 1: (0.5-2): 1.
further, in the step (3), the diameter of the spray hole of the atomizer is 0.1-0.5mm, the diameter of the joint of the output end of the atomizer and the Laval nozzle is 0.1-20mm, the diameter of the orifice of the powder feeder is 0.1-0.5mm, and the diameter of the powder feeding pipe is 0.1-20 mm.
Furthermore, in the step (3), the laval nozzle, the powder feeder, the powder feeding pipe, the atomizer and the output end thereof are made of stainless steel, so that the airtightness of the whole cold spraying process is ensured.
Further, the position of the output end of the atomizer in the step (3) is 1/3-2/3 of the length of the whole nozzle expanding section.
Further, in the step (3), the flow rate of the atomizer is 0.01-0.3L/min, the atomization pressure is 1-10MPa, the flow rate of the powder feeder is 10-150g/min, the high-temperature and high-pressure airflow pressure, namely the airflow pressure of the cold spraying nitrogen is 1-10MPa, the atomization pressure is generally required to be larger than the main airflow pressure, the spraying temperature is 100-.
Further, in the step (4), the atomization amount of the atomizer is controlled by adjusting the pressure of the injection pump, the powder feeding amount of the powder feeder is controlled by adjusting the pulse frequency of the stepping motor, after the copper-silicon composite powder sent by the powder feeder and liquid drops atomized by the atomizer impact and mix at the expansion section of the spray pipe, the copper-silicon composite powder is accelerated by the main air flow of the cold spraying system, the spraying direction is downward and vertical to the horizontally placed copper foil substrate, and the deposition thickness is 0.1-1mm, so that the composite coating is prepared.
Further, in the step (5), the composite coating is dried for 1-12h at 70-150 ℃. And then moving the porous carbon material into a nitrogen atmosphere, heating the porous carbon material to 500-1500 ℃ at the heating rate of 5 ℃/min, and carbonizing the porous carbon material for 1-24 hours to obtain the C @ Cu @ Si composite porous negative electrode material.
The application of the C @ Cu @ Si composite porous anode material prepared by the preparation method disclosed by the invention is as follows: the half cell is assembled by taking a metal lithium sheet as a counter electrode, a single-layer polypropylene as a diaphragm (Celgard 2300), a mixed solution of a 1mol/L lithium hexafluorophosphate solution and a solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) 1:1 (volume ratio) as an electrolyte, and the C @ Cu @ Si composite porous negative electrode material as a negative electrode (for the half cell, the C @ Cu @ Si composite porous negative electrode material is actually used as a positive electrode).
Further, the half-cell installation is required to be performed in an argon glove box.
Further, the assembly process of the half cell is as follows: firstly, the negative electrode shell is placed on an insulating table board, the gasket and the metal lithium piece are sequentially placed in the center of the negative electrode shell by using insulating tweezers, then the metal lithium piece is flattened by using a pressing die, a proper amount of electrolyte is taken by using a pipettor to be added to the surface of the lithium piece, the diaphragm is placed in the center and placed on the surface of the electrolyte, the proper amount of electrolyte is taken by using the pipettor to be dripped to the surface of the diaphragm, and the negative electrode piece, the gasket, the elastic piece and the positive electrode shell are sequentially placed on the diaphragm.
According to the invention, copper-silicon composite powder with different structures and sizes is prepared by adjusting the volume ratio of silicon powder to copper powder in the experimental preparation process. The C @ Cu @ Si composite coating with different element concentrations and porosities is prepared by adjusting the dissolution ratio of the asphalt powder, the deionized water and the tetrahydrofuran and carrying out atomization and cold spray deposition. C @ Cu @ Si composite coatings with different bonding strengths and deposition efficiencies are prepared by adjusting the position of a liquid drop output end of an atomizer.
The invention has the beneficial effects that:
1. the metal copper with better conductivity is selected to be ball-milled and compounded with the copper, so that the volume effect is favorably relieved, the electronic conductivity is favorably enhanced, and the experimental controllability is improved by adopting a physical process.
2. The copper selected in the invention is used as a binder, and in order to realize good connection in the silicon-based cathode, an organic solution is doped and carbonization treatment is carried out, so that a stable conductive network is constructed, a porous structure is formed, a lithium ion transmission channel is increased, and the ionic conductivity and the electronic conductivity are improved.
3. The invention can realize the high-efficiency compounding of the copper-silicon composite powder and the carbon-based material, and prepare the composite coating with uniformly dispersed elements and controllable thickness of the composite material.
4. The lithium ion battery C @ Cu @ Si composite porous cathode prepared by the invention has the advantages of excellent conductivity, high first coulombic efficiency, good cycle performance and the like.
5. The lithium ion battery prepared by the invention has the advantages of excellent conductivity, high first coulombic efficiency, good cycle performance and the like because of the lithium ion battery C @ Cu @ Si composite porous negative electrode prepared by the invention.
6. The preparation method is simple and easy to operate, reduces the cost while relieving the volume expansion of silicon, improves the efficiency, and has higher feasibility of large-scale production.
Drawings
FIG. 1 is a process flow diagram for preparing a lithium ion battery C @ Cu @ Si composite porous anode according to the present invention.
Fig. 2 is a schematic view of the internal structure of the half cell according to the present invention.
Fig. 3 shows electrochemical cycling test results of electrodes prepared by spraying after ball milling for 24h with Cu: Si =1:1 (volume ratio).
Fig. 4 shows EIS test results after 200 cycles of spraying-prepared electrodes after ball milling for 24h with Cu: Si =1:1 (volume ratio).
Detailed Description
The present invention will be described in detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given the full breadth of the appended claims and any and all non-essential modifications and variations thereof.
Example 1
The metal lithium sheet is used as a negative electrode active material of the lithium ion battery, and the C @ Cu @ Si composite porous negative electrode prepared in the embodiment is used as a positive electrode active material of the lithium ion battery. The method comprises the following specific implementation steps: weighing copper powder of 5 mu m and silicon powder of 10 mu m according to a volume ratio of 1:1 (the mass is 17.8g and 4.6g respectively), mixing and placing the mixture into a grinding tank, taking zirconium dioxide as grinding balls, the ball material ratio of 10:1, the rotating speed of a ball mill is 300rpm, carrying out continuous forward rotation dry grinding for 12h, then adding the mixture into a powder feeder, mixing asphalt powder, deionized water and tetrahydrofuran according to the volume ratio of 1:0.5:1, adding the mixture into an injector after magnetic stirring for 1h, adjusting the temperature of a heater of a cold spraying system to be kept at 300 ℃, keeping the spraying pressure at 2MPa, keeping the pressure of an injection pump (namely the pressure of an atomizer) at 2.5MPa, controlling the flow rate of the atomizer at 0.01L/min, controlling the flow rate of the powder feeder at 10g/min, connecting the liquid drop output end of the atomizer to an expansion section 1/3 of a spray pipe, keeping the distance of a nozzle at 30mm from a substrate and the scanning speed of the spray pipe at 0.1m/s, keeping the pulse frequency of a stepping motor at 500Hz, the thickness of the copper foil substrate at 0.2mm, the spraying pass at 2 and the deposition thickness at 0.1mm, preparing a composite coating, drying the composite coating at 70 ℃ for 10h, transferring the composite coating into a nitrogen atmosphere, heating to 900 ℃ at a heating rate of 5 ℃/min, and carbonizing for 3h to obtain the cathode material. The half cell was assembled in the order described with a positive electrode material, a polypropylene microporous separator (Celgard 2300), and a 1mol/L solution of lithium hexafluorophosphate mixed with a 1:1 (by volume) solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in an argon glove box. The lithium ion battery with the composite porous cathode is charged for the first time for 2 hours at room temperature at a constant current of 0.05C, is discharged for the first time at a constant current of 0.5C, and is tested for the first cycle, the coulombic efficiency of the first reversible cycle and the capacity retention rate after 500 cycles.
Example 2
This embodiment differs from embodiment 1 only in that: the rotation speed of the ball mill is 500 rpm.
Example 3
This embodiment differs from embodiment 1 only in that: the volume ratio of the copper powder to the silicon powder is 1: 2.
example 4
This embodiment differs from embodiment 1 only in that: and continuously carrying out forward rotation ball milling for 24 hours.
Example 5
This embodiment differs from embodiment 1 only in that: the volume ratio of the asphalt powder to the deionized water to the tetrahydrofuran is 1:1: 1.
Example 6
This embodiment differs from embodiment 1 only in that: the spraying temperature was 500 ℃.
Example 7
This embodiment differs from embodiment 1 only in that: the nozzle scanning speed was 0.2 m/s.
Example 8
This embodiment differs from embodiment 1 only in that: the pressure of the injection pump and the pressure of the powder feeder are both kept at 3 MPa.
Example 9
This embodiment differs from embodiment 1 only in that: the first charge was carried out at 0.5C constant current for 2 h.
Example 10
This embodiment differs from embodiment 1 only in that: the first discharge was performed with a constant current of 1C.
Example 11
The metal lithium sheet is used as a negative electrode active material of the lithium ion battery, and the C @ Cu @ Si composite porous negative electrode prepared by the method is used as a positive electrode active material of the lithium ion battery. The method comprises the following specific implementation steps: mixing 500 mu m copper powder and 30 mu m silicon powder according to a volume ratio of 1:1, putting the mixture into a grinding tank, taking zirconium dioxide as grinding balls, taking a ball material ratio of 10:1, carrying out continuous forward rotation dry grinding for 10h at a ball mill rotation speed of 600rpm, adding the mixture into a powder feeder, mixing asphalt powder, deionized water and tetrahydrofuran according to a volume ratio of 1:2:1, adding the mixture into an injector after carrying out magnetic stirring for 1h, adjusting the temperature of a heater of a cold spraying system to be kept at 300 ℃, the spraying pressure to be kept at 5MPa, the pressure of an injection pump (namely the pressure of an atomizer) to be kept at 10MPa, the flow of the atomizer to be 0.3L/min, the flow of the powder feeder to be 150g/min, the liquid drop output end of the atomizer to be connected to an expansion section 1/3 of a spraying pipe, the distance of the spraying nozzle to a substrate to be 30mm, the scanning speed of the spraying pipe to be 1m/s, the pulse frequency of a stepping motor to be 100Hz, and the thickness of the copper foil substrate to be 0.2mm, and 5, preparing a composite coating, drying the composite coating for 1h at 150 ℃, transferring the composite coating into a nitrogen atmosphere, heating to 1200 ℃ at a heating rate of 5 ℃/min, and carbonizing for 6h to obtain the cathode material, wherein the deposition thickness is 1 mm. The half cell was assembled in the order described with a positive electrode material, a polypropylene microporous separator (Celgard 2300), and a 1mol/L solution of lithium hexafluorophosphate mixed with a 1:1 (by volume) solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in an argon glove box. The lithium ion battery with the composite porous cathode is charged for the first time for 2 hours at room temperature at a constant current of 0.05C, is discharged for the first time at a constant current of 0.5C, and is tested for the first cycle, the coulombic efficiency of the first reversible cycle and the capacity retention rate after 500 cycles.
Example 12
The metal lithium sheet is used as a negative electrode active material of the lithium ion battery, and the C @ Cu @ Si composite porous negative electrode prepared by the method is used as a positive electrode active material of the lithium ion battery. The method comprises the following specific implementation steps: mixing 500nm copper powder and 500nm silicon powder according to a volume ratio of 1:2, putting the mixture into a grinding tank, taking zirconium dioxide as grinding balls, taking a ball material ratio of 10:1, carrying out continuous forward rotation dry grinding for 12h at a ball mill rotation speed of 200rpm, adding the mixture into a powder feeder, mixing asphalt powder, deionized water and tetrahydrofuran according to a volume ratio of 1:0.5:1, adding the mixture into an injector after magnetic stirring for 1h, adjusting the temperature of a heater of a cold spraying system to be kept at 500 ℃, keeping the spraying pressure at 10MPa, keeping the pressure of an injection pump (namely the pressure of an atomizer) at 10MPa, keeping the flow of the atomizer at 0.2L/min, keeping the flow of the powder feeder at 150g/min, connecting a liquid drop output end of the atomizer to an expansion section 1/3 of a spraying pipe, keeping the distance of the spraying nozzle at 30mm from a substrate, keeping the scanning speed of the spraying pipe at 0.1m/s, keeping the pulse frequency of a stepping motor at 500Hz, and keeping the thickness of the copper foil substrate at 0.2mm, and the spraying pass is 2, the deposition thickness is 0.5mm, the composite coating is prepared, then the composite coating is dried for 5 hours at the temperature of 100 ℃, then the composite coating is moved into a nitrogen atmosphere to be heated to 500 ℃ at the heating rate of 5 ℃/min, and the composite coating is carbonized for 24 hours, so that the cathode material is obtained. The half cell was assembled in the order described with a positive electrode material, a polypropylene microporous separator (Celgard 2300), and a 1mol/L solution of lithium hexafluorophosphate mixed with a 1:1 (by volume) solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in an argon glove box. The lithium ion battery with the composite porous cathode is charged for the first time for 2 hours at room temperature at a constant current of 0.05C, is discharged for the first time at a constant current of 0.5C, and is tested for the first cycle, the coulombic efficiency of the first reversible cycle and the capacity retention rate after 500 cycles.
Example 13
The metal lithium sheet is used as a negative electrode active material of the lithium ion battery, and the C @ Cu @ Si composite porous negative electrode prepared by the method is used as a positive electrode active material of the lithium ion battery. The method comprises the following specific implementation steps: mixing 1 mu m copper powder and 1 mu m silicon powder according to the volume ratio of 1:1, putting the mixture into a grinding tank, taking zirconium dioxide as grinding balls, the ball-material ratio of 10:1, the rotating speed of a ball mill of 400rpm, carrying out continuous forward rotation dry grinding for 4h, then adding the mixture into a powder feeder, mixing asphalt powder, deionized water and tetrahydrofuran according to the volume ratio of 1:1:1, adding the mixture into an injector after magnetic stirring for 1h, adjusting the temperature of a heater of a cold spraying system to be kept at 1000 ℃, the spraying pressure to be kept at 1MPa, the pressure of an injection pump (namely the pressure of an atomizer) to be kept at 1MPa, the flow of the atomizer to be 0.05L/min, the flow of the powder feeder to be 50g/min, the liquid drop output end of the atomizer to be connected to an expansion section 1/3 of a spraying pipe, the distance of the spraying nozzle to a substrate to be 30mm, the scanning speed of the spraying pipe to be 0.1m/s, the pulse frequency of a stepping motor to be 500Hz, and the thickness of the copper foil substrate to be 0.2mm, and the spraying pass is 2, the deposition thickness is 0.5mm, the composite coating is prepared, then the composite coating is dried for 10 hours at the temperature of 90 ℃, then the composite coating is moved into a nitrogen atmosphere and heated to 1500 ℃ at the heating rate of 5 ℃/min, and the composite coating is carbonized for 1 hour, so that the cathode material is obtained. The half cell was assembled in the order described with a positive electrode material, a polypropylene microporous separator (Celgard 2300), and a 1mol/L solution of lithium hexafluorophosphate mixed with a 1:1 (by volume) solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in an argon glove box. The lithium ion battery with the composite porous cathode is charged for the first time for 2 hours at room temperature at a constant current of 0.05C, is discharged for the first time at a constant current of 0.5C, and is tested for the first cycle, the coulombic efficiency of the first reversible cycle and the capacity retention rate after 500 cycles.
Fig. 3 shows electrochemical cycling test results of electrodes prepared by spraying after ball milling for 24h with Cu: Si =1:1 (volume ratio). The circulation mode is constant current charging and discharging, 100mA/g is carried out for the first 3 times, 500mA/g is carried out for the last 197 times, and the circulation times are 200 times. The initial specific capacity is greatly different, Cu @The initial specific capacities of Si-sprayed and C @ Cu @ Si-sprayed electrodes were 76 mAh · g, respectively-1，880 mAh·g-1After 200 times of circulation, the specific capacity of the Cu @ Si-spraying electrode is only 9 mAh g-1And the specific capacity of the C @ Cu @ Si-spraying electrode reaches 186 mAh.g-1. The capacity retention rates of the Cu @ Si-spray electrode at 1,2 and 200 times of cycle are respectively 68.4%, 81.5% and 11.8%, and the capacity retention rates of the C @ Cu @ Si-spray electrode at 1,2 and 200 times of cycle are respectively 43.9%, 40.9% and 21.1%.
Fig. 4 shows EIS test results after 200 cycles of spraying-prepared electrodes after ball milling for 24h with Cu: Si =1:1 (volume ratio). In conjunction with the analysis of the cyclic performance diagram, although Cu is incorporated to design the conductive network to enhance conductivity, the subsequent incorporation of C actually constructs a good conductive network. After 200 cycles, the lithium ion diffusion coefficient of the Cu @ Si-sprayed electrode was 3.98X 10-17 cm² s-1The lithium ion diffusion coefficient of the C @ Cu @ Si-sprayed electrode was 2.22X 10-15 cm² s-1The lithium ion diffusion coefficient of the C @ Cu @ Si-spraying electrode is far greater than that of the Cu @ Si-spraying electrode, and the fact that a complete lithium ion transport channel is constructed by adding the C is proved, the transfer of lithium ions in the electrode can be accelerated, and the electrode shows high electrochemical activity.
The research methods, the basic contents and the beneficial effects of the invention are introduced above. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various modifications and improvements may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A preparation method of a lithium ion battery C @ Cu @ Si composite porous negative electrode material is characterized by comprising the following steps: the method comprises the following steps:
(1) mixing silicon powder and copper powder in proportion, and grinding and compounding by adopting a high-energy ball milling method to obtain copper-silicon composite powder;
(2) mixing asphalt powder, deionized water and tetrahydrofuran in proportion at room temperature, and magnetically stirring to obtain a uniform mixed solution;
(3) establishing a cold spraying system, taking a pre-cleaned copper foil as a substrate, configuring a pressure balancing device outside a powder feeder to realize gravity powder feeding, driving the fed powder through high-temperature and high-pressure airflow, introducing the powder into a Laval nozzle, and connecting the output end of an atomizer to an expansion section of the Laval nozzle;
(4) introducing the copper-silicon composite powder obtained in the step (1) into a powder feeder by adopting a double powder feeding mode, filling the mixed solution obtained in the step (2) into an atomizer through an injection pump, carrying the copper-silicon composite powder sent out by gravity into a Laval nozzle through high-temperature and high-pressure airflow in the spraying process, penetrating through the throat part of the Laval nozzle to reach the nozzle expansion section, colliding with and being wrapped by liquid drops atomized by the atomizer, and colliding with the surface of a substrate at a high speed to realize deposition to obtain a composite coating;
(5) and (4) drying the composite coating obtained in the step (4), and carbonizing to obtain the lithium ion battery C @ Cu @ Si composite porous negative electrode material.
2. The method of claim 1, wherein: the volume ratio of the copper powder to the silicon powder in the step (1) is 1 (1-2); the average grain diameter of the silicon powder is 500nm-50 μm, and the average grain diameter of the copper powder is 500nm-30 μm.
3. The method of claim 1, wherein: the rotating speed range of the ball mill in the step (1) is 200-600rpm, the ball-material ratio is 10:1, and the ball milling time is 4-24 h.
4. The method of claim 1, wherein: in the step (2), the volume ratio of the asphalt powder to the deionized water to the tetrahydrofuran is 1 (0.5-2) to 1.
5. The method of claim 1, wherein: in the step (3), the diameter of the spray hole of the atomizer is 0.1-0.5mm, the diameter of the joint of the output end of the atomizer and the Laval nozzle is 0.1-20mm, the diameter of the orifice of the powder feeder is 0.1-0.5mm, and the diameter of the powder feeding pipe is 0.1-20mm, and in the step (3), the Laval nozzle, the powder feeder, the powder feeding pipe, the atomizer and the output end thereof are made of stainless steel, so that the airtightness in the whole cold spraying process is ensured; and (3) the connection position of the output end of the atomizer and the Laval nozzle in the step (3) is positioned at 1/3-2/3 of the length of the expansion section of the whole Laval nozzle.
6. The method of claim 1, wherein: in the step (4), the flow rate of the atomizer is 0.01-0.3L/min, the atomization pressure is 1-10MPa, the flow rate of the powder feeder is 10-150g/min, the high-temperature high-pressure airflow adopts nitrogen, the pressure of the high-temperature high-pressure airflow is 1-10MPa, the spraying temperature is 100-1000 ℃, the pulse frequency of the stepping motor is 100-3000Hz, the distance between the Laval nozzle and the substrate is 1-50mm, the spraying path is in a bow shape, the spraying scanning speed is 0.1-1m/s, the spraying pass range is 1-5 times, and the accelerating gas used in the spraying process is nitrogen.
7. The method of claim 1, wherein: in the step (4), the atomization amount of the atomizer is controlled by adjusting the pressure of the injection pump, the powder feeding amount of the powder feeder is controlled by adjusting the pulse frequency of the stepping motor, the copper-silicon composite powder sent out by the powder feeder and liquid drops atomized by the atomizer collide and are mixed in the expansion section of the laval nozzle, the mixture is accelerated by main air flow of a cold spraying system, the spraying direction is downward and vertical to a horizontally placed copper foil substrate, and the deposition thickness is 0.1-1mm, so that the composite coating is prepared.
8. The method of claim 1, wherein: in the step (5), the composite coating is dried for 1-12h at 70-150 ℃, then is moved into a nitrogen atmosphere and is heated to 500-1500 ℃ at a heating rate of 5 ℃/min, and is carbonized for 1-24h, so that the lithium ion battery C @ Cu @ Si composite porous negative electrode material is obtained.
9. The application of the carbon-copper-silicon composite porous negative electrode material of the lithium ion battery prepared by the preparation method according to any one of claims 1 to 8 is characterized in that: and (2) assembling a half cell by taking a metal lithium sheet as a counter electrode, taking single-layer polypropylene as a diaphragm (Celgard 2300), taking a mixed solution of a 1mol/L lithium hexafluorophosphate solution and a solvent of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1 as an electrolyte and taking the C @ Cu @ Si composite porous negative electrode material as a negative electrode.
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