CN113707858A - Porous carbon-silicon composite negative electrode material and preparation method thereof - Google Patents
Porous carbon-silicon composite negative electrode material and preparation method thereof Download PDFInfo
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- 239000011868 silicon-carbon composite negative electrode material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- 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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- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H01M4/00—Electrodes
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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Abstract
The invention discloses a porous carbon-silicon composite negative electrode material, wherein an inner core is a silicon particle or a silicon graphene composite with the particle size less than or equal to 5 microns, and an outer layer is a porous carbon layer; the porous carbon layer is prepared from a phenol compound, formaldehyde and a surfactant, and the mass of carbon accounts for 5-80% of the total mass of the material; the thickness of the porous carbon layer is 10-5000 nm, and the diameter of pores of the porous carbon layer is 2-100 nm; and its preparing process are also disclosed. The carbon layer coated by the porous carbon-silicon composite negative electrode material limits the expansion of the volume during the lithiation of silicon, and the cycle life of the battery is prolonged; the nano-pores in the carbon layer are passages for lithium ions to enter and exit the composite material, so that the lithium ions can enter and exit rapidly, the reaction kinetic balance is achieved, the activation cycle times required by the carbon-silicon composite material are reduced, the manufacturing cost is reduced, and the rapid charging capability of the battery is improved; the preparation method has the advantages of easily controlled process and low cost, and is suitable for large-scale batch production.
Description
Technical Field
The invention relates to the technical field of lithium ion rechargeable battery materials, in particular to a porous carbon-silicon composite negative electrode material and a preparation method thereof.
Background
The lithium ion battery cathode materials adopted by the current global lithium ion battery manufacturers mainly comprise graphite materials, but with the rapid development and wide use of electric vehicles, the problem of low battery energy of the electric vehicles is increasingly prominent, and the low energy density of the graphite cathode materials becomes one of the bottlenecks restricting the mileage of the electric vehicles.
Of all the potential high energy anode materials, silicon has long been considered to be the most likely anode material to replace graphite. The theoretical gram capacity of silicon is 4200 ma-hrs per gram, relative to graphite, approximately ten times higher than that of graphite (372 ma-hrs per gram), and the theoretical energy density of the cell with silicon as the negative electrode is 15% higher than that of graphite. However, silicon has technical difficulties as a negative electrode material of a lithium ion battery, and when silicon reacts with lithium, the volume of silicon increases, and the volume of fully lithiated silicon is 130% of the volume of pure silicon. The huge change of the silicon volume before and after lithiation damages the stability of silicon surface SEI (solid-liquid interface) and reduces the cycle life and safety performance of the battery, and on the other hand, the volume change of the battery and the shape change of the battery are caused, and the damage to equipment is possibly caused.
Carbon coating is a conventional method to improve the cycle life and safety performance of silicon cathodes. Carbon-coated silicon (silicon carbon composite) has a reduced gram capacity but a greatly improved cycle life. It is clear that this improvement depends on the thickness and structure of the surface carbon coating layer: the carbon coating layer is too thin, the carbon coating is incomplete, the capacity of the silicon-carbon composite negative electrode is quickly attenuated, the cycle life of the battery is too short, and no commercial advantage exists; the carbon coating layer is too thick, lithium ions hardly penetrate through the thick carbon layer, the silicon-carbon composite negative electrode can be stable only by repeated charge-discharge cycle activation, the manufacturing cost is increased, and the potential safety problem of the battery is increased. Based on these technical difficulties, silicon or silicon carbon composites have not been applied to lithium ion batteries on a large scale.
Disclosure of Invention
In order to solve the problems, the invention provides a carbon-silicon composite negative electrode material of porous carbon coated silicon and a preparation method thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a porous carbon-silicon composite negative electrode material is characterized in that an inner core of the porous carbon-silicon composite negative electrode material is a silicon particle or a silicon graphene composite with the particle size less than or equal to 5 micrometers, and an outer layer of the porous carbon-silicon composite negative electrode material is a porous carbon layer; the porous carbon layer is prepared from a phenol compound, formaldehyde and a surfactant, and the mass of carbon accounts for 5-80% of the total mass of the material; the thickness of the porous carbon layer is 10-5000 nm, and the diameter of the porous carbon layer is 2-100 nm.
According to the porous carbon-silicon composite anode material, the porous carbon layer is honeycomb-shaped, and the mass of carbon accounts for 5% -30% of the total mass of the material; the thickness of the porous carbon layer is 100-500 nm, and the diameter of the porous carbon layer hole is 10-50 nm.
The preparation method of the porous carbon-silicon composite negative electrode material comprises the following steps:
s1 preparation of carbon-silicon composite:
dissolving phenol compounds and surfactants in a solvent, adding formaldehyde and a catalyst for mixing, adding silicon particles or a silica graphene compound after stirring, continuously stirring for 12 hours, filtering out clear liquid, washing the jelly for 5 times, and drying in vacuum to obtain a carbon-silicon compound;
s2, preparing a porous carbon-silicon composite negative electrode material:
s1, thermally cracking the dried carbon-silicon composite solid at 450-750 ℃ for 5-10 h, naturally cooling to room temperature to obtain a black porous carbon-silicon composite negative electrode material, and ball-milling to obtain a particle size of 5-15 mu m.
In the preparation method of the porous carbon-silicon composite negative electrode material, the phenol compound in S1 is phenol, benzenediol or phloroglucinol; the surfactant is long-chain alkyl quaternary ammonium salt positive ion surfactant, alkyl sodium sulfate negative ion surfactant, sulfonic group anionic surfactant, nonionic ether high molecular surfactant, polar high molecular copolymer or graft polymer; the solvent is 10-30% ethanol water solution; the catalyst is concentrated hydrochloric acid or strong base; the addition amounts of the phenol compound, the formaldehyde, the solvent, the surfactant and the catalyst are designed and calculated according to the requirements of the diameter of the porous carbon and the thickness of the carbon layer.
According to the preparation method of the porous carbon-silicon composite negative electrode material, the surfactant is cetyl trimethylammonium bromide, sodium dodecyl sulfate, a polyether surfactant F127, a polyoxyethylene-polyoxypropylene nonionic high-molecular surfactant, polyethylene glycol octyl phenyl ether Triton X-100 or polyoxyethylene-21 stearyl ether Brij 721; the strong base is NaOH or KOH. The auxiliary agents with different structures have different molecular weights and molecular structures, and the diameter of the carbon layer hole can be accurately controlled by selecting the type of the surfactant.
In the preparation method of the porous carbon-silicon composite negative electrode material, the diameter of the silicon particle or silica graphene composite is 50-200 nm in S1.
In the preparation method of the porous carbon-silicon composite negative electrode material, the vacuum drying is 80 ℃ in S1.
In the preparation method of the porous carbon-silicon composite negative electrode material, the thermal cracking method of S2 is: the quartz tube was filled with nitrogen gas and exhausted, then replaced with a mixed gas of 5%/95% by volume of hydrogen/argon gas, and thermally cracked at 750 ℃ for 5 hours.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a carbon-silicon composite negative electrode material with porous carbon coated with silicon and a preparation method thereof. The inner core of the carbon-silicon composite negative electrode material is silicon particles or silicon graphene composite, the outer layer is cellular porous carbon, and the outer shell is completely covered by the porous carbon, so that the carbon-silicon composite negative electrode material has the advantages that: a) the coated carbon layer limits the expansion of the volume during the lithiation of the silicon, and the cycle life of the battery is prolonged; b) the nano-pores in the carbon layer are passages for lithium ions to enter and exit the composite material, so that the lithium ions can enter and exit rapidly, the reaction kinetic balance is achieved, the activation cycle times required by the carbon-silicon composite material are reduced, the designed capacitance of the battery can be reached more rapidly than that of the cathode material prepared by other methods, the manufacturing cost is reduced, and the rapid charging capability of the battery is improved. The preparation method can design and accurately control the thickness of the carbon layer and the diameter and distribution state of the holes on the carbon layer according to the required battery performance, and the carbon layers obtained by other porous carbon layer preparation methods have insufficient thickness and are disordered and uncontrollable in diameter and distribution; the preparation method is simple, the process parameter requirement is high in elasticity, industrial production is easy to realize, and the material manufacturing cost is reduced.
Drawings
FIG. 1 is a scanning electron microscope image of a porous carbon-silicon composite negative electrode material of the invention;
FIG. 2 shows the electrochemical performance of the porous carbon-silicon composite negative electrode material of the present invention after being made into a battery negative electrode.
Detailed Description
Embodiment 1 of the present invention: a porous carbon-silicon composite negative electrode material:
the inner core of the porous carbon-silicon composite negative electrode material is 100nm silicon particles, and the outer layer is a honeycomb porous carbon layer; the porous carbon layer is prepared from phloroglucinol, formaldehyde and a surfactant of cetyltrimethylammonium bromide, and the mass of carbon accounts for 10% of the total mass of the material; the thickness of the cellular porous carbon layer is 100nm, and the diameter of the pores of the porous carbon layer is 2 nm.
Example 2: a porous carbon-silicon composite negative electrode material:
the inner core of the porous carbon-silicon composite negative electrode material is a 20nm silicon graphene composite, and the outer layer is a porous carbon layer; the porous carbon layer is prepared from hydroquinone, formaldehyde and sodium dodecyl sulfate anion surfactant, and the mass of carbon accounts for 50% of the total mass of the material; the thickness of the porous carbon layer is 200nm, and the diameter of the pores of the porous carbon layer is 2 nm.
Example 3: a porous carbon-silicon composite negative electrode material:
the inner core of the porous carbon-silicon composite negative electrode material is 5 micron silicon particles, and the outer layer is a porous carbon layer; the porous carbon layer is prepared from phloroglucinol, formaldehyde and a surfactant PEO-PPO diblock copolymer, and the mass of carbon accounts for 10% of the total mass of the material; the thickness of the porous carbon layer is 100nm, and the diameter of the porous carbon layer is 10 nm.
Example 4: a porous carbon-silicon composite negative electrode material:
the inner core of the porous carbon-silicon composite negative electrode material is a silicon graphene composite, and the outer layer is a porous carbon layer; the porous carbon layer is prepared from phloroglucinol, formaldehyde and a polyether surfactant F127, and the mass of carbon accounts for 50% of the total mass of the material; the thickness of the porous carbon layer is 50nm, and the diameter of the pores of the porous carbon layer is 20 nm.
Example 5: a porous carbon-silicon composite negative electrode material:
the inner core of the porous carbon-silicon composite negative electrode material is silicon particles, and the outer layer is a honeycomb-shaped porous carbon layer; the porous carbon layer is prepared from phloroglucinol, formaldehyde and polyoxyethylene-21 stearyl alcohol ether Brij721, and the mass of carbon accounts for 5% of the total mass of the material; the thickness of the porous carbon layer is 1000nm, and the diameter of the porous carbon layer is 50 nm.
Example 6: a porous carbon-silicon composite negative electrode material:
the inner core of the porous carbon-silicon composite negative electrode material is silicon particles, and the outer layer is a honeycomb-shaped porous carbon layer; the porous carbon layer is prepared from phenol, formaldehyde and polyethylene glycol octyl phenyl ether Triton X-100, and the mass of carbon accounts for 60% of the total mass of the material; the thickness of the porous carbon layer is 3000nm, and the diameter of the porous carbon layer is 90 nm.
Example 7: the preparation method of the porous carbon-silicon composite negative electrode material in the embodiment 1 comprises the following steps:
dissolving 2.7 g of phloroglucinol and 6 g of hexadecyl trimethyl ammonium bromide in 20% ethanol water solution at room temperature under stirring, adding 4.0 g of formaldehyde and 0.6 g of concentrated hydrochloric acid, stirring for 1 hour, adding 20 g of silicon powder with the diameter of 100 nanometers, and stirring the mixed solution for 12 hours; filtering to remove clear liquid, soaking and washing the obtained colloidal mixture with 95% ethanol water solution for 5 times, and vacuum drying in an oven at 80 deg.C; filling the dried solid into a muffle furnace quartz tube, filling nitrogen gas for exhausting, replacing by hydrogen/argon gas mixed gas (5%/95%), heating to 650 ℃, and keeping for 5 hours; stopping heating, naturally cooling to room temperature to obtain black porous carbon-silicon composite negative electrode material solid, and performing ball milling until the particle size is 5-15 mu m, and storing.
Example 8: the preparation method of the porous carbon-silicon composite negative electrode material in the embodiment 2 comprises the following steps:
dissolving 8 g of hydroquinone and 9 g of sodium dodecyl sulfate in 15% ethanol aqueous solution at room temperature under stirring, adding 10 g of formaldehyde and 0.4 g of concentrated hydrochloric acid, stirring for 1h, adding 15 g of silicon graphene compound with the diameter of 20nm, and stirring the mixed solution for 12 h; filtering to remove clear liquid, soaking and washing the obtained colloidal mixture for 5 times, and vacuum drying in an oven at 80 ℃; filling the dried solid into a muffle furnace quartz tube, filling nitrogen gas for exhausting, replacing by hydrogen/argon gas mixed gas (5%/95%), heating to 450 ℃, and keeping for 5 hours; stopping heating, naturally cooling to room temperature to obtain black porous carbon-silicon composite negative electrode material solid, and performing ball milling until the particle size is 5-15 mu m, and storing.
Example 9: the preparation method of the porous carbon-silicon composite negative electrode material in the embodiment 3 comprises the following steps:
dissolving 2.7 g of phloroglucinol and 3.5 g of PEO-PPO diblock copolymer into 25% ethanol aqueous solution at room temperature under stirring, adding 4.0 g of formaldehyde and 1 g of 10% NaOH, stirring for 1h, adding 10 g of silicon powder with the diameter of 5 microns, and stirring the mixed solution for 12 h; filtering to remove clear liquid, soaking the obtained colloidal mixture in water/ethanol mixed solution for 5 times, and vacuum drying in an oven at 80 deg.C; filling nitrogen into the dried solid in a container, exhausting, replacing with hydrogen/argon mixed gas (5%/95%), heating to 700 deg.C, and maintaining for 5 hr; stopping heating, naturally cooling to room temperature to obtain black porous carbon-silicon composite negative electrode material solid, and performing ball milling until the particle size is 5-15 mu m, and storing.
Example 10: the preparation method of the porous carbon-silicon composite negative electrode material in the embodiment 4 comprises the following steps:
dissolving 7 g of phloroglucinol and 8.5 g of F127 in 30% ethanol aqueous solution at room temperature under stirring, adding 8.8 g of formaldehyde and 2 g of 10% KOH, stirring for 1h, adding 15 g of silicon graphene compound with the diameter of 20nm, and stirring the mixed solution for 12 h; filtering to remove clear liquid, soaking and washing the obtained colloidal mixture with 95% ethanol water solution for 5 times, and vacuum drying in an oven at 80 deg.C; filling nitrogen into the dried solid in a container, exhausting, replacing with hydrogen/argon mixed gas (5%/95%), heating to 700 deg.C, and maintaining for 5 hr; stopping heating, naturally cooling to room temperature to obtain black porous carbon-silicon composite negative electrode material solid, and performing ball milling until the particle size is 5-15 mu m, and storing.
Experimental example:
application of the porous carbon-silicon composite negative electrode materials obtained in examples 1 to 6:
mechanically stirring 0.35 g of sodium carboxymethylcellulose, dissolving in 15 ml of deionized water, then adding 0.9 g of porous silicon-carbon composite material and 0.5 g of Super P-Li carbon black, adding 10 ml of deionized water after 2 hours, continuously stirring for 3 hours, adding 0.3 g of styrene-butadiene rubber emulsion (with the concentration of 50%), and stirring for 2 hours; pouring the prepared mixture on a copper foil with the thickness of 12 microns, coating by a scraper, and heating to evaporate water to obtain a negative plate; and (3) drying the negative plate in vacuum at 80 ℃ for 12 hours in a vacuum box.
And (3) gram capacity test:
and (3) preparing the obtained porous carbon-silicon composite material negative plate into a 2032 button cell, and testing the gram capacity of the cell. The porous carbon-silicon composite material negative plate is used as a positive electrode, the lithium plate with the thickness of 250 micrometers is used as a negative electrode, and the electrolyte is as follows: 1.0M LiPF6Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) (EC and EMC in a 2: 3 volume ratio). The charge and discharge multiplying power of the battery is 0.1C, the voltage is cut off to 0.01 volt during discharging (lithiation), and the voltage is cut off to 1.5 volt during charging (delithiation).
The gram capacity test result of the 2032 coin cell obtained by the test is shown in figure 2. The battery has high capacity reaching 800mAh/g, good stability and small change of a numerical curve; the battery capacity does not decay after 140 cycles; the stable state is quickly reached in the initial charging stage, and the maximum gram capacity of the battery is reached after about 10 cycles; the reaction kinetics of the battery is stable, the activation cycle of the battery is quickly achieved, and the designed capacity requirement is met.
Claims (8)
1. A porous carbon-silicon composite negative electrode material is characterized in that: the inner core of the porous carbon-silicon composite negative electrode material is silicon particles or silicon graphene composite with the particle size less than or equal to 5 microns, and the outer layer is a porous carbon layer; the porous carbon layer is prepared from a phenol compound, formaldehyde and a surfactant, and the mass of carbon accounts for 5-80% of the total mass of the material; the thickness of the porous carbon layer is 10-5000 nm, and the diameter of the porous carbon layer is 2-100 nm.
2. The porous carbon-silicon composite anode material of claim 1, wherein: the porous carbon layer is honeycomb-shaped, and the mass of carbon accounts for 5% -30% of the total mass of the material; the thickness of the porous carbon layer is 100-500 nm, and the diameter of the porous carbon layer hole is 10-50 nm.
3. The preparation method of the porous carbon-silicon composite anode material as claimed in claim 1 or 2, characterized by comprising the following steps:
s1 preparation of carbon-silicon composite:
dissolving phenol compounds and surfactants in a solvent, adding formaldehyde and a catalyst for mixing, adding silicon particles or a silica graphene compound after stirring, continuously stirring for 12 hours, filtering out clear liquid, washing the jelly for 5 times, and drying in vacuum to obtain a carbon-silicon compound;
s2, preparing a porous carbon-silicon composite negative electrode material:
s1, thermally cracking the dried carbon-silicon composite solid at 450-750 ℃ for 5-10 h, naturally cooling to room temperature to obtain a black porous carbon-silicon composite negative electrode material, and ball-milling to obtain a particle size of 5-15 mu m.
4. The preparation method of the porous carbon-silicon composite anode material as claimed in claim 2, wherein the preparation method comprises the following steps: s1, the phenol compound is phenol, benzenediol or phloroglucinol; the surfactant is long-chain alkyl quaternary ammonium salt positive ion surfactant, alkyl sodium sulfate negative ion surfactant, nonionic ether high molecular surfactant, polar high molecular copolymer or graft polymer; the solvent is 10-30% ethanol solution; the catalyst is concentrated hydrochloric acid or strong base.
5. The preparation method of the porous carbon-silicon composite anode material as claimed in claim 4, wherein the preparation method comprises the following steps: the surfactant is cetyl trimethylammonium bromide, sodium dodecyl sulfate, a polyether surfactant F127, a polyoxyethylene-polyoxypropylene nonionic polymer surfactant, polyethylene glycol octyl phenyl ether Triton X-100 or polyoxyethylene-21 stearyl ether Brij 721; the strong base is NaOH or KOH.
6. The preparation method of the porous carbon-silicon composite anode material as claimed in claim 3, wherein the preparation method comprises the following steps: s1 the diameter of the silicon particle or silica graphene composite is 50-200 nm.
7. The preparation method of the porous carbon-silicon composite anode material as claimed in claim 3, wherein the preparation method comprises the following steps: the vacuum drying of S1 was 80 ℃.
8. The preparation method of the porous carbon-silicon composite anode material as claimed in claim 3, wherein the preparation method comprises the following steps: s2 the thermal cracking method comprises the following steps: the quartz tube was filled with nitrogen gas and exhausted, then replaced with a mixed gas of 5%/95% by volume of hydrogen/argon gas, and thermally cracked at 750 ℃ for 5 hours.
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