CN115387028A - Porous Si/C composite material packaged by conductive fiber network and preparation method and application thereof - Google Patents
Porous Si/C composite material packaged by conductive fiber network and preparation method and application thereof Download PDFInfo
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- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 239000000835 fiber Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002028 Biomass Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 26
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 21
- 235000009566 rice Nutrition 0.000 claims abstract description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000011856 silicon-based particle Substances 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 239000010903 husk Substances 0.000 claims abstract description 3
- 240000007594 Oryza sativa Species 0.000 claims abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000012535 impurity Substances 0.000 claims description 19
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
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- 238000000498 ball milling Methods 0.000 claims description 9
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- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229940078494 nickel acetate Drugs 0.000 claims description 6
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- 238000003756 stirring Methods 0.000 claims description 6
- 229910019018 Mg 2 Si Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- 239000002322 conducting polymer Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 abstract description 36
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
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- 239000013543 active substance Substances 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 37
- 241000209094 Oryza Species 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
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- 238000011056 performance test Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
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- 239000006245 Carbon black Super-P Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
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- 238000000576 coating method Methods 0.000 description 2
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- 241000233866 Fungi Species 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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 Si/C composite material packaged by a conductive fiber network, and preparation and application thereof. Using rice husk as SiO 2 The precursor is prepared by magnesium thermal method 2 Si, then removed with hydrochloric acidAnd (3) forming porous Si by redundant Mg and MgO, then packaging porous Si particles into a graphitized carbon fiber network by adopting an electrostatic spinning method, and finally calcining in protective gas to obtain the porous Si/C composite material. The method is convenient and easy to operate, the reaction condition is controllable, the obtained biomass porous Si/C packaged by the conductive fiber network has a special structure and a large specific surface area, the full contact between electrolyte and active substances is facilitated, the volume expansion of the material in the charge-discharge process is effectively relieved, and the electrochemical performance of the material is greatly improved when the material is used as a lithium ion battery cathode material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery cathode materials, in particular to a porous Si/C composite material packaged by a conductive fiber network and a preparation method and application thereof.
Background
At present, the market of electric automobiles has continuously increased demand for maximizing the energy density of energy storage devices, and the capacity of the traditional graphite anode cannot meet the demand. Silicon has the highest theoretical capacity (10 times that of carbon-based materials), a relatively low operating potential plus its mature processing industry is considered a candidate for the next generation of lithium ion battery negative electrodes. The main components of rice hulls are cellulose, lignin and silica (10-20%). The rice hulls are renewable resources, approximately 6 million tons of rice and more than 1.2 million tons of rice hulls are produced in the world every year, and China produces approximately 2 million tons of rice products and approximately 4000 million tons of rice hulls as a large agricultural country every year. Wherein only a small part of the rice hulls are used for organic fertilizer or edible fungus cultivation, and the rest most of the rice hulls are burned or abandoned in the field, so that the development and utilization of the part of resources have strategic significance and economic value. Therefore, if the rice hulls are used as precursors to prepare the lithium ion battery cathode material, the method has high practical significance for reducing environmental pollution and improving residual value of the rice hulls.
However, silicon expands greatly (> 300%) in volume during lithiation, decreases to different sizes during delithiation, electrode interfaces continue to grow unstable Solid Electrolyte (SEI) films, and silicon has poor conductivity as a semiconductor material, which results in too rapid a decline in the capacity of silicon negative electrodes and low first-week coulombic efficiency (ICE) increasing its commercial difficulty. Therefore, silicon-based materials need to be modified (such as micro-nano structure design, porous silicon structure design, carbon-coated three-dimensional structure design and the like), the volume expansion of the materials is relieved, a stable SEI film is continuously generated, the electrochemical performance of the SEI film is enhanced, and the requirements of commercial production are met. A simple and reasonable modification strategy is developed, the electrochemical performance of the silicon negative electrode material is optimized, and the method is an important research direction for the application of the rice hulls in the field of lithium ion battery negative electrodes.
In the invention, the biomass porous Si/C structure encapsulated by the conductive fiber network is successfully prepared by combining a magnesiothermic reduction method and an electrostatic spinning method and then by a simple heat treatment process. The final product uniformly wraps the porous Si particles in the graphitized carbon fiber network, so that the conductivity can be improved, the transmission of ions and electrons can be promoted, and the volume expansion can be relieved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a porous Si/C composite material packaged by a conductive fiber network, a preparation method and application thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of a porous Si/C composite material encapsulated by a conductive fiber network comprises the following steps: porous Si particles are encapsulated in a conductive fiber network C material.
The porous Si particles are biological porous Si with the particle size of 3-5 microns.
The preparation method of the biomass porous Si comprises the following steps:
1) The crushed biomass is subjected to heat treatment, then hydrochloric acid is used for removing metal oxides in the biomass, and pure SiO is obtained after filtration 2 ；
2) Pure SiO 2 Mixing with Mg at a certain mass ratio, and heat treating in protective atmosphere to obtain Mg 2 Si, removing excessive Mg and MgO impurities by hydrochloric acid, and filtering to obtain the porous Si.
In the step 1), the biomass comprises at least one of rice hulls, diatomite and corn husks, and the particle size of the biomass is 8-10 micrometers; preferably ball milling in a ball mill for 2-6 h; preferably 4 to 6 hours, and more preferably 5 hours.
Step 1), the heat treatment temperature of a muffle furnace is 800-1000 ℃, and the heat treatment time is 1-3 h; preferably 900 ℃; the heat treatment time is 2h.
Step 1), the concentration of hydrochloric acid is 1-3 mol/L; preferably 2mol/L.
SiO in step 2) 2 The mass ratio of Mg to Mg is 0.5-1: 1, preferably 0.5:1.
the invention finds that the biomass has different silicon dioxide and magnesium proportions, and the products obtained by magnesium heating are different. The reduction of Mg is too little and incomplete, and residual SiO is generated 2 . SiO with increasing Mg content 2 Continuously decrease of Si and Mg 2 Si is gradually increased. Until the SiO of biomass 2 : when Mg is 1 2 And Si completely disappears to obtain pure Mg 2 Si and MgO. When SiO 2 When the mass ratio of Mg is less than 1 2 And the residue was found to be incompletely reduced. When the SiO of the biomass 2 : when the Mg mass ratio is higher than 1. So that the SiO of the biomass 2 : mg is 1. The relevant conclusions are shown in FIG. 5.
Step 2), the heat treatment temperature is 600-800 ℃, and the heat treatment time is 8-12 h; preferably 700 ℃; the heat treatment time is 10h.
The concentration of hydrochloric acid in the step 2) is 1-3 mol/L; preferably 2mol/L.
The conductive fiber network C material is obtained by conducting polymers in an electrostatic spinning heating treatment mode.
The method specifically comprises the following steps:
(1) Adding the polymer into DMF or a mixture of DMF and PVP according to a certain liquid-solid ratio, and uniformly stirring to obtain a viscous clear liquid A;
(2) Adding porous Si and ferric acetylacetonate or nickel acetate into the solution A according to a certain mass ratio, and uniformly stirring to obtain a viscous brown solution B;
(3) Putting the viscous brown solution B into an electrostatic spinning machine, and performing electrostatic spinning at a certain electrostatic voltage and feeding speed to obtain a product C;
(4) Preheating the product C to obtain a product D, and carrying out heat treatment on the product D under a protective atmosphere to obtain a one-dimensional product E;
(5) And putting the product E into hydrochloric acid to remove ferric acetylacetonate or nickel acetate to obtain the conductive fiber network encapsulated biomass porous Si/C composite material.
The polymer in step (1) is a high molecular weight organic matter comprising polyvinylpyrrolidone (PVP M) w = 1300000), polyacrylonitrile (PAN M) w = 150000); polyacrylonitrile (PAN M) is preferred w ＝150000)。
The liquid-solid ratio in the step (1) is 0.8-1.2; preferably 1.
The mass ratio of the porous Si to the ferric acetylacetonate or the nickel acetate in the step (2) is 8. Preferably 10.
Setting the electrostatic spinning voltage in the step (3) to be 15-25 kV, and setting the feeding speed to be 0.3-0.6 ml/h; preferably 20kV; the feed rate was 0.5ml/h.
The preheating treatment temperature in the step (4) is 200-300 ℃, the treatment time is 1-3 h, preferably 250 ℃, and the treatment time is 1h.
The protective heat treatment temperature in the step (4) is 700-900 ℃, and the treatment time is 2-4 h; preferably 800 ℃; the treatment time was 3h.
The concentration of hydrochloric acid in the step (5) is 1-3 mol/L; preferably 2mol/L.
The biomass porous Si/C composite material packaged by the conductive fiber network is prepared by the preparation method.
The invention also provides application of the biomass porous Si/C composite material packaged by the conductive fiber network in preparation of a battery cathode material; in particular to the application of the negative electrode material of the lithium ion battery.
Compared with the prior art, the invention has the advantages that:
1. the method has the advantages of simple raw materials, short process flow, environmental friendliness and less carried impurities;
2. the invention adopts the electrostatic spinning method for direct synthesis, the process is simple and easy to implement, and the product appearance is controllable;
3. the product synthesized by the method has a special structure, a one-dimensional biomass porous structure, a large number of porous silicon particles are encapsulated inside the product, and the structure is stable;
4. according to the invention, rice hulls are used as biomass raw materials for preparing porous silicon for the first time, and magnesium thermal reaction and proper raw material proportion are combined, so that the specific surface area of the obtained porous silicon is obviously larger than that of porous silicon materials prepared by other raw materials and methods, and the specific surface area can reach 269.4558m 2 Per g, the specific surface area of the porous silicon prepared by the common ferrosilicon alloy is 165m 2 And about/g.
5. The product synthesized by the method is uniform in distribution and large in specific surface area, and is favorable for improving the electrochemical performance when used as a lithium ion battery cathode material.
Drawings
Fig. 1 is an SEM picture of one-dimensional biomass porous Si obtained in example 1 of the present invention.
Fig. 2 is an XRD picture of the conductive fiber network encapsulated biomass porous Si/C composite obtained in example 2 of the present invention.
Fig. 3 is an SEM picture of the conductive fiber network encapsulated biomass porous Si/C composite obtained in example 2 of the present invention.
Fig. 4 is a picture of the electrochemical performance of the conductive fiber network encapsulated biomass porous Si/C composite obtained in example 2 of the present invention.
FIG. 5 is an XRD pattern of the product of the thermal magnesium reaction of the present invention using biomass silica and magnesium in varying proportions.
FIG. 6 is a graph comparing electrochemical properties of the composite materials obtained in example 2 of the present invention and comparative example.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Example 1:
ball milling rice hull for 4 hr to obtain powder (8-10 μm in particle size)Heat treating in a muffle furnace at 900 deg.C for 2h, removing impurities in 2mol/L hydrochloric acid for 12h, filtering to obtain pure SiO 2 . Pure SiO 2 And Mg in a ratio of 1:2 mass ratio, and performing 700 ℃ heat treatment for 10 hours in a tube furnace under the argon atmosphere to obtain Mg 2 And (3) Si. Mixing Mg 2 And (4) putting the Si into 2mol/L hydrochloric acid to remove redundant Mg and MgO impurities (the impurity removal time is 6 h), and filtering to obtain porous Si. The resulting samples were analyzed using a Japanese Denko model D/max-2500X-ray diffraction analyzer. Scanning electron microscopy using Nova Nano SEM 230 from FEI corporation, usa, found that silicon was a porous structure, as shown in fig. 1.
The FEI company Nova Nano SEM 230 in USA finds that the average particle size after ball milling is (8-10 microns). The partial particle size distribution was obtained by using a Mastersizer 3000 laser particle size analyzer, with the pore size distribution of p-Si ranging from 0.1 to 0.3 microns. The specific surface area is measured by a physical adsorption apparatus (SORB-1-MP), the specific surface area of the obtained porous silicon is obviously larger than that of the porous silicon material prepared by other raw materials and methods, and can reach 269.4558m 2 /g。
Example 2:
ball-milling rice hull for 4h to obtain powder (particle size of 8-10 μm), heat treating at 900 deg.C in muffle furnace for 2h, removing impurities in 2mol/L hydrochloric acid (time 12 h), and filtering to obtain pure SiO 2 . Pure SiO 2 Mixing with Mg according to the proportion of 1:2 mass ratio, and performing 700 ℃ heat treatment for 10 hours in a tube furnace under the argon atmosphere to obtain Mg 2 And (3) Si. Mixing Mg 2 And (4) putting the Si into 2mol/L hydrochloric acid to remove redundant Mg and MgO impurities (the impurity removal time is 6 h), and filtering to obtain porous Si. 0.5g PAN was added to 5ml DMF solution and stirred well to give viscous clear solution A. 0.5g of porous Si and 0.03g of ferric acetylacetonate were added to the solution A and stirred uniformly to obtain a brown viscous solution B. And (3) performing electrostatic spinning (voltage 20kV; feeding speed 0.5 ml/h) on the brown viscous solution B to obtain a product C, putting the product C into a muffle furnace for pretreatment at 250 ℃ for 1h to obtain a product D, performing heat treatment on the product D at 800 ℃ for 3h in an argon atmosphere in a tube furnace to obtain a product E, putting the product E into 2mol/L hydrochloric acid to remove ferric acetylacetonate (time 6 h), and obtaining the conductive fiber network encapsulated biomass porous Si/C composite material. Using X-ray diffraction of Japan science D/max-2500 typeThe sample was analyzed by a radiation analyzer, and the results are shown in FIG. 2. The sample was observed by scanning electron microscopy using Nova Nano SEM 230, FEI, usa, and the composite was found to be composed of a network of fibers. And uniformly mixing the prepared biomass porous Si/C composite material packaged by the conductive fiber network according to 80wt.% of active material, 10wt.% of Super-P and 10wt.% of PVDF to prepare slurry, uniformly coating the slurry on copper foil, and vacuum-drying the slurry to assemble a button cell for electrochemical performance test. The voltage range of the cycle performance test is 0.005-1.5V, and the current density is 0.1Ag -1 The following steps. The cycle performance results are shown in fig. 4, which shows good electrochemical performance.
Example 3:
ball-milling rice hull for 4 hr to obtain powder (particle size of 8-10 μm), heat treating at 900 deg.C in muffle furnace for 2 hr, removing impurities in 2mol/L hydrochloric acid for 12 hr, filtering to obtain pure SiO 2 . Pure SiO 2 Mixing and stirring the mixture and Mg according to the mass ratio of 5 to 6, and performing heat treatment for 10 hours at 700 ℃ in a tube furnace under the argon atmosphere to obtain Mg 2 And (3) Si. And (3) putting the silicon-magnesium alloy into 2mol/L hydrochloric acid to remove redundant Mg and MgO impurities (the impurity removal time is 6 hours), and filtering to obtain the porous Si. 0.5g PAN was added to 5ml DMF solution and stirred well to give viscous clear solution A. 0.5g of porous Si and 0.05g of ferric acetylacetonate are added to the solution A and stirred uniformly to obtain a brown viscous solution B. And (3) performing electrostatic spinning (voltage 20kV; feeding speed 0.5 ml/h) on the brown viscous solution B to obtain a product C, putting the product C into a muffle furnace to perform pretreatment at 250 ℃ for 1h to obtain a product D, performing heat treatment on the product D at 800 ℃ for 3h in a tubular furnace under the argon atmosphere to obtain a product E, and putting the product E into 2mol/L hydrochloric acid to remove ferric acetylacetonate (time 6 h) to obtain the conductive fiber network-encapsulated biomass porous Si/C composite material. A sample is observed by using a Nova Nano SEM 230 scanning electron microscope of FEI company in America, and the composite material is found to be formed by a fiber network and have a multilayer porous structure, wherein porous Si particles are well coated in the fiber network.
Example 4: ball-milling rice hull for 4h to obtain powder (particle size of 8-10 μm), heat treating at 900 deg.C in muffle furnace for 2h, removing impurities in 2mol/L hydrochloric acid for 12h, and filtering to obtain pure SiO 2 . Pure SiO 2 Mixing with Mg according to the proportion of 5:8, and performing heat treatment at 700 ℃ for 10 hours in a tube furnace under the atmosphere of argon to obtain Mg 2 And (3) Si. Mixing Mg 2 And (4) putting the Si into 2mol/L hydrochloric acid to remove redundant Mg and MgO impurities (the impurity removal time is 6 h), and filtering to obtain porous Si. 0.5g PAN was added to 5ml DMF solution and stirred well to give viscous clear solution A. 0.5g of porous Si and 0.05g of ferric acetylacetonate were added to the solution A and stirred uniformly to obtain a brown viscous solution B. And (3) performing electrostatic spinning (voltage 20kV; feeding speed 0.5 ml/h) on the brown viscous solution B to obtain a product C, putting the product C into a muffle furnace to perform pretreatment at 250 ℃ for 1h to obtain a product D, performing heat treatment on the product D at 800 ℃ for 3h in a tubular furnace under the argon atmosphere to obtain a product E, and putting the product E into 2mol/L hydrochloric acid to remove ferric acetylacetonate (time 6 h) to obtain the conductive fiber network-encapsulated biomass porous Si/C composite material.
Example 5:
ball-milling rice hull for 4h to obtain powder (particle size of 8-10 μm), heat treating at 900 deg.C in muffle furnace for 2h, removing impurities in 2mol/L hydrochloric acid for 12h, and filtering to obtain pure SiO 2 . Pure SiO 2 Mixing and stirring the mixture and Mg according to the mass ratio of 1 to 2.4, and carrying out heat treatment for 10 hours at 600 ℃ in a tubular furnace under the atmosphere of argon to obtain Mg 2 And (3) Si. Mixing Mg 2 And (3) putting the Si into 2mol/L hydrochloric acid to remove redundant Mg and MgO impurities (the impurity removal time is 6 hours), and filtering to obtain the porous Si. 0.5g PAN was added to 5ml DMF solution and stirred well to give viscous clear solution A. 0.5g of porous Si and 0.05g of ferric acetylacetonate are added to the solution A and stirred uniformly to obtain a brown viscous solution B. And (3) performing electrostatic spinning (voltage 20kV; feeding speed 0.5 ml/h) on the brown viscous solution B to obtain a product C, putting the product C into a muffle furnace to perform pretreatment at 250 ℃ for 1h to obtain a product D, performing heat treatment on the product D at 800 ℃ for 3h in a tubular furnace under the argon atmosphere to obtain a product E, and putting the product E into 2mol/L hydrochloric acid to remove ferric acetylacetonate (time 6 h) to obtain the conductive fiber network-encapsulated biomass porous Si/C composite material.
Comparative example:
ball-milling rice hull for 4h to obtain powder (particle size of 8-10 μm), heat treating at 900 deg.C in muffle furnace for 2h, adding 2mol/L hydrochloric acid, removing impurities for 12h to obtain pure SiO 2 . Will be provided withSiO 2 NaCl and Mg are mixed according to the mass ratio of 1.
And replacing porous silicon with non-porous pure Si particles on the basis of the example 2, and preparing the biomass Si/C composite material encapsulated by the conductive fiber network under the same condition. The samples were observed by scanning electron microscopy using Nova Nano SEM 230, FEI company, usa, and the composite was found to consist of a network of fibers. And uniformly mixing the prepared biomass Si/C composite material packaged by the conductive fiber network according to 80wt.% of active material, 10wt.% of Super-P and 10wt.% of PVDF to prepare slurry, uniformly coating the slurry on copper foil, and assembling the slurry into a button cell after vacuum drying for electrochemical performance test. The voltage range of the cycle performance test is 0.005-1.5V, and the current density is 0.1Ag -1 And (5) the following. The cycle performance results are shown in fig. 6.
Claims (10)
1. A preparation method of a porous Si/C composite material encapsulated by a conductive fiber network is characterized by comprising the following steps: porous Si particles are encapsulated in a conductive fiber network C material.
2. The method for preparing a composite material according to claim 1, characterized in that: the porous Si particles are biological porous Si, and the particle size is 3-5 microns.
3. A method for preparing a composite material according to claim 2, characterized in that: the preparation method of the biomass porous Si comprises the following steps:
1) The crushed biomass is subjected to heat treatment, then hydrochloric acid is used for removing metal oxides in the biomass, and pure SiO is obtained after filtration 2 ；
2) Pure SiO 2 Mixing with Mg at a certain mass ratio, and heat treating in protective atmosphere to obtain Mg 2 Si, removing excessive Mg and MgO impurities by hydrochloric acid, and filtering to obtain the porous Si.
4. A method for preparing a composite material according to claim 3, characterized in that: in the step 1), the biomass comprises at least one of rice hulls, diatomite and corn husks, and the particle size of the biomass is 8-10 micrometers; preferably ball milling for 2-6 h in a ball mill; the heat treatment temperature of the muffle furnace is 800-1000 ℃, and the heat treatment time is 1-3 h; the concentration of the hydrochloric acid is 1-3 mol/L.
5. A method for preparing a composite material according to claim 3, characterized in that: siO in step 2) 2 The mass ratio of Mg to Mg is 0.5-1: 1, preferably 0.5:1; the heat treatment temperature is 600-800 ℃, and the heat treatment time is 8-12 h; the concentration of hydrochloric acid in the step 2) is 1-3 mol/L.
6. The method for preparing a composite material according to claim 1, characterized in that: the conductive fiber network C material is obtained by conducting polymers in an electrostatic spinning heating treatment mode.
7. The method for preparing a composite material according to claim 6, characterized in that: the method comprises the following steps:
(1) Adding the polymer into DMF or a mixture of DMF and PVP according to a certain liquid-solid ratio, and uniformly stirring to obtain a viscous clear liquid A;
(2) Adding porous Si and ferric acetylacetonate or nickel acetate into the solution A according to a certain mass ratio, and uniformly stirring to obtain a viscous brown solution B;
(3) Putting the viscous brown solution B into an electrostatic spinning machine, and carrying out electrostatic spinning under a certain electrostatic voltage and feeding speed to obtain a product C;
(4) Preheating the product C to obtain a product D, and carrying out heat treatment on the product D under a protective atmosphere to obtain a one-dimensional product E;
(5) And putting the product E into hydrochloric acid to remove ferric acetylacetonate or nickel acetate to obtain the conductive fiber network encapsulated biomass porous Si/C composite material.
8. The method for preparing a composite material according to claim 7, characterized in that:
the polymer in step (1) is a high molecular weight organic matter comprising polyvinylpyrrolidone (PVP M) w = 1300000), polyacrylonitrile (PAN M) w = 150000); the liquid-solid ratio in the step (1) is 0.8-1.2;
the mass ratio of the porous Si to the ferric acetylacetonate or the nickel acetate in the step (2) is (8);
setting the electrostatic spinning voltage in the step (3) to be 15-25 kV, and setting the feeding speed to be 0.3-0.6 ml/h;
the preheating treatment temperature in the step (4) is 200-300 ℃, the treatment time is 1-3 h, the protective heat treatment temperature is 700-900 ℃, and the heat treatment time is 2-4 h;
the concentration of hydrochloric acid in the step (5) is 1-3 mol/L.
9. A biomass porous Si/C composite material encapsulated by a conductive fiber network is characterized in that: prepared by the preparation method of any one of claims 1 to 8.
10. Use of the conductive fiber network encapsulated biomass porous Si/C composite of claim 9 in the preparation of battery negative electrode materials.
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