CN110459732B - Silicon/graphene/carbon composite fiber membrane negative electrode plate, preparation method thereof and lithium ion battery - Google Patents
Silicon/graphene/carbon composite fiber membrane negative electrode plate, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a silicon/graphene/carbon composite fiber membrane negative pole piece, which comprises the following steps: the silicon/graphene/carbon composite fiber membrane negative pole piece is prepared by carrying out electrostatic spinning on SiOxThe/graphene/carbon composite nanofiber membrane is attached to SiO in situxThe value range of x is more than or equal to 0 and less than or equal to x<2. The invention overcomes the problems of low conductivity and large volume expansion rate of silicon materials, and the problems of short circuit and performance reduction of batteries caused by corrosion of current collectors. According to the invention, the adhesive force between the active material and the current collector is increased, and the contact resistance between the current collector and the active material is reduced, so that the silicon/graphene/carbon composite fiber membrane negative pole piece can improve the electrochemical performance and prolong the service life of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a silicon/graphene/carbon composite fiber membrane negative electrode piece, a preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode piece, and a lithium ion battery using the silicon/graphene/carbon composite fiber membrane negative electrode piece.
Background
Silicon materials are currently a popular research object as negative electrode materials of lithium ion batteries due to their high lithium storage capacity and low discharge plateau. However, the commercial application of the silicon material is limited by its low conductivity and large volume expansion rate during the charge and discharge processes. Meanwhile, metals such as copper foil, aluminum foil and the like are often adopted as current collectors in the conventional lithium ion battery, but the technical scheme has the following defects: 1. the metal density is high, the proportion of active materials in the electrode is reduced, and the improvement of the energy density of the battery is limited. 2. The electrochemical stability is poor, and the problems of anode corrosion and the like exist in the long-term circulation process, so that the capacity attenuation of the battery is accelerated, and the service life of the battery is shortened. 3. The interface resistance of the contact surface of the metal current collector and the active material is large, and the rate capability under the condition of large-current charge and discharge is limited. Therefore, how to develop a novel lithium ion battery silicon/graphene/carbon composite fiber membrane negative electrode plate can overcome the above problems in the prior art, and is the direction of research needed by those skilled in the art.
Disclosure of Invention
The invention aims to provide a preparation method of a silicon/graphene/carbon composite fiber membrane negative electrode piece, which solves the problems of low conductivity and high volume expansion rate of a silicon material and easy corrosion of a current collector.
The technical scheme is as follows:
a preparation method of a silicon/graphene/carbon composite fiber membrane negative pole piece comprises the following steps: the silicon/graphene/carbon composite fiber membrane negative pole piece is prepared by carrying out electrostatic spinning on SiOxThe/graphene/carbon composite nanofiber membrane is attached to SiO in situxThe value range of x is more than or equal to 0 and less than or equal to x<2。
Preferably, the preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode plate comprises the following steps: s1: dispersing graphite oxide in deionized water, and uniformly dispersing by using a high-pressure homogenizer to obtain graphene oxide slurry; s2: dispersing a silicon-containing compound in water to obtain a silicon-containing compound solution; s3: adding the silicon-containing compound solution obtained in the step S2 into the graphene oxide slurry obtained in the step S1 under the stirring condition, uniformly stirring, and continuously and uniformly dispersing by using a high-pressure homogenizer to obtain a silicon-containing compound/graphene oxide slurry; s4: coating the silicon-containing compound/graphene oxide slurry obtained in the step S3 on a PET (polyethylene terephthalate) substrate or a non-woven fabric substrate, and drying to obtain the silicon-containing compound/oxidized stoneA graphene film; s5: placing the silicon-containing compound/graphene oxide film obtained in S4 in an inert atmosphere for high-temperature treatment, and rolling after the high-temperature treatment to obtain SiOxA graphene membrane; s6: dispersing graphite oxide in a solvent to obtain a graphene oxide solution; s7: slowly adding a silicon-containing compound into the graphene oxide solution obtained in the step S6 under the stirring condition to obtain a silicon-containing compound/graphene oxide solution; s8: adding the silicon-containing compound/graphene oxide solution obtained in the step S7 into the polymer dispersion liquid, and uniformly dispersing to obtain a silicon-containing compound/graphene oxide spinning solution; s9: spinning the silicon-containing compound/graphene oxide spinning solution obtained in S8 by using electrostatic spinning equipment to obtain SiO obtained in S5xGenerating a silicon-containing compound/graphene oxide/polymer composite nanofiber membrane on the graphene membrane; s10: putting the product obtained in S7 into a high-temperature furnace, performing high-temperature treatment under the protection of inert gas, and performing high-temperature treatment on the product in SiOxFormation of SiO on the surface of graphene filmxGraphene/carbon composite nanofiber membrane, SiO formed therebyxGraphene/carbon composite nanofiber membrane/SiOxThe graphene film is a silicon/graphene/carbon composite fiber film negative pole piece.
By adopting the technical scheme: with SiOxThe/graphene/carbon composite nanofiber membrane is attached to SiO in situxThe surface of the graphene film forms a silicon/graphene/carbon composite fiber film negative pole piece, so that a conductive agent and an adhesive are not required to be introduced. The graphene serving as a novel carbon nano material has excellent conductivity, electrochemical stability, mechanical properties and lower density, and provides a better electronic channel for the composite material. The graphene film replaces metal to serve as a current collector of the lithium ion battery, so that the contact resistance between the graphene film and an active material is reduced, and the electrochemical performance of the battery is improved. And the problems of internal short circuit and performance reduction of the battery caused by corrosion of the metal current collector are avoided. SiO double-protection by graphene and carbonxThe particles prevent the silicon material from expanding in the charging and discharging process, and the electrochemical performance and the service life of the battery are improved.
Preferably, in the preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode plate, the following steps are carried out: the silicon-containing compoundThe compound adopts nano SiOxAny one of powder, silane coupling agent, orthosilicate ester, sodium silicate, silicone and diatom.
More preferably, in the preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode plate, the following steps are carried out: the drying treatment in the step S4 is carried out in the temperature environment below 80 ℃; the high-temperature treatment in the step S5 is carried out within the temperature range of 1000-2600 ℃, the temperature rise rate is 0.5-10 ℃/min, and the treatment time is 2-6 hours.
Further preferably, in the preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode plate, the following steps are carried out: the working voltage of the spinning treatment in the step S9 is 8-15 kV; the high-temperature treatment in the step S10 is carried out in the temperature range of 800-2600 ℃, the temperature rise rate is 0.5-10 ℃/min, and the treatment time is 2-8 hours.
Still more preferably, in the preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode plate, the following steps are carried out: the solvent in step S6 is any one or a mixture of any two of water, N-Dimethylformamide (DMF), ethylene glycol, and xylene, and the polymer dispersion in step S8 is any one or a mixture of any two of polyvinyl alcohol (PVA), Waterborne Polyurethane (WPU), Polyacrylonitrile (PAN), polyacrylic acid (PAA), polylactic acid (PLA), and polyvinylpyrrolidone (PVP).
The invention also discloses a silicon/graphene/carbon composite fiber membrane negative electrode plate which is prepared by the preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode plate.
Preferably, in the silicon/graphene/carbon composite fiber membrane negative electrode sheet: the SiOx: graphene: the mass ratio of carbon is (5-60): (2-40): (38-55); the SiOxThe graphene film has a thickness of 6 to 30 μm and an electrical conductivity of 0.2 to 1.2 × 105S/m; the SiOxSiO in graphene filmx: the mass ratio of the graphene is (0-3): (100: 97); the SiOxThe thickness of the/graphene/carbon composite nanofiber membrane is 0.5-100 mu m; the SiOxSiO in/graphene/carbon composite nanofiber membranex: graphene: the mass ratio of carbon is (2-60): (0:20): (40-78).
More preferably, in the silicon/graphene/carbon composite fiber membrane negative electrode sheet: the SiOxThe particle size is 10-500 nm; the SiOxIn the/graphene/carbon composite nanofiber membrane, SiOxThe diameter of the/graphene/carbon composite nanofiber is 100-1500 nm.
The invention also discloses a lithium ion battery, which comprises: the cathode electrode piece, the diaphragm, the electrolyte and the silicon/graphene/carbon composite fiber membrane cathode electrode piece manufactured by the scheme.
Compared with the prior art, the invention overcomes the problems of low conductivity and large volume expansion rate of silicon materials, and the problems of short circuit and performance reduction of the battery caused by corrosion of the current collector. The invention increases the adhesive force between the active material and the current collector, and simultaneously reduces the contact resistance between the current collector and the active material.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 shows a silicon/graphene/carbon composite fiber membrane negative electrode plate obtained in example 1, and 1M LiPF6(DMC: EC 1:1 vol%) as electrolyte, polypropylene film as diaphragm to form button lithium ion battery charge-discharge curve at current density of 0.5C;
FIG. 3 shows a silicon/graphene/carbon composite fiber membrane negative electrode plate obtained in example 1, and 1M LiPF6(DMC: EC ═ 1:1 vol%) is an electrolyte, and a polypropylene film is a separator, to construct a coulombic efficiency map of the button lithium ion battery at a current density of 0.5C.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the following will be further described with reference to various embodiments.
It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention. In the following examples, all percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1 as shown in fig. 1-3:
a silicon/graphene/carbon composite fiber membrane negative electrode piece is prepared by the following steps:
1. preparation of SiOxGraphene membrane:
dispersing graphite oxide in deionized water, and uniformly dispersing the graphite oxide in a high-pressure homogenizer to obtain 3% graphene oxide slurry; while the particle diameter is 20nmSiOxDispersing the powder or the silicon-containing compound in water to obtain 5% SiOxA powder or a silicon-containing compound solution; then adding SiOx powder or silicon-containing compound solution into the graphene oxide slurry under the condition of stirring, and continuously and uniformly dispersing by using a high-pressure homogenizer to obtain SiOxA powder or a silicon-containing compound/graphene oxide slurry; then nano SiO is addedxCoating the powder or the silicon-containing compound/graphene oxide slurry on a PET or non-woven fabric substrate, and drying at 75 ℃ for 4h to obtain SiOxOr a silicon-containing compound/graphene oxide film; finally, SiO is mixedxPlacing the powder or the silicon-containing compound/graphene oxide film in an argon atmosphere at 2600 ℃ for 2h, and rolling to obtain SiO with the thickness of 10 mu mxGraphene membranes.
2. Preparation of SiOxGraphene/carbon composite nanofiber membrane:
preparing 0.5% graphene oxide solution, carrying out ultrasonic treatment for 0.5h, and slowly adding 20nm SiO under stirring at a rotation speed of 1500 rpmxAdding silicon-containing compounds such as powder or silicate ester and the like into 10% PAN dispersion liquid, and uniformly stirring to obtain spinning solution; then using SiOxUsing graphene membrane as receiving medium, spinning the spinning solution by using electrostatic spinning equipment, and spinning on SiOxObtaining a nanofiber membrane containing graphene oxide and Si in situ on the graphene membrane; under the protection of nitrogen gas, SiO loaded with the nanofiber membranexAnd carrying out high-temperature treatment on the graphene film at 1200 ℃, and keeping the temperature for 3 h. Finally obtaining SiO loaded with the thickness of 20 mu mxGraphene/carbon composite nano-particlesSiO of fiber filmxGraphene membranes.
And (3) detecting data: in the silicon/graphene/carbon composite fiber membrane negative pole piece, SiOx: graphene: the mass ratio of carbon is 36: 9: 55. under the condition that the current density is 0.5C (1C is 2286mA/g (Si/C is 1:1)), the specific discharge capacity is 2700mAh/g, the first efficiency reaches 95.5 percent, after 100 cycles, 96 percent of capacity can be kept, and the high-efficiency lithium ion battery has good cycling stability.
Example 2:
a silicon/graphene/carbon composite fiber membrane negative electrode piece is prepared by the following steps:
1. preparation of SiOxGraphene membrane:
dispersing graphite oxide in deionized water, and uniformly dispersing the graphite oxide in a high-pressure homogenizer to obtain 5% graphene oxide slurry; simultaneously SiO with the grain diameter of 300nmxDispersing the powder or the silicon-containing compound in water to obtain 8% SiOxA powder or a silicon-containing compound solution; then SiOxAdding the powder or the silicon-containing compound solution into the graphene oxide slurry under the stirring condition, and continuously and uniformly dispersing by using a high-pressure homogenizer to obtain SiOxA powder or a silicon-containing compound/graphene oxide slurry; then nano SiO is addedxCoating the powder or the silicon-containing compound/graphene oxide slurry on a PET or non-woven fabric substrate, and drying at 60 ℃ for 6h to obtain SiOxOr a silicon-containing compound/graphene oxide film; finally, SiO is mixedxPlacing the powder or silicon-containing compound/graphene oxide film in an argon atmosphere at 2500 ℃ for 2.5h, and rolling to obtain SiO with the thickness of 20 mu mxGraphene membranes.
2. Preparation of SiOxGraphene/carbon composite nanofiber membrane:
preparing 0.4% graphene oxide solution, carrying out ultrasonic treatment for 0.5h, and slowly adding 300nm SiO under stirring at a rotation speed of 1500 rpmxAdding silicon-containing compounds such as powder or silicate ester and the like into 8% of PVA dispersion liquid, and uniformly stirring to obtain spinning solution; then using SiOxUsing graphene membrane as receiving medium, spinning the spinning solution by using electrostatic spinning equipment, and spinning on SiOxGraphene membranesObtaining a nanofiber membrane containing graphene oxide and Si in situ; under the protection of nitrogen gas, SiO loaded with the nanofiber membranexAnd/carrying out high-temperature treatment on the graphene film at 1500 ℃, and keeping the temperature for 2 h. Finally obtaining SiO with the thickness of 50 mu mxSiO of/graphene/carbon composite nanofiber membranexGraphene membranes.
And (3) detecting data: in the silicon/graphene/carbon composite fiber membrane negative pole piece, SiOx: graphene: the mass ratio of carbon is 10: 15: 75. under the condition that the current density is 0.5C (1C is 2286mA/g (Si/C is 1:1)), the specific discharge capacity can reach 2300mAh/g, the first efficiency is 92%, 97% of capacity can be maintained after 100 cycles, and the high-capacity lithium ion battery has good cycle stability.
Example 3
A silicon/graphene/carbon composite fiber membrane negative electrode piece is prepared by the following steps:
1. preparation of SiOxGraphene membrane:
dispersing graphite oxide in deionized water, and uniformly dispersing the graphite oxide in a high-pressure homogenizer to obtain 4% graphene oxide slurry; simultaneously the particle size of SiO is 100nmxDispersing the powder or the silicon-containing compound in water to obtain 5% SiOxA powder or a silicon-containing compound solution; then SiOxAdding the powder or the silicon-containing compound solution into the graphene oxide slurry under the stirring condition, and continuously and uniformly dispersing by using a high-pressure homogenizer to obtain SiOxA powder or a silicon-containing compound/graphene oxide slurry; then nano SiO is addedxCoating the powder or the silicon-containing compound/graphene oxide slurry on a PET or non-woven fabric substrate, and drying for 3h at 80 ℃ to obtain SiOxOr a silicon-containing compound/graphene oxide film; finally, SiO is mixedxPlacing the powder or the silicon-containing compound/graphene oxide film in an argon atmosphere at 2600 ℃ for 2.5h, and rolling to obtain SiO with the thickness of 12 micronsxGraphene membranes.
2. Preparation of SiOxGraphene/carbon composite nanofiber membrane:
preparing 0.5% graphene oxide solution, performing ultrasonic treatment for 1h, and slowly adding 100nm graphene oxide solution under the stirring condition of 1500 rpmSiOxAdding silicon-containing compounds such as powder or silicate ester and the like into 10% of PVA dispersion liquid, and uniformly stirring to obtain spinning solution; then using SiOxUsing graphene membrane as receiving medium, spinning the spinning solution by using electrostatic spinning equipment, and spinning on SiOxObtaining a nanofiber membrane containing graphene oxide and Si in situ on the graphene membrane; under the protection of nitrogen gas, SiO loaded with the nanofiber membranexAnd/carrying out high-temperature treatment on the graphene film at 1500 ℃, and keeping the temperature for 2 h. Finally obtaining SiO with the thickness of 10 mu mxSiO of/graphene/carbon composite nanofiber membranexGraphene membranes.
And (3) detecting data: in the silicon/graphene/carbon composite fiber membrane negative pole piece, SiOx: graphene: the mass ratio of carbon is 58: 2: 40. under the condition that the current density is 0.5C (1C is 2286mA/g (Si/C is 1:1)), the specific discharge capacity can reach 2800mAh/g, the first efficiency is 92%, after 100 cycles, 95% of capacity can be still maintained, and the high-capacity lithium ion battery has good cycle stability.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. The protection scope of the present invention is subject to the protection scope of the claims.
Claims (8)
1. A preparation method of a silicon/graphene/carbon composite fiber membrane negative pole piece is characterized by comprising the following steps: the silicon/graphene/carbon composite fiber membrane negative pole piece is formed by attaching a SiO x/graphene/carbon composite nanofiber membrane on the surface of a SiO x/graphene membrane in situ by an electrostatic spinning method, wherein the value range of x is more than or equal to 0 and less than 2;
the method for attaching the SiO x/graphene/carbon composite nanofiber membrane to the surface of the SiO x/graphene membrane in situ by using an electrostatic spinning method comprises the following steps:
s1: dispersing graphite oxide in deionized water, and uniformly dispersing by using a high-pressure homogenizer to obtain graphene oxide slurry;
s2: dispersing a silicon-containing compound in water to obtain a silicon-containing compound solution;
s3: adding the silicon-containing compound solution obtained in the step S2 into the graphene oxide slurry obtained in the step S1 under the stirring condition, uniformly stirring, and continuously and uniformly dispersing by using a high-pressure homogenizer to obtain a silicon-containing compound/graphene oxide slurry;
s4: coating the silicon-containing compound/graphene oxide slurry obtained in the step S3 on a PET (polyethylene terephthalate) substrate or a non-woven fabric substrate, and drying to obtain a silicon-containing compound/graphene oxide film;
s5: placing the silicon-containing compound/graphene oxide film obtained in the step S4 in an inert atmosphere for high-temperature treatment, and rolling after the high-temperature treatment to obtain a SiO x/graphene film;
s6: dispersing graphite oxide in a solvent to obtain a graphene oxide solution;
s7: slowly adding a silicon-containing compound into the graphene oxide solution obtained in the step S6 under the stirring condition to obtain a silicon-containing compound/graphene oxide solution;
s8: adding the silicon-containing compound/graphene oxide solution obtained in the step S7 into the polymer dispersion liquid, and uniformly dispersing to obtain a silicon-containing compound/graphene oxide spinning solution;
s9: spinning the silicon-containing compound/graphene oxide spinning solution obtained in the step S8 by using electrostatic spinning equipment to generate a silicon-containing compound/graphene oxide/polymer composite nanofiber membrane on the SiO x/graphene membrane obtained in the step S5;
s10: and (3) placing the product obtained in the step (S9) into a high-temperature furnace, performing high-temperature treatment under the protection of inert gas, and forming a SiO x/graphene/carbon composite nanofiber membrane on the surface of the SiO x/graphene membrane, wherein the formed SiO x/graphene/carbon composite nanofiber membrane/SiO x/graphene membrane is the silicon/graphene/carbon composite fiber membrane negative electrode plate.
2. The preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode plate of claim 1, which is characterized by comprising the following steps: the silicon-containing compound adopts any one of nano SiO x powder, silane coupling agent, orthosilicate ester, sodium silicate, organic silicon and diatom.
3. The preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode plate as claimed in claim 2, characterized in that: the drying treatment in the step S4 is carried out in the temperature environment below 80 ℃; the high-temperature treatment in the step S5 is carried out within the temperature range of 1000-2600 ℃, the temperature rise rate is 0.5-10 ℃/min, and the treatment time is 2-6 hours.
4. The preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode plate as claimed in claim 3, characterized in that: the working voltage of the spinning treatment in the step S9 is 8-15 kV; the high-temperature treatment in the step S10 is carried out in the temperature range of 800-2600 ℃, the temperature rise rate is 0.5-10 ℃/min, and the treatment time is 2-8 hours.
5. The preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode plate of claim 1, which is characterized by comprising the following steps: the solvent in the step S6 is any one or a mixture of any several of water, N-dimethylformamide, ethylene glycol and xylene; the polymer dispersion liquid in the step S8 is any one of or a mixture of any several of polyvinyl alcohol, aqueous polyurethane, polyacrylonitrile, polyacrylic acid, polylactic acid and polyvinylpyrrolidone.
6. The utility model provides a silicon/graphite alkene/carbon composite fiber membrane negative pole piece which characterized in that: the silicon/graphene/carbon composite fiber membrane negative electrode plate is prepared by the preparation method of the silicon/graphene/carbon composite fiber membrane negative electrode plate according to any one of claims 1 to 5.
7. The silicon/graphene/carbon composite fiber membrane negative electrode plate of claim 6, wherein: the particle size of the SiO x is 10-500 nm; in the SiO x/graphene/carbon composite nanofiber membrane, the diameter of the SiO x/graphene/carbon composite nanofiber is 100-1500 nm.
8. A lithium ion battery, characterized by: the silicon/graphene/carbon composite fiber membrane negative electrode plate comprises the silicon/graphene/carbon composite fiber membrane negative electrode plate as claimed in claim 6.
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| CN111769274A (en) * | 2020-07-17 | 2020-10-13 | 昆山宝创新能源科技有限公司 | SiOx-C composite fiber felt negative electrode material and preparation method and application thereof |
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| WO2014160174A1 (en) * | 2013-03-14 | 2014-10-02 | Cornell University | Carbon and carbon precursors in nanofibers |
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