CN115064666B - Conductive polymer grafted graphene coated silicon anode material and preparation method thereof - Google Patents
Conductive polymer grafted graphene coated silicon anode material and preparation method thereof Download PDFInfo
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- CN115064666B CN115064666B CN202210513552.7A CN202210513552A CN115064666B CN 115064666 B CN115064666 B CN 115064666B CN 202210513552 A CN202210513552 A CN 202210513552A CN 115064666 B CN115064666 B CN 115064666B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 98
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 38
- 239000010703 silicon Substances 0.000 title claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000010405 anode material Substances 0.000 title claims abstract description 34
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000002210 silicon-based material Substances 0.000 claims abstract description 19
- 229920000767 polyaniline Polymers 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
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- 238000006243 chemical reaction Methods 0.000 claims description 28
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 23
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 11
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 235000010288 sodium nitrite Nutrition 0.000 claims description 11
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- 238000010008 shearing Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
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- 239000002131 composite material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 230000008569 process Effects 0.000 description 3
- 239000011856 silicon-based particle Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
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- 229910001416 lithium ion Inorganic materials 0.000 description 1
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- 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
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- H01M4/606—Polymers containing aromatic main chain polymers
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention relates to the field of battery anode materials, in particular to a conductive polymer grafted graphene coated silicon anode material and a preparation method thereof, wherein the conductive polymer grafted graphene coated silicon anode material is silicon-based material particles coated with polyaniline grafted graphene oxide. According to the invention, the conductive polymer is used for grafting the graphene coating layer, so that the surface performance of graphene is changed, the interaction between graphene and a binder is improved, the bonding effect is enhanced, and the circulation stability is improved; meanwhile, the graphene grafted by the conductive polymer is used for coating, and the conductive filler is matched, so that a multi-dimensional and highly interpenetrating conductive network of point-line-surface can be realized, the conductivity of the pole piece is further improved, and the internal resistance is reduced.
Description
Technical Field
The invention relates to the field of battery anode materials, in particular to a silicon anode material coated by conductive polymer grafted graphene and a preparation method thereof.
Background
The high-performance negative electrode material is a main bottleneck for limiting the realization of high energy density, excellent cycle stability and good quick charge performance of the lithium ion secondary battery at present. Currently, most of the main commercial negative electrode materials are natural graphite or artificial graphite, and the theoretical specific capacity of the main commercial negative electrode materials is 370mAh/g, so that the main commercial negative electrode materials can not meet the requirements of high-performance equipment. The silicon-based material is used as an active substance, and has the advantages of high specific capacity (4200 mAh/g of theoretical capacity of silicon), good safety, wide source, environmental friendliness and the like. However, there is a great volume expansion effect in the alloying process of silicon material and lithium, and the expansion rate is as high as 300%. After long-time charge-discharge cycle, repeated expansion causes silicon particles to be broken and pulverized, and gradually loses electrical contact with a current collector, and in addition, the newly increased surface continuously consumes active lithium in the electrolyte, so that the specific capacity is greatly attenuated. Currently, the main improvement strategy is to coat metal materials, inorganic materials, polymer materials and the like on the surface of silicon-based materials.
The patent with publication number CN104916826B proposes a graphene coated silicon anode material and a preparation method thereof, wherein the preparation method comprises the following steps: A. preparing graphene oxide suspension; B. preparing a nano silicon particle suspension; C. and preparing the graphene coated silicon anode material. The preparation method adopts the electrostatic self-assembly synthesis technology, has the advantages of wide raw material sources, low price, simple synthesis method, easily controlled process conditions, strong operability and good repeatability. The prepared graphene coated silicon anode material has high specific capacity, excellent cycle performance and rate capability, and the initial discharge specific capacity reaches 2746mAh/g under the current density of 0.01-1.2V and 200mA/g, and the specific capacity is kept at 803.8mAh/g after 100 times of cycle discharge.
The patent with publication number CN106935834A discloses a porous silicon anode material coated by a composite carbon layer and a preparation method thereof, wherein the porous silicon anode material is based on dealloyed porous silicon, the first coating of loose carbon and the integral coating of external high-density carbon are realized by the composite carbon layer coating of graphene and high-density carbon or low-density carbon and high-density carbon, the internal conductivity of the whole micron structure can be improved by the internal low-density carbon layer, and electrolyte can be well prevented from penetrating through the carbon layer and entering the interior of micron particles by the external high-density carbon layer, so that the problem of reaction of a silicon material and battery liquid is well solved, and higher coulombic efficiency is ensured, and the cycle performance of a battery is well ensured. The core innovation point is double-layer carbon coating, and the combination of low density and high density carbon realizes the preparation of the silicon/carbon composite anode material.
The patent with publication number CN108630925A proposes a preparation method of graphene coated silicon oxide anode material, which comprises the following steps: 1) Mixing the silicon oxide micro powder and the graphite micro powder, adding the mixture into graphene oxide dispersion liquid, adding a dispersing agent, and performing ultrasonic dispersion treatment to form suspension, wherein graphene oxide is prepared by the steps of: the mass ratio of the silica micropowder to the graphite micropowder is 1:10-15:10-15; 2) Performing spray drying and pelletizing on the suspension obtained in the step 2), and performing heat treatment at 500-800 ℃ in a reducing atmosphere to obtain graphene-coated silica micropowder and graphite micropowder composite anode material; the heat treatment process comprises the following steps: 2.1 Heat treatment is carried out for 1 to 2 hours in hydrogen atmosphere at 500 to 600 ℃;2.2 Then adjusting the atmosphere to be a hydrogen-helium mixed atmosphere; and heating to 700-800 ℃ at a speed of 2-3 ℃/min, preserving heat for 4-5 h after reaching a set temperature, wherein the volume percentage of hydrogen in the mixed atmosphere is 10-20%, and naturally cooling after the heat preservation is finished.
Patent publication No. CN111048757A discloses a B, N co-doped graphene coated silicon nano negative electrode material and a preparation method thereof, wherein the negative electrode material is prepared from B, N co-doped graphene coated silicon nano particles. The preparation method comprises the following steps: (1) Adding graphene oxide powder into water, and performing ultrasonic dispersion to obtain graphene oxide aqueous dispersion; (2) Adding silicon nano particles and a nitrogen source into graphene oxide aqueous dispersion, performing primary ultrasonic dispersion, adding a boron source, performing secondary ultrasonic dispersion, and performing freeze drying to obtain a graphene oxide coated silicon nanocomposite containing B, N; (3) And (3) carrying out heat treatment, water washing and drying on the graphene oxide coated silicon nanocomposite material containing B, N in an inert atmosphere.
The patent with the publication number of CN113078322A discloses a graphene-silicon negative electrode material with the cycling stability of a lithium battery and a preparation method, and the graphene-silicon negative electrode material comprises the steps of adding graphene oxide powder and nanometer silicon powder into deionized water, adding a dispersing agent for ultrasonic dispersion, then adding a thickening agent, stirring and uniformly mixing to prepare slurry, adding the slurry into a mechanical ball mill, adding terephthalyl acid into the slurry after ball milling is completed, continuing ball milling, placing the slurry obtained after ball milling into a water bath kettle, heating in the water bath after sealing, centrifugally separating and drying to obtain powder, annealing the obtained powder in a reducing atmosphere, washing and drying to obtain the negative electrode material powder.
The silicon-based negative electrode mainly has three failure mechanisms: pulverizing silicon-based particles; the SEI layer is unstable and the electrode sheet is overall swelled and ruptured. The graphene and other carbon materials are coated on the surfaces of the silicon-based material particles, so that the problem that the silicon-based particles are crushed and pulverized due to expansion can be well restrained. However, the expansion suppression of the whole electrode sheet is mainly accomplished by the adhesive force of the adhesive. Because intrinsic graphene materials have poor affinity with high polymer materials, strong acting force is difficult to form at an interface. Therefore, in the prior art, the silicon-based material particles are coated by graphene only, so that a good bonding effect is difficult to achieve, and the prior art adopts the traditional graphene-coated silicon-based negative electrode conductive network, which is single in form, mainly comprises surface-to-surface contact and surface-to-point contact, and has relatively low pole piece conductivity and relatively high internal resistance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a silicon anode material coated by conductive polymer grafted graphene and a preparation method thereof, wherein the graphene is grafted by using a polymer, so that the affinity with a polymer binder can be effectively improved, the binding force is improved, the cracking of a pole piece is inhibited, the circulation stability is improved, and the point-line-surface multidimensional conductive network can be realized by using the graphene coated grafted by the conductive polymer and matching with a conductive filler, the conductivity of the pole piece is further improved, and the internal resistance is reduced.
In order to achieve the above purpose, the present invention adopts the following technical scheme: the silicon anode material coated with the conductive polymer grafted graphene is silicon-based material particles coated with polyaniline grafted graphene oxide.
According to the invention, the polymer is used for grafting the graphene, so that the surface performance of the graphene is changed, the interaction between the graphene and the binder can be effectively improved, the binding force is improved, the cracking of the pole piece is inhibited, and the circulation stability is improved; and the graphene grafted by the conductive polymer is used for coating, and the conductive filler is matched, so that a multi-dimensional and highly interpenetrating conductive network of point-line-surface can be realized, the conductivity of the pole piece is further improved, and the internal resistance is reduced.
A preparation method of a silicon anode material coated by conductive polymer grafted graphene comprises the following steps:
i) Adding silicon-based material particles and polyaniline-grafted graphene oxide powder into an organic solvent, performing ultrasonic and shearing dispersion to obtain a uniform solution, adding a hydrazine hydrate solution, stirring to be homogeneous, continuously stirring to react at room temperature for 10-48 hours, and filtering and washing the obtained mixed solution for multiple times by using water and absolute ethyl alcohol to obtain reduced polyaniline-grafted graphene;
ii) adding the reduced polyaniline grafted graphene into water, performing ultrasonic dispersion to prepare a dispersion liquid, and granulating by a spray drying method to obtain the silicon anode material coated with the conductive polymer grafted graphene.
Preferably, the silicon-based material particles comprise one or more of elemental silicon, silicon oxide and silicon oxide, and/or the particle size of the silicon-based material particles is smaller than the lateral dimension of the reduced polyaniline-grafted graphene.
Preferably, the lateral dimension of the polyaniline-grafted graphene is greater than or equal to 10 times of the particle size of the silicon-based material particles.
Preferably, in the step i), the mass ratio of the graphene oxide to the hydrazine hydrate is 1:0.7-1:1; and/or the organic solvent comprises one or more of N, N-dimethylformamide, N-methylpyrrolidone and tetrahydrofuran.
Preferably, in the dispersion liquid in the step ii), the concentration of the silicon-based material particles and the polyaniline-grafted graphene is 0.1-30wt%.
Preferably, the preparation method of the polyaniline grafted graphene oxide powder comprises the following steps:
(1) Adding graphene oxide into water to prepare uniform graphene oxide aqueous dispersion;
(2) Adding a hydrochloric acid solution and a phenylenediamine solution into graphene oxide aqueous dispersion, stirring and mixing uniformly, standing, slowly adding sodium nitrite into the mixed solution, dissolving, mixing uniformly, standing, and reacting at a constant temperature of 50-70 ℃ for 3-6 h; after the reaction is finished, adding water for dilution and cooling, filtering and washing a product by using water, and re-dispersing the filtered product into water to obtain a surface functionalized graphene oxide dispersion liquid;
(3) Under the ice bath environment, taking a certain amount of graphene oxide dispersion liquid with functionalized surface, adding hydrochloric acid and aniline, stirring uniformly, adding ammonium persulfate and hydrochloric acid mixed solution into the mixed solution, reacting for 6-10 h under the ice bath condition, filtering the obtained mixture, repeatedly filtering and washing with water and absolute ethyl alcohol, and drying to obtain polyaniline grafted graphene oxide powder.
Preferably, in the step (1), the concentration of the graphene oxide aqueous dispersion is 0.5 to 2mg/mL.
Preferably, in the step (2): the mass ratio of graphene oxide to phenylenediamine to sodium nitrite is 1: (0.5-1.5): (0.1 to 1); and/or the concentration of the hydrochloric acid solution is 0.05-0.2 mol/L; and/or the standing time is 10-60 min.
Preferably, in the step (3): the mass ratio of the graphene oxide with the functionalized surface to the aniline monomer is 1:1-40; and/or the mass ratio of aniline to ammonium persulfate is 1:1 to 4; and/or hydrochloric acid concentration is 0.5-2 mol/L; and/or the drying temperature is 30-60 ℃ and the drying time is 10-15 h.
In summary, the invention has the following beneficial effects: (1) The conductive polymer is used for grafting the graphene coating layer, so that the surface performance of graphene is changed, the interaction between graphene and a binder is improved, the bonding effect is enhanced, and the circulation stability is improved; (2) The graphene grafted by the conductive polymer is used for coating, and the conductive filler is matched, so that a multi-dimensional and highly interpenetrating conductive network of point-line-surface can be realized, the conductivity of the pole piece is further improved, and the internal resistance is reduced.
Detailed Description
In order to facilitate understanding of the technical means, the creation characteristics, the achievement of the objects and the effects achieved by the present invention, the present invention is further described below with reference to specific examples, but the following examples are only preferred examples of the present invention, not all of which are described in detail below. Based on the examples in the embodiments, those skilled in the art can obtain other examples without making any inventive effort, which fall within the scope of the invention. The experimental methods in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used in the following examples are commercially available unless otherwise specified.
Example 1
(1) 1000mg of graphene oxide powder is weighed and added into 1000mL of pure water, and the mixture is stirred for 2 hours at room temperature after ultrasonic treatment for 30 minutes;
(2) 15mL of 12M hydrochloric acid and 0.6g of phenylenediamine were slowly added to the solution of (1), and the mixture was stirred uniformly and allowed to stand for half an hour. Continuously adding 0.2g of sodium nitrite into the solution in a sweat diffusion way, uniformly stirring, and then placing the mixture into an oil bath at 60 ℃ for reaction for 4 hours. After that, the reaction flask was taken out and allowed to stand to room temperature. The product solution was vacuum filtered and washed with copious amounts of deionized water. After thorough washing, re-dispersing the filtrate into 1000mL of pure water to obtain a-GO dispersion;
(3) 83mL of 12M hydrochloric acid and 0.97mL of aniline are added dropwise to 1000mL of the surface functionalized graphene oxide (a-GO) dispersion in an ice bath environment, and after stirring uniformly, 100mL of a mixed solution containing 4g of ammonium persulfate and 0.1mol of hydrochloric acid is added to the mixed solution. The reaction was kept at 0℃for 8 hours. After the reaction is finished, the mixture is filtered in vacuum, and is repeatedly filtered and washed by deionized water and absolute ethyl alcohol. Drying the obtained filtrate in an oven at 45 ℃ for 12 hours under normal pressure to obtain PANi-g-GO powder;
(4) 20g of silica nanoparticles and 1g of polyaniline-grafted graphene oxide (PANi-g-GO) powder were mixed and added to 200mL of N, N-dimethylformamide, and the mixture was sonicated for 15mins and stirred at room temperature for 2h. And adding 0.55g of hydrazine hydrate solution into the mixed solution, uniformly stirring, and continuously stirring at a low speed at room temperature for 24 hours. And (3) carrying out suction filtration on the reacted mixture, filtering and washing the mixture by deionized water and absolute ethyl alcohol, adding the obtained filtrate into pure water, carrying out ultrasonic treatment, shearing and dispersing, and then carrying out spray drying treatment to obtain the conductive polymer grafted graphene coated silicon anode material.
Example 2
(1) Weighing 500mg of graphene oxide powder, adding the graphene oxide powder into 500mL of pure water, and stirring at room temperature for 2 hours after ultrasonic treatment for 30 min;
(2) 13mL of 2M hydrochloric acid and 0.5g of phenylenediamine were slowly added to the solution of (1), and the mixture was stirred uniformly and allowed to stand for half an hour. Continuously adding 0.5g of sodium nitrite into the solution in a sweat diffusion way, uniformly stirring, and then placing the mixture into an oil bath at 60 ℃ for reaction for 4 hours. After that, the reaction flask was taken out and allowed to stand to room temperature. The product solution was vacuum filtered and washed with copious amounts of deionized water. After thorough washing, re-dispersing the filtrate into 500mL of pure water to obtain a-GO dispersion;
(3) 15mL of 12M hydrochloric acid and 195mL of aniline are added dropwise to 5mL of a-GO dispersion liquid under an ice bath environment, and after being stirred uniformly, 10mL of mixed solution containing 0.2g of ammonium persulfate and 0.01mol of hydrochloric acid is added to the mixed solution. The reaction was kept at 0℃for 8 hours. After the reaction is finished, the mixture is filtered in vacuum, and is repeatedly filtered and washed by deionized water and absolute ethyl alcohol. Drying the obtained filtrate in an oven at 45 ℃ for 12 hours under normal pressure to obtain PANi-g-GO powder;
(4) 5g of silica nanoparticles and 0.5g of PANi-g-GO powder were mixed and added to 100mL of N-methylpyrrolidone, sonicated for 15mins and stirred at room temperature for 2h. To the mixed solution, 0.014g of hydrazine hydrate solution was added, and after stirring uniformly, stirring was continued at room temperature for 24 hours at a low speed. And (3) carrying out suction filtration on the reacted mixture, filtering and washing the mixture by deionized water and absolute ethyl alcohol, adding the obtained filtrate into pure water, carrying out ultrasonic treatment, shearing and dispersing, and then carrying out spray drying treatment to obtain the conductive polymer grafted graphene coated silicon anode material.
Example 3
(1) 1000mg of graphene oxide powder is weighed and added into 1000mL of pure water, and the mixture is stirred for 2 hours at room temperature after ultrasonic treatment for 30 minutes;
(2) 15mL of 12M hydrochloric acid and 1.3g of phenylenediamine were slowly added to the solution of (1), and the mixture was stirred uniformly and allowed to stand for half an hour. Continuously adding 0.9g of sodium nitrite into the solution in a sweat diffusion way, uniformly stirring, and then placing the mixture into an oil bath at 60 ℃ for reaction for 4 hours. After that, the reaction flask was taken out and allowed to stand to room temperature. The product solution was vacuum filtered and washed with copious amounts of deionized water. After thorough washing, re-dispersing the filtrate into 500mL of pure water to obtain a-GO dispersion;
(3) 50mL of 2M hydrochloric acid and 0.5mL of aniline are added dropwise to 50mL of a-GO dispersion liquid under an ice bath environment, and 50mL of a mixed solution containing 5g of ammonium persulfate and 0.05mol of hydrochloric acid is added to the mixed solution after uniform stirring. The reaction was kept at 0℃for 8 hours. After the reaction is finished, the mixture is filtered in vacuum, and is repeatedly filtered and washed by deionized water and absolute ethyl alcohol. Drying the obtained filtrate in an oven at 45 ℃ for 12 hours under normal pressure to obtain PANi-g-GO powder;
(4) 10g of silica nanoparticles and 1g of PANi-g-GO powder were mixed and added to 100mL of N-methylpyrrolidone, sonicated for 15mins and stirred at room temperature for 2h. And adding 0.2g of hydrazine hydrate solution into the mixed solution, uniformly stirring, and continuously stirring at a low speed at room temperature for 24 hours. And (3) carrying out suction filtration on the reacted mixture, filtering and washing the mixture by deionized water and absolute ethyl alcohol, adding the obtained filtrate into pure water, carrying out ultrasonic treatment, shearing and dispersing, and then carrying out spray drying treatment to obtain the conductive polymer grafted graphene coated silicon anode material.
The conductive polymer grafted graphene coated silicon anode material obtained in the embodiment 1-3 is made into a 7Ah soft-packed battery, and the soft-packed battery is prepared from the common graphene coated silicon anode material, and the anode is evaluated as shown in the following table:
| sample of | The cathode is made into gram capacity | DCR/Ohem | Full charge expansion rate | Capacity retention after 1000 weeks of cycling |
| Example 1 | 420mAh/g | 13.8 | 26.8％ | 83.4％ |
| Example 2 | 450mAh/g | 13.7 | 27.5％ | 80.2％ |
| Example 3 | 500mAh/g | 15.3 | 32.4％ | 76.8％ |
| Contrast sample | 420mAh/g | 19.3 | 30.6％ | 79.2％ |
As can be seen from the performance evaluation comparison of the invention and the comparison sample, the soft-package battery prepared from the silicon anode material coated by the conductive polymer grafted graphene has larger gram capacity and smaller DCR value, which shows that the invention has smaller impedance, mainly because the conductive polymer and the conductive filler added subsequently form a multi-dimensional and highly interpenetrating conductive network, the internal resistance is reduced; meanwhile, the soft package battery prepared in the follow-up steps of the embodiment 1 and the embodiment 2 has relatively low full charge expansion rate, and has high capacity retention rate after 1000 weeks of circulation, and the conductive polymer grafted graphene coated silicon anode material has better bonding effect and high circulation stability.
Example 4
(1) 1000mg of graphene oxide powder is weighed and added into 1000mL of pure water, and the mixture is stirred for 2 hours at room temperature after ultrasonic treatment for 30 minutes;
(2) 15mL of 12M hydrochloric acid and 0.5g of phenylenediamine were slowly added to the solution of (1), and the mixture was stirred uniformly and allowed to stand for 10 minutes. Continuously adding 0.1g of sodium nitrite into the solution in a sweat diffusion way, uniformly stirring, and then placing the mixture into an oil bath at 50 ℃ for reaction for 6 hours. After that, the reaction flask was taken out and allowed to stand to room temperature. The product solution was vacuum filtered and washed with copious amounts of deionized water. After thorough washing, re-dispersing the filtrate into 1000mL of pure water to obtain a-GO dispersion;
(3) 83mL of 12M hydrochloric acid and 0.97mL of aniline are added dropwise to 1000mL of the surface functionalized graphene oxide (a-GO) dispersion in an ice bath environment, and after stirring uniformly, 100mL of a mixed solution containing 4g of ammonium persulfate and 0.1mol of hydrochloric acid is added to the mixed solution. The reaction was kept at 0℃for 6 hours. After the reaction is finished, the mixture is filtered in vacuum, and is repeatedly filtered and washed by deionized water and absolute ethyl alcohol. Drying the obtained filtrate in an oven at 60 ℃ for 10 hours under normal pressure to obtain PANi-g-GO powder;
(4) 20g of silica nanoparticles and 1g of polyaniline-grafted graphene oxide (PANi-g-GO) powder were mixed and added to 200mL of N, N-dimethylformamide, and the mixture was sonicated for 15mins and stirred at room temperature for 2h. And adding 0.55g of hydrazine hydrate solution into the mixed solution, uniformly stirring, and continuously stirring at a low speed at room temperature for 48 hours. And (3) carrying out suction filtration on the reacted mixture, filtering and washing the mixture by deionized water and absolute ethyl alcohol, adding the obtained filtrate into pure water, carrying out ultrasonic treatment, shearing and dispersing, and then carrying out spray drying treatment to obtain the conductive polymer grafted graphene coated silicon anode material.
Example 5
(1) Weighing 500mg of graphene oxide powder, adding the graphene oxide powder into 500mL of pure water, and stirring at room temperature for 2 hours after ultrasonic treatment for 30 min;
(2) 13mL of 2M hydrochloric acid and 0.75g of phenylenediamine were slowly added to the solution of (1), and the mixture was stirred uniformly and allowed to stand for 60 minutes. Continuously adding 0.5g of sodium nitrite into the solution in a sweat diffusion way, uniformly stirring, and then placing the mixture into an oil bath at 70 ℃ for reaction for 3 hours. After that, the reaction flask was taken out and allowed to stand to room temperature. The product solution was vacuum filtered and washed with copious amounts of deionized water. After thorough washing, re-dispersing the filtrate into 500mL of pure water to obtain a-GO dispersion;
(3) 15mL of 12M hydrochloric acid and 195mL of aniline are added dropwise to 5mL of a-GO dispersion liquid under an ice bath environment, and after being stirred uniformly, 10mL of mixed solution containing 0.2g of ammonium persulfate and 0.01mol of hydrochloric acid is added to the mixed solution. The reaction was kept at 0℃for 10 hours. After the reaction is finished, the mixture is filtered in vacuum, and is repeatedly filtered and washed by deionized water and absolute ethyl alcohol. Drying the obtained filtrate in an oven at 30 ℃ for 15 hours under normal pressure to obtain PANi-g-GO powder;
(4) 5g of silica nanoparticles and 1g of PANi-g-GO powder were mixed and added to 100mL of tetrahydrofuran, sonicated for 15mins and stirred at room temperature for 2h. And adding 0.4g of hydrazine hydrate solution into the mixed solution, uniformly stirring, and continuously stirring at a low speed at room temperature for 10 hours. And (3) carrying out suction filtration on the reacted mixture, filtering and washing the mixture by deionized water and absolute ethyl alcohol, adding the obtained filtrate into pure water, carrying out ultrasonic treatment, shearing and dispersing, and then carrying out spray drying treatment to obtain the conductive polymer grafted graphene coated silicon anode material.
Example 6
(1) 1000mg of graphene oxide powder is weighed and added into 500mL of pure water, and the mixture is stirred for 2 hours at room temperature after ultrasonic treatment for 30 minutes;
(2) 13mL of 2M hydrochloric acid and 0.75g of phenylenediamine were slowly added to the solution of (1), and the mixture was stirred uniformly and allowed to stand for 60 minutes. Continuously adding 1g of sodium nitrite into the solution in a sweat diffusion way, uniformly stirring, and then placing the mixture into an oil bath at 70 ℃ for reaction for 3 hours. After that, the reaction flask was taken out and allowed to stand to room temperature. The product solution was vacuum filtered and washed with copious amounts of deionized water. After thorough washing, re-dispersing the filtrate into 500mL of pure water to obtain a-GO dispersion;
(3) 15mL of 12M hydrochloric acid and 195mL of aniline are added dropwise to 5mL of a-GO dispersion liquid under an ice bath environment, and after being stirred uniformly, 10mL of mixed solution containing 0.2g of ammonium persulfate and 0.01mol of hydrochloric acid is added to the mixed solution. The reaction was kept at 0℃for 10 hours. After the reaction is finished, the mixture is filtered in vacuum, and is repeatedly filtered and washed by deionized water and absolute ethyl alcohol. Drying the obtained filtrate in an oven at 30 ℃ for 15 hours under normal pressure to obtain PANi-g-GO powder;
(4) 5g of silica nanoparticles and 0.5g of PANi-g-GO powder were mixed and added to 100mL of N-methylpyrrolidone, sonicated for 15min and stirred at room temperature for 2h. To the mixed solution, 0.014g of hydrazine hydrate solution was added, and after stirring uniformly, stirring was continued at room temperature for 10 hours at low speed. And (3) carrying out suction filtration on the reacted mixture, filtering and washing the mixture by deionized water and absolute ethyl alcohol, adding the obtained filtrate into pure water, carrying out ultrasonic treatment, shearing and dispersing, and then carrying out spray drying treatment to obtain the conductive polymer grafted graphene coated silicon anode material.
Claims (8)
1. The silicon anode material coated with the conductive polymer grafted graphene is characterized in that the silicon anode material coated with the conductive polymer grafted graphene is silicon-based material particles coated with polyaniline grafted graphene oxide, and is prepared by the following steps:
i) Adding silicon-based material particles and polyaniline-grafted graphene oxide powder into an organic solvent, performing ultrasonic and shearing dispersion to obtain a uniform solution, adding a hydrazine hydrate solution, stirring to be uniform, continuously stirring to react at room temperature for 10-48 hours, and filtering and washing the obtained mixed solution for multiple times by using water and absolute ethyl alcohol to obtain reduced polyaniline-grafted graphene;
ii) adding the reduced polyaniline grafted graphene into water, performing ultrasonic dispersion to prepare a dispersion liquid, and granulating by a spray drying method to obtain a silicon anode material coated by the conductive polymer grafted graphene;
the preparation method of the polyaniline grafted graphene oxide powder comprises the following steps:
(1) Adding graphene oxide into water to prepare uniform graphene oxide aqueous dispersion;
(2) Adding a hydrochloric acid solution and a phenylenediamine solution into graphene oxide aqueous dispersion, stirring and mixing uniformly, standing, slowly adding sodium nitrite into the mixed solution, dissolving, mixing uniformly, standing, and reacting at a constant temperature of 50-70 ℃ for 3-6 hours; after the reaction is finished, adding water for dilution and cooling, filtering and washing a product by using water, and re-dispersing the filtered product into water to obtain a surface functionalized graphene oxide dispersion liquid;
(3) And in an ice bath environment, taking a certain amount of graphene oxide dispersion liquid with the surface functionalized, adding hydrochloric acid and aniline, stirring uniformly, adding a mixed solution of ammonium persulfate and hydrochloric acid into the mixed solution, reacting for 6-10 hours under the ice bath condition, filtering the obtained mixture, repeatedly filtering and washing with water and absolute ethyl alcohol, and drying to obtain polyaniline grafted graphene oxide powder.
2. The method for preparing the conductive polymer grafted graphene coated silicon anode material according to claim 1, which is characterized by comprising the following steps:
i) Adding silicon-based material particles and polyaniline-grafted graphene oxide powder into an organic solvent, performing ultrasonic and shearing dispersion to obtain a uniform solution, adding a hydrazine hydrate solution, stirring to be uniform, continuously stirring to react at room temperature for 10-48 hours, and filtering and washing the obtained mixed solution for multiple times by using water and absolute ethyl alcohol to obtain reduced polyaniline-grafted graphene;
ii) adding the reduced polyaniline grafted graphene into water, performing ultrasonic dispersion to prepare a dispersion liquid, and granulating by a spray drying method to obtain a silicon anode material coated by the conductive polymer grafted graphene;
the preparation method of the polyaniline grafted graphene oxide powder comprises the following steps:
(1) Adding graphene oxide into water to prepare uniform graphene oxide aqueous dispersion;
(2) Adding a hydrochloric acid solution and a phenylenediamine solution into graphene oxide aqueous dispersion, stirring and mixing uniformly, standing, slowly adding sodium nitrite into the mixed solution, dissolving, mixing uniformly, standing, and reacting at a constant temperature of 50-70 ℃ for 3-6 hours; after the reaction is finished, adding water for dilution and cooling, filtering and washing a product by using water, and re-dispersing the filtered product into water to obtain a surface functionalized graphene oxide dispersion liquid;
(3) And in an ice bath environment, taking a certain amount of graphene oxide dispersion liquid with the surface functionalized, adding hydrochloric acid and aniline, stirring uniformly, adding a mixed solution of ammonium persulfate and hydrochloric acid into the mixed solution, reacting for 6-10 hours under the ice bath condition, filtering the obtained mixture, repeatedly filtering and washing with water and absolute ethyl alcohol, and drying to obtain polyaniline grafted graphene oxide powder.
3. The method of claim 2, wherein the silicon-based material particles comprise one or more of elemental silicon, silicon oxide, and/or
The particle size of the silicon-based material particles is smaller than the lateral dimension of the reduced polyaniline-grafted graphene.
4. The method of claim 3, wherein the polyaniline-grafted graphene has a lateral dimension of 10 times or more than the particle size of the silicon-based material particles.
5. The preparation method according to claim 2, wherein in the step i), the mass ratio of graphene oxide to hydrazine hydrate is 1:0.7-1:1; and/or
The organic solvent comprises one or more of N, N-dimethylformamide, N-methylpyrrolidone and tetrahydrofuran.
6. The preparation method according to claim 2, wherein in the step (1), the concentration of the graphene oxide aqueous dispersion is 0.5-2 mg/mL.
7. The method according to claim 2, wherein in the step (2): the mass ratio of graphene oxide to phenylenediamine to sodium nitrite is 1: (0.5 to 1.5): (0.1-1); and/or
The concentration of the hydrochloric acid solution is 0.05-0.2 mol/L; and/or
The standing time is 10-60 min.
8. The method according to claim 2, wherein in the step (3): the mass ratio of the graphene oxide with the functionalized surface to the aniline monomer is 1:1-40; and/or
The mass ratio of aniline to ammonium persulfate is 1: 1-4; and/or
The concentration of hydrochloric acid is 0.5-2 mol/L; and/or
The drying temperature is 30-60 ℃ and the drying time is 10-15 h.
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