CN111653734A - Ferrosilicon/carbon composite lithium ion battery cathode material and preparation method and application thereof - Google Patents
Ferrosilicon/carbon composite lithium ion battery cathode material and preparation method and application thereof Download PDFInfo
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- CN111653734A CN111653734A CN202010039372.0A CN202010039372A CN111653734A CN 111653734 A CN111653734 A CN 111653734A CN 202010039372 A CN202010039372 A CN 202010039372A CN 111653734 A CN111653734 A CN 111653734A
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- 229910000519 Ferrosilicon Inorganic materials 0.000 title claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 18
- 239000010406 cathode material Substances 0.000 title claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 43
- 239000000956 alloy Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000011858 nanopowder Substances 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000010935 stainless steel Substances 0.000 claims description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 10
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- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
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- 238000003828 vacuum filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 3
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910001021 Ferroalloy Inorganic materials 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 5
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- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910005347 FeSi Inorganic materials 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910018619 Si-Fe Inorganic materials 0.000 description 3
- 229910008289 Si—Fe Inorganic materials 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 238000004154 testing of material Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 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
- H01M4/364—Composites as mixtures
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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
-
- 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
-
- 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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- 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
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention aims to provide a ferrosilicon/carbon composite lithium ion battery cathode material and a preparation method thereof, wherein the ferrosilicon/carbon composite lithium ion battery cathode material is prepared from bulk ferrosilicon (FeSi)x) The preparation method comprises the steps of preparing ferrosilicon alloy nanopowder by adopting a mechanical ball milling method, mixing the ferrosilicon alloy nanopowder with a carbon source, coating silicon material on the carbon source in situ in the reaction process, and calcining to obtain the ferrosilicon and carbon composite material. The method does not use corrosive acid, adopts chemical coating to coat the carbon material, is environment-friendly, has low energy consumption and simple process, and is beneficial to large-scale production.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a preparation method of a lithium ion battery cathode material.
Background
Lithium ion batteries are widely used in electronic devices, optoelectronic devices, and electric vehicles, and with the rapid development of these industries, there is an increasing demand for lithium ion batteries with high energy density and long life. The specific capacity (372 mA.h.g < -1 >) and the rate capability of the commercial graphite negative electrode material can not meet the application requirements of a large power supply. Therefore, the search for high performance negative electrode materials that can replace graphite has become a focus of research. Silicon is considered to be a promising anode material for lithium ion batteries because of its theoretical specific capacity up to 3580mAh/g (Li)3.75Si, formed at room temperature), and has advantages of a suitable intercalation/deintercalation lithium potential (about 0.4V), low reactivity with an electrolyte, good safety, abundant resources in the earth crust, and the like. However, the silicon material may generate huge volume expansion (up to 300%) during charging and discharging, easily cause crushing, pulverization and shedding of the active material, greatly reduce the electrical activity, and show poor cycle stability. In addition, silicon materials have low conductivity and slow charge transport.
Researches show that volume expansion of silicon can be relieved through nanocrystallization, an ion diffusion path is shortened, electrochemical activity of the material is improved, and secondly, because metal generally has the characteristics of high conductivity and high mechanical strength, volume change of the silicon material in the lithium intercalation/deintercalation process can be effectively buffered through synthesis of various silicon-based alloys, and structural stability and conductivity of the material are improved. The ferrosilicon alloy is widely applied to the production of steel industry, casting industry and other industries, the process is mature, and the cost of raw materials is low. The amorphous carbon is used for coating, so that the conductivity of the composite material can be effectively improved, more paths are provided for electron transfer and lithium ion transmission, and the reversible capacity, the rate capability and the cycle performance of the composite material are improved.
The existing preparation method of the ferrosilicon alloy and carbon compound generally comprises the steps of carrying out high-energy ball milling and high-temperature annealing treatment on elementary substance iron and elementary substance silicon to obtain the ferrosilicon alloy, then carrying out ball milling on the ferrosilicon alloy and a carbon source, calcining, and carrying out acid treatment to obtain the compound, wherein the method has the main defects that firstly, hydrochloric acid, sulfuric acid, nitric acid and the like adopted by the method have strong corrosivity and volatility, and environmental pollution is easily caused; secondly, the process is complex, the energy consumption of the carbon coating method is high, and the material is adhered to equipment to cause waste, so that the production cost is high, and the large-scale and commercial application of the carbon coating method is limited.
Disclosure of Invention
The invention aims to provide a ferrosilicon/carbon composite lithium ion battery cathode material and a preparation method thereof, which do not use corrosive acid treatment, adopt chemical coating to coat a carbon material, are environment-friendly, have low energy consumption and simple process, and are beneficial to large-scale production.
The invention is mainly characterized in that bulk ferrosilicon (FeSi) is usedx) The preparation method comprises the steps of preparing ferrosilicon alloy nanopowder by adopting a mechanical ball milling method, mixing the ferrosilicon alloy nanopowder with a carbon source, coating silicon material on the carbon source in situ in the reaction process, and calcining to obtain the ferrosilicon and carbon composite material.
The method provided by the invention comprises the following specific steps:
1) preparation of ferrosilicon alloy nanopowder
Adding the ferrosilicon alloy, the stainless steel balls and absolute ethyl alcohol into a stainless steel ball milling tank for full ball milling to obtain a mixed solution A according to the mass ratio of the ferrosilicon alloy to the stainless steel balls to the absolute ethyl alcohol in a ratio of 1 to (1-20) to (0-1), wherein the mass unit is g and the volume unit is mL; ultrasonically crushing the obtained mixed solution A, and drying to obtain ferrosilicon alloy nano powder;
2) preparation of ferrosilicon and carbon composite
According to the mass ratio of the mass of the ferrosilicon alloy nano powder to the mass of the carbon source of 1: 0.25-4, wherein the mass unit is g, and the volume unit is mL, stirring and mixing the ferrosilicon alloy nano powder, the carbon source and deionized water to obtain a mixed solution B; performing solid-liquid separation on the obtained mixed solution B, collecting solid precipitates, and repeatedly washing the solid precipitates by using deionized water and absolute ethyl alcohol until the filtrate is neutral (pH is 7); and drying the obtained solid precipitate, heating to 400-800 ℃ in an inert protective atmosphere, preserving the heat for 1-6 hours, and taking out to obtain the ferrosilicon and carbon composite material.
Further, the ball milling time in the step (1) is 0.5-6 hours.
Further, the drying condition in the step (1) is drying for 6-24 hours at 50-80 ℃.
Further, the ultrasonic conditions in the step (1) are as follows: ultrasonic power 200W-1200W, pulse gap: 1s-10s, and the ultrasonic time is 0.5-2 h.
Further, the drying in the step (2) is to dry the obtained solid precipitate at 50-80 ℃ for 6-24 h.
Further, the carbon source in step (2) is selected from at least one of dopamine hydrochloride, resorcinol, citric acid, glucose, polyvinyl alcohol, asphalt and the like.
Further, the diameter of the stainless steel ball in the step (1) is 1 mm-20 mm.
Further, the stirring and mixing manner in the step (2) includes magnetic stirring or electric stirring.
Further, the solid-liquid separation in the step (2) is centrifugal separation or vacuum filtration. The rotation speed of centrifugal separation is 3000-10000 r/min, and the vacuum degree during vacuum filtration is 0.85-0.95 MPa.
Further, the inert atmosphere in step (2) comprises nitrogen or argon.
Further, in the step (1), the ferrosilicon alloy is firstly coarsely crushed into small pieces
The invention also provides the composite material prepared by the method, and the composite material can be used as a lithium ion battery cathode material. The nano silicon-iron alloy prepared by the method can relieve the serious volume expansion and contraction brought by silicon in the process of lithium ion intercalation and deintercalation, and the uniform coating of the amorphous carbon can greatly increase the conductivity of the composite and provide more paths for electron transfer and lithium ion transmission, thereby improving the reversible capacity, rate capability and cycle performance of the composite material.
Compared with the prior art, the invention has the following beneficial effects:
1. the method adopts the procedures of mechanical ball milling, stirring and mixing and the like, has simple process and convenient operation, is beneficial to realizing large-scale production, and is convenient to popularize and apply.
2. The lithium ion battery cathode material prepared by the method has the advantages of good conductivity, good electrochemical activity and excellent rate performance, effectively inhibits the volume expansion of silicon in the charging and discharging processes, and improves the cycle performance of the electrode material.
3. The ferrosilicon alloy and carbon composite material prepared by the method has the advantages of small using amount, good dispersibility, uniform coating and the like because the carbon source is used for synthesizing the carbon in situ in the coating process.
4. The method disclosed by the invention can obtain excellent rate performance without using hydrochloric acid, sulfuric acid, nitric acid and the like, is green and environment-friendly, has low energy consumption and low production cost, and is beneficial to large-scale production.
Drawings
FIG. 1 is a 10K magnification of a Scanning Electron Microscope (SEM) of the Si-Fe alloy/carbon composite prepared in example 2;
fig. 2 is a graph of cycling curves at a current density of 200mA/g for composite assembled button cells prepared in examples 1, 2, and 3.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and examples, but it should not be construed that the scope of the above-described subject matter is limited to the examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1
Preparation of ferrosilicon alloy
1) Adding the ferrosilicon alloy, the stainless steel balls and the absolute ethyl alcohol into a stainless steel ball milling tank according to the ratio of the mass (g) of the ferrosilicon alloy (coarse crushed blocks) to the mass (g) of the stainless steel balls to the volume (mL) of the absolute ethyl alcohol of 1: 20: 0.6, and carrying out ball milling for 3 hours to obtain a mixed solution A;
2) putting the mixed solution A into a beaker, carrying out ultrasonic crushing for 2 hours, and drying at 60 ℃ for 12 hours to prepare ferrosilicon alloy nano powder;
example 2:
preparation of ferrosilicon/carbon composite
1) Preparation of ferrosilicon alloy nanopowder
Adding the ferrosilicon alloy, the stainless steel ball and absolute ethyl alcohol into a stainless steel ball milling tank according to the ratio of the mass (g) of the ferrosilicon alloy to the mass (g) of the stainless steel ball to the volume (mL) of the absolute ethyl alcohol of 1: 20: 0.6, and carrying out ball milling for 3 hours to obtain a mixed solution A;
putting the mixed solution A into a beaker, carrying out ultrasonic crushing for 2 hours, and drying at 60 ℃ for 12 hours to prepare ferrosilicon alloy nano powder;
2) preparation of ferrosilicon/carbon composite
Dissolving 0.24225g of tris base in 200mL of deionized water and 20mL of absolute ethyl alcohol, mixing according to the weight ratio of 1: 0.5 of the ferrosilicon alloy to the dopamine hydrochloride, and magnetically stirring for 18h to obtain a mixed solution B;
performing solid-liquid separation on the obtained mixed solution B, collecting solid precipitates, and repeatedly washing the solid precipitates by using deionized water and absolute ethyl alcohol until the filtrate is neutral (pH is 7);
and drying the obtained solid precipitate at 60 ℃ for 12h, heating to 600 ℃ under an inert protective atmosphere, preserving heat for 2h, and taking out to obtain the ferrosilicon/carbon composite.
Example 3
1) Preparation of ferrosilicon alloy nanopowder
Adding the ferrosilicon alloy, the stainless steel balls and the absolute ethyl alcohol into a stainless steel ball milling tank according to the ratio of the mass (g) of the ferrosilicon alloy to the mass (g) of the stainless steel balls to the volume (mL) of the absolute ethyl alcohol of 1: 20: 1, and carrying out ball milling for 6 hours to obtain a mixed solution A;
putting the mixed solution A into a beaker, carrying out ultrasonic crushing for 1h, and drying at the temperature of 60 ℃ for 12 hours to prepare ferrosilicon alloy nano powder;
2) preparation of ferrosilicon/carbon composite
According to the mass (g) of the ferrosilicon alloy to the mass (g) of the resorcinol: mass of CTAB (g): mass of formaldehyde (g): the volume ratio of ammonia water (mL) is 1: 4: 0.36: 10, and mixed solution B is obtained by magnetic stirring;
performing solid-liquid separation on the obtained mixed solution B, collecting solid precipitates, and repeatedly washing the solid precipitates by using deionized water and absolute ethyl alcohol until the filtrate is neutral (pH is 7);
and drying the obtained solid precipitate at 60 ℃ for 12h, heating to 800 ℃ under an inert protective atmosphere, preserving heat for 6h, and taking out to obtain the ferrosilicon/carbon composite.
Testing of Material Properties
The composite material of silicon-iron alloy and carbon prepared in example 1 was observed by a scanning electron microscope at 10K, and the results are shown in FIG. 1. A button cell was assembled with commercial silicon (100nm), silicon-iron alloy (example 1), and silicon-iron alloy/carbon composite (example 2) as active materials, respectively: according to the mass ratio of active substances to carbon black to sodium alginate of 7: 2: 1, and mixing. And (3) uniformly coating the fully ground slurry on a copper foil current collector, and performing vacuum drying at 80 ℃ for 12 h. And (3) preparing the prepared copper foil electrode plate into a circular electrode plate with the diameter of l.4cm for later use. A button cell is assembled by taking a composite electrode as a positive electrode, a lithium sheet as a negative electrode (reference electrode) and a commercial lmol/L LiPF6/EC + DMC + DEC solution as an electrolyte in a glove box filled with argon in sequence. The assembled battery was subjected to a conventional constant current charge and discharge experiment, and the result is shown in fig. 2.
As shown in FIG. 1, the grain size of the Si-Fe alloy is in the nanometer range, and the amorphous carbon is coated on the surface of the Si-Fe alloy, so that the surface becomes very smooth.
As can be seen from fig. 2, the initial capacity of the ferrosilicon alloy is not high but the cycle performance is significantly improved compared to commercial silicon powder, indicating that the alloy phase effectively relieves the volume expansion of silicon. Compared with the ferrosilicon alloy, the cycle performance of the ferrosilicon alloy/carbon composite prepared by the invention is further improved.
Claims (10)
1. A preparation method of a ferrosilicon/carbon composite lithium ion battery cathode material is characterized by comprising the following steps:
1) preparation of ferrosilicon alloy nanopowder
Adding the ferrosilicon alloy, the stainless steel balls and absolute ethyl alcohol into a stainless steel ball milling tank for full ball milling to obtain a mixed solution A according to the mass ratio of the ferrosilicon alloy to the stainless steel balls to the absolute ethyl alcohol in a ratio of 1 to (1-20) to (0-1), wherein the mass unit is g and the volume unit is mL; ultrasonically crushing the obtained mixed solution A, and drying to obtain ferrosilicon alloy nano powder;
2) preparation of ferrosilicon and carbon composite
According to the mass ratio of the mass of the ferrosilicon alloy nano powder to the mass of the carbon source of 1: 0.25-4, wherein the mass unit is g, and the volume unit is mL, stirring and mixing the ferrosilicon alloy nano powder, the carbon source and deionized water to obtain a mixed solution B; performing solid-liquid separation on the obtained mixed solution B, collecting solid precipitates, and repeatedly washing the solid precipitates by using deionized water and absolute ethyl alcohol until the filtrate is neutral (pH is 7); and drying the obtained solid precipitate, heating to 400-800 ℃ in an inert protective atmosphere, preserving the heat for 1-6 hours, and taking out to obtain the ferrosilicon and carbon composite material.
2. The method according to claim 1, wherein the ball milling time in step (1) is 0.5 to 6 hours.
3. The method according to claim 1, wherein the drying condition in the step (1) is drying at 50 ℃ to 80 ℃ for 6 to 24 hours.
4. The method according to claim 1, wherein the ultrasonic conditions in step (1) are as follows: ultrasonic power 200W-1200W, pulse gap: 1s-10s, and the ultrasonic time is 0.5-2 h.
5. The method according to claim 1, wherein the drying in the step (2) is drying the obtained solid precipitate at 50-80 ℃ for 6-24 h.
6. The method according to claim 1, wherein the carbon source in step (2) is at least one selected from dopamine hydrochloride, resorcinol, citric acid, glucose, polyvinyl alcohol, asphalt, etc.
7. The method according to claim 1, wherein the diameter of the stainless steel ball in step (1) is 1mm to 20 mm.
8. The method according to claim 1, wherein the solid-liquid separation in step (2) is performed by centrifugal separation or vacuum filtration. The rotation speed of centrifugal separation is 3000-10000 r/min, and the vacuum degree during vacuum filtration is 0.85-0.95 MPa.
9. The ferroalloy/carbon composite lithium ion battery negative electrode material prepared by the method of any one of claims 1 to 8.
10. Use of the material according to claim 9 as a negative electrode material for lithium ion batteries.
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