CN110993899B - Nano-copper particle modified micron-sized porous silicon composite material and preparation method thereof - Google Patents
Nano-copper particle modified micron-sized porous silicon composite material and preparation method thereof Download PDFInfo
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- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 88
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 72
- 239000010949 copper Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000002245 particle Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 72
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 37
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005530 etching Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000002210 silicon-based material Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 33
- 239000011787 zinc oxide Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000011065 in-situ storage Methods 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 16
- 150000001879 copper Chemical class 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 9
- 239000008139 complexing agent Substances 0.000 claims description 9
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 5
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 59
- 239000002994 raw material Substances 0.000 abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 6
- 238000003486 chemical etching Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000001360 synchronised effect Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 54
- 239000000243 solution Substances 0.000 description 36
- 230000007935 neutral effect Effects 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 17
- 230000001276 controlling effect Effects 0.000 description 16
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000002905 metal composite material Substances 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018067 Cu3Si Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000001476 sodium potassium tartrate Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910001845 yogo sapphire 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
- H01M4/38—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
- 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
- H01M4/362—Composites
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- H—ELECTRICITY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a nano-copper particle modified micron-sized porous silicon composite structure material and a preparation method thereof. The synthesis method comprises the steps of firstly, forming a zinc particle modified micron-sized porous silicon structure by one-step alkaline reduction/etching of commercial silicon-aluminum alloy, chemically replacing copper nanoparticles on the basis, and then carrying out heat treatment and secondary acid etching treatment to obtain the nanoscale copper particle modified micron-sized porous silicon composite material. The method is different from the common acid chemical etching method at present, particularly utilizes the higher reducibility of an aluminum component in an alkaline environment to carry out synchronous reduction/etching, has higher universality and high efficiency, can finish large-scale preparation production in a short time, has low price of used raw materials, is economic and environment-friendly, has higher atom utilization rate, better improves the conductivity and lithium battery performance of the silicon material, and has extremely wide application prospect and commercial value.
Description
Technical Field
The invention belongs to the field of inorganic nano composite materials, and relates to a method for preparing a copper nano particle in-situ modified micron-sized porous silicon structure composite material by using a silicon-aluminum alloy as a raw material, in particular to a method for preparing a porous silicon-based metal composite material, which is innovative, simple and convenient to operate, green and environment-friendly.
Background
With the national subsidy policy on new energy in 2020 comprehensive grade withdrawal, the pure electric vehicle with high endurance mileage has greater competitive advantage in the future market. In order to increase the capacity of lithium ion batteries, more and more scientific researches and enterprise researches are focusing on a new generation of silicon which is the most potential anode material. Compared with the traditional commercial graphite anode material (342mAh g)-1) Silicon materials have the highest theoretical capacity known at present (4200 mAhg)-1) Lower charging voltage. However, the silicon negative electrode material of the alloy lithium storage mechanism is accompanied by huge volume expansion in the charging and discharging processes, which can cause the shedding of the active material silicon and the current collector copper foil and the pulverization of the silicon material itself; silicon materials are used as semiconductors, and have the limitation of poor conductivity. At present, the more common methods for improving the lithium storage performance of porous silicon include outer carbon coating and internal metal doping. Although the silicon-carbon composite material has better cycle stability, the first coulombic efficiency of the silicon-carbon composite material is always lower. The silicon-based metal composite materials are generally divided into two types, the first type is that silicon materials are compounded with lithium-storage-free active metals and metal compound materials, such as Cu, Ag and Cu3Si,Ni,Al2O3The metal components can not only improve the overall conductivity of the material, but also relieve the stress in the volume change process of the material in the lithium intercalation/lithium deintercalation process; the second type is that silicon materials are compounded with lithium storage active metals and metal compounds, including Ge, Sn, Sb, ZnO and the like, and because lithium insertion/lithium removal potentials of different active materials are different, the silicon materials can be used as buffer layers in the volume expansion process, so that the stability of the whole structure of the material is favorably maintained, and theoretical calculation shows that the compound of various active metals has higher theoretical capacity and better cycling stability than a single lithium storage active component.
At present, the method for preparing the silicon-based metal composite material is mainly an alloy removing method, and comprises an acid-base etching method and a vacuum evaporation method. The silicon material with a porous structure can be obtained by removing active metal components (metals capable of reacting with acid or alkali, such as Al, Mg and the like) or low-melting-point metals (such as Zn, Mg and the like), and then introducing new metal components by an electroless plating or vapor deposition method on the basis of the silicon material to form the silicon-based metal composite material. The methods not only have complex preparation process and harsh reaction conditions (the porous silicon surface needs to be treated for seed crystal growth or high-temperature vacuum evaporation), but also have the autocatalysis effect of metal particles generated by new chemical plating, so that the reaction is easy to be uneven and the metal is easy to form a separate phase. According to the invention, the silicon-aluminum alloy material is etched/reduced by a one-step method, the zinc nanoparticles can be replaced on the surface and the inner in situ of the silicon-aluminum alloy microspheres, the copper nanoparticles are regulated and controlled by a replacement reaction on the basis, and then heat treatment and secondary acid etching are carried out to obtain the copper nanoparticle in-situ modified porous silicon composite material, so that the method for preparing the silicon-based metal composite material is simple to operate and high-efficiency.
Disclosure of Invention
The invention aims to provide a simple and efficient preparation method of a copper nanoparticle modified micron-sized porous silicon composite material and a preparation method thereof. The material is characterized in that copper nanoparticles are uniformly distributed on the surface and inside of a micron-sized porous silicon framework, the micron-sized porous silicon is formed by etching a silicon-aluminum alloy through a two-step method, the copper nanoparticles are introduced by secondary replacement of zinc nanoparticles deposited by aluminum alkaline replacement, and the copper nanoparticles are embedded inside the silicon framework and are formed by metal diffusion in the heat treatment process.
The technical scheme of the invention is as follows:
the preparation method of the nano-copper particle in-situ modified micron-sized porous silicon composite structure material comprises the following steps:
(1) dispersing alkali and zinc oxide in deionized water to obtain a solution A;
(2) dispersing a copper salt and a copper salt complexing agent in deionized water to obtain a solution B;
(3) adding silicon-aluminum alloy powder into the solution A for reaction to obtain a porous silicon material modified by zinc nanoparticles after the reaction is finished;
(4) adding the obtained porous silicon material modified by the zinc nanoparticles into the solution B, and obtaining a porous silicon composite material modified by the copper nanoparticles after the reaction is finished;
(5) taking the porous silicon composite material obtained in the step (4) as a precursor, and carrying out heat treatment in the atmosphere of mixing hydrogen and inert gas;
(6) and (5) carrying out acid etching on the powder material obtained in the step (5), and washing and drying to obtain the copper nanoparticle in-situ modified micron-sized porous silicon composite material.
As a preferred embodiment of the present invention, the molar ratio of the alkali to the zinc oxide is in the range of 2:1 to 7: 1; further preferably 5: 1; in the step (1), the base is added in an amount such that OH in the solution A is present at the beginning of the reaction-The concentration ratio of (B) is in the range of 1.0 to 7.0M, more preferably 1.4M.
As a preferable scheme of the invention, the copper salt is one or more of copper chloride, copper sulfate and copper nitrate; the copper salt complexing agent is selected from one or more of disodium ethylene diamine tetraacetate, potassium sodium tartrate and sodium citrate; the molar ratio of the copper salt to the copper salt complexing agent is 1:1 to 1:5, and is more preferably 1: 2.
as a preferable scheme of the invention, the content range of silicon in the silicon-aluminum alloy powder is 5-50% by mass; the grain diameter of the silicon-aluminum alloy powder is 0.5-10 microns, and the shape is spherical; the ratio of the amount of aluminum component in the silicon aluminum alloy powder to the amount of hydroxide ion species in solution a ranges from 1/3 to 2/3; the reaction temperature of the step (3) is room temperature, and the reaction time is 5-10 min.
As a preferable scheme of the invention, the reaction temperature of the step (4) is normal temperature, and the reaction time is 10-60 min; the mass ratio of the porous silicon material modified by the zinc nanoparticles to the solution B is 1:800-1: 200.
As a preferable scheme of the invention, in the step (5), the volume percentage of the hydrogen in the mixed atmosphere of the hydrogen and the inert gas is 5-10%, the temperature range of the heat treatment is 250-500 ℃, the time is 2.0-10.0h, and the heating rate is 2-3 ℃ for min-1More preferably, the temperature of the heat treatment is 300 ℃, the time is 2.0h, and the heating rate is 3 ℃ for min-1。
According to the preferable scheme of the invention, in the micron-sized porous silicon composite structure material modified by the nano-copper particles in situ, the copper nanoparticles are uniformly distributed on the surface and inside of the micron-sized porous silicon skeleton, and the particle size of the copper nanoparticles is 5-20 nm.
According to the preparation method of the copper nanoparticle modified micron-sized porous silicon composite material, silicon-aluminum alloy powder, an alkali solution, zinc oxide, a copper salt and a copper salt complexing agent are used as raw materials, deionized water is used as a reaction solvent, a precursor silicon-based metal compound of the material is obtained through chemical etching/replacement, and then the copper nanoparticle modified micron-sized porous silicon composite material is finally obtained through heat treatment and secondary hydrochloric acid etching and drying. The preparation process mainly comprises the following stages:
1. etching/replacement of silicon-aluminum alloy under alkaline condition
Under alkaline conditions, Al has lower reduction potential and higher reactivity and can react with OH in solution-And ZnO2 2-And simultaneously reacting to form a porous silicon structure modified by zinc particles. In the reaction process, as zinc is difficult to dissolve in alkaline solution, the zinc can be deposited on the shell of the silicon-aluminum ball in situ, and the aluminum component in the silicon-aluminum alloy continuously reacts to form a porous structure and a zinc deposition interface along with the continuous inward proceeding of the etching reaction, so that the deposition of the zinc in the silicon framework is more uniform.
2. Complexing agent for regulating and controlling displacement process of nano copper particles
By complexing agent EDTA with cation Zn2+And Cu2+The chelation can change the reaction path of the zinc nanoparticles for replacing the copper nanoparticles, and avoid the agglomeration of the copper nanoparticles, thereby obtaining the copper nanoparticles with smaller particle size.
3. Heat treatment promotes metal reduction and diffusion
By subjecting the obtained silicon-based metal material to Ar/H2(5%) heat treatment, possibly by means of hydrogen reduction, of the copper nanoparticles produced; the copper nanoparticles can form an alloy with zinc, and the alloy and the diffusion of the copper nanoparticles in a silicon skeleton structure are facilitated, so that a novel structure that the copper nanoparticles are embedded in the silicon skeleton is formed; meanwhile, the final acid etching can further reduce the silicon skeletonThe size of the silicon-aluminum alloy is increased, a richer pore channel structure is obtained, and the micron-sized porous silicon modified by the copper nanoparticles keeps the original spherical shape of the silicon-aluminum alloy.
The invention has the advantages that:
(1) according to the invention, a micron-sized porous silicon material coated with zinc particles is obtained by utilizing commercial silicon-aluminum alloy etching/reduction, and then the porous silicon composite material modified by copper nanoparticles is obtained by regulating and controlling copper replacement reaction, heat treatment and hydrochloric acid etching. Compared with the traditional chemical plating method, the method has the advantages of simpler operation flow, more uniform and controllable reaction, capability of completing large-scale preparation production in a short time, low price of used raw materials, economy and environmental protection.
(2) The prepared copper nanoparticle modified porous silicon negative electrode material maintains the original micron spherical appearance, wherein the copper nanoparticles are uniformly distributed on the surface and inside of the porous silicon skeleton, and the particle size is 10-20 nm.
In the synthesis strategy of the invention, aluminum metal in the silicon-aluminum alloy is fully and effectively utilized for alkaline replacement and etching, the atom utilization rate is improved, and the whole preparation process is environment-friendly and safe and conforms to the development concept of green chemistry. Meanwhile, the process is based on the basic principle of the displacement reaction, has strong universality and applicability, and provides a method for industrially applying the copper nano-modified micron-sized porous silicon composite material in the future. The introduced copper nanoparticles can well improve the limitation of poor conductivity of the porous silicon material and relieve the cycling stability of the porous silicon material in the charging and discharging processes, so that the silicon-based metal composite material is very hopefully applied to the next generation of new energy commercial lithium ion battery.
Drawings
FIG. 1 is a scanning electron microscope SEM (a), (b), a transmission electron microscope TEM (c), (d) and an element scanning (e) for forming zinc nanoparticle modified micro-scale porous silicon by alkaline replacement/etching.
Fig. 2 is an X-ray powder diffraction pattern XRD of micron-sized porous silicon modified by alkaline substitution/etching to form zinc nanoparticles.
FIG. 3 is a scanning electron microscope SEM (a), (b), (c), (d) and element scanning (e) of the micron-sized porous silicon composite material modified by the copper nanoparticles.
FIG. 4 is a TEM image of the micron-sized porous silicon composite material modified by copper nanoparticles.
Fig. 5 is an X-ray powder diffraction pattern XRD of the substituted copper nanoparticle porous silicon precursor after heat treatment and acid etching.
Detailed Description
In order to explain and illustrate the invention more specifically, the following exemplary experimental protocol cases are listed, but the invention is not limited to these embodiments.
The structure and the morphology of the micron-sized porous silicon composite material and the precursor modified by the copper nano particles in situ are mainly characterized by means such as an X-ray powder diffractometer (XRD), a Scanning Electron Microscope (SEM), a Transmission Electron Microscope (TEM) and the like,
example 1
The method for preparing the copper nano particle in-situ modified micron-sized porous silicon by taking the silicon-aluminum alloy, the potassium hydroxide, the zinc oxide, the copper sulfate pentahydrate and the disodium ethylene diamine tetraacetate as raw materials comprises the following specific steps:
(1) weighing silicon-aluminum alloy (wherein the weight percentage of Si is 12%) powder (1.0g), potassium hydroxide (56mmol), zinc oxide (1.6mmol), copper sulfate pentahydrate (1mmol) and disodium ethylenediamine tetraacetic acid (2 mmol);
(2) potassium hydroxide and zinc oxide were dispersed in 40mL H2In the presence of oxygen in the atmosphere of O,
(3) dispersing copper sulfate pentahydrate and disodium edetate in 20mLH2In O, forming a blue transparent solution B;
(4) adding 1.0g of silicon-aluminum powder into the solution A, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and re-dispersing in 20mL of H2Obtaining solution C in O; the morphology structure is shown in fig. 1, and it can be seen that zinc nanoparticles are mainly deposited on the surface and inside of the micron-sized silicon skeleton, and the inside has rich pore channel structures; the phase change can be analyzed by XRD (figure)2) It can be seen that the peak of elemental aluminum almost disappears and a distinct peak of elemental zinc particles appears.
(5) Adding the obtained zinc nanoparticle modified porous silicon mixed solution C into the solution B, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain porous silicon with copper nanoparticles introduced;
(6) taking the porous silicon composite material obtained in the step (5) as a precursor, and performing Ar/H2(5％H2) Heating to 300 ℃ at a speed of 3 ℃/min in a tube furnace under the atmosphere and keeping for 2h for heat treatment;
(7) adding the powder material obtained in the step (6) into 0.5M hydrochloric acid for etching for 12h, washing to be neutral and drying to obtain the micron-sized porous silicon composite material modified by the copper nanoparticles, wherein the morphology structure of the micron-sized porous silicon composite material is shown in fig. 3 and 4, the copper nanoparticles are uniformly distributed in the porous silicon composite material, the micron-sized porous silicon composite material comprises the surface and the embedded inner part of a silicon framework, and the particle size of the micron-sized porous silicon composite material is 5-20 nm; the phase change of the copper element can be analyzed by XRD (figure 5), and the copper element nanoparticles formed by replacement have smaller size and are beneficial to being diffused into the silicon skeleton structure in the heat treatment process; diffraction peaks for elemental copper were visible after acid etching.
Example 2
The method for preparing the copper nano particle in-situ modified micron-sized porous silicon by taking the silicon-aluminum alloy, the potassium hydroxide, the zinc oxide, the copper sulfate pentahydrate and the disodium ethylene diamine tetraacetate as raw materials comprises the following specific steps:
(1) weighing silicon-aluminum alloy (wherein Si accounts for 25 wt%) powder (1.0g), potassium hydroxide (56mmol), zinc oxide (1.6mmol), copper sulfate pentahydrate (1mmol) and disodium ethylenediamine tetraacetic acid (2 mmol);
(2) potassium hydroxide and zinc oxide were dispersed in 40mL H2In the presence of oxygen in the atmosphere of O,
(3) dispersing copper sulfate pentahydrate and disodium edetate in 20mLH2In O, forming a blue transparent solution B;
(4) adding 1.0g of silicon-aluminum powder into the solution A, controlling the reaction time for 5min, and then performing reaction at 5000r/min by using a centrifugal machineCentrifuging for 5min, washing with deionized water and anhydrous ethanol to neutrality, and re-dispersing in 20mL H2Obtaining solution C in O;
(5) adding the obtained zinc nanoparticle modified porous silicon mixed solution C into the solution B, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain porous silicon with copper nanoparticles introduced;
(6) taking the porous silicon composite material obtained in the step (5) as a precursor, and performing Ar/H2(5％H2) Heating to 300 ℃ at a speed of 3 ℃/min in a tube furnace under the atmosphere and keeping for 2h for heat treatment;
(7) and (4) adding the powder material obtained in the step (6) into 0.5M hydrochloric acid for etching for 12h, washing to be neutral, and drying to obtain the micron-sized porous silicon composite material modified by the copper nanoparticles.
Example 3
The method for preparing the copper nano particle in-situ modified micron-sized porous silicon by taking the silicon-aluminum alloy, the potassium hydroxide, the zinc oxide, the copper sulfate pentahydrate and the disodium ethylene diamine tetraacetate as raw materials comprises the following specific steps:
(1) weighing silicon-aluminum alloy (wherein the weight percentage of Si is 40%) powder (1.0g), potassium hydroxide (56mmol), zinc oxide (1.6mmol), copper sulfate pentahydrate (1mmol) and disodium ethylene diamine tetraacetate (2 mmol);
(2) potassium hydroxide and zinc oxide were dispersed in 40mL H2In the presence of oxygen in the atmosphere of O,
(3) dispersing copper sulfate pentahydrate and disodium edetate in 20mLH2In O, forming a blue transparent solution B;
(4) adding 1.0g of silicon-aluminum powder into the solution A, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and re-dispersing in 20mL of H2Obtaining solution C in O;
(5) adding the obtained zinc nanoparticle modified porous silicon mixed solution C into the solution B, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain porous silicon with copper nanoparticles introduced;
(6) taking the porous silicon composite material obtained in the step (5) as a precursor, and performing Ar/H2(5％H2) Heating to 300 ℃ at a speed of 3 ℃/min in a tube furnace under the atmosphere and keeping for 2h for heat treatment;
(7) and (4) adding the powder material obtained in the step (6) into 0.5M hydrochloric acid for etching for 12h, washing to be neutral, and drying to obtain the micron-sized porous silicon composite material modified by the copper nanoparticles.
Example 4
The method for preparing the copper nano particle in-situ modified micron-sized porous silicon by taking silicon-aluminum alloy, potassium hydroxide, zinc oxide, copper chloride and potassium sodium tartrate as raw materials comprises the following specific steps:
(1) weighing silicon-aluminum alloy (wherein the weight percentage of Si is 12%) powder (1.0g), potassium hydroxide (56mmol), zinc oxide (1.6mmol), copper chloride (1mmol) and potassium sodium tartrate (2 mmol);
(2) potassium hydroxide and zinc oxide were dispersed in 40mL H2In the presence of oxygen in the atmosphere of O,
(3) dispersing copper chloride and sodium potassium tartrate in 20mLH2In O, forming a blue transparent solution B;
(4) adding 1.0g of silicon-aluminum powder into the solution A, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and re-dispersing in 20mL of H2Obtaining solution C in O;
(5) adding the obtained zinc nanoparticle modified porous silicon mixed solution C into the solution B, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain porous silicon with copper nanoparticles introduced;
(6) taking the porous silicon composite material obtained in the step (5) as a precursor, and performing Ar/H2(5％H2) Heating to 300 ℃ at a speed of 3 ℃/min in a tube furnace under the atmosphere and keeping for 2h for heat treatment;
(7) and (4) adding the powder material obtained in the step (6) into 0.5M hydrochloric acid for etching for 12h, washing to be neutral, and drying to obtain the micron-sized porous silicon composite material modified by the copper nanoparticles.
Example 5
The method for preparing the copper nano particle in-situ modified micron-sized porous silicon by taking the silicon-aluminum alloy, the potassium hydroxide, the zinc oxide, the copper nitrate and the ethylene diamine tetraacetic acid as raw materials comprises the following specific steps:
(1) weighing silicon-aluminum alloy (wherein the weight percentage of Si is 12%) powder (1.0g), potassium hydroxide (56mmol), zinc oxide (1.6mmol), copper nitrate (1mmol) and disodium ethylene diamine tetraacetate (2 mmol);
(2) potassium hydroxide and zinc oxide were dispersed in 40mL H2In the presence of oxygen in the atmosphere of O,
(3) dispersing copper nitrate and disodium ethylene diamine tetraacetate in 20mLH2In O, forming a blue transparent solution B;
(4) adding 1.0g of silicon-aluminum powder into the solution A, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and re-dispersing in 20mL of H2Obtaining solution C in O;
(5) adding the obtained zinc nanoparticle modified porous silicon mixed solution C into the solution B, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain porous silicon with copper nanoparticles introduced;
(6) taking the porous silicon composite material obtained in the step (5) as a precursor, and performing Ar/H2(5％H2) Heating to 300 ℃ at a speed of 3 ℃/min in a tube furnace under the atmosphere and keeping for 2h for heat treatment;
(7) and (4) adding the powder material obtained in the step (6) into 0.5M hydrochloric acid for etching for 12h, washing to be neutral, and drying to obtain the micron-sized porous silicon composite material modified by the copper nanoparticles.
Example 6
The method for preparing the copper nano particle in-situ modified micron-sized porous silicon by taking the silicon-aluminum alloy, the sodium hydroxide, the zinc oxide, the copper sulfate pentahydrate and the disodium ethylene diamine tetraacetate as raw materials comprises the following specific steps:
(1) weighing silicon-aluminum alloy (wherein the weight percentage of Si is 12%) powder (1.0g), sodium hydroxide (56mmol), zinc oxide (1.6mmol), copper sulfate pentahydrate (1mmol) and disodium ethylenediamine tetraacetic acid (2 mmol);
(2) sodium hydroxide and zinc oxide were dispersed in 40mL H2In the presence of oxygen in the atmosphere of O,
(3) dispersing copper sulfate pentahydrate and disodium edetate in 20mLH2In O, forming a blue transparent solution B;
(4) adding 1.0g of silicon-aluminum powder into the solution A, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and re-dispersing in 20mL of H2Obtaining solution C in O;
(5) adding the obtained zinc nanoparticle modified porous silicon mixed solution C into the solution B, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain porous silicon with copper nanoparticles introduced;
(6) taking the porous silicon composite material obtained in the step (5) as a precursor, and performing Ar/H2(5％H2) Heating to 300 ℃ at a speed of 3 ℃/min in a tube furnace under the atmosphere and keeping for 2h for heat treatment;
(7) and (4) adding the powder material obtained in the step (6) into 0.5M hydrochloric acid for etching for 12h, washing to be neutral, and drying to obtain the micron-sized porous silicon composite material modified by the copper nanoparticles.
Example 7
The method for preparing the copper nano particle in-situ modified micron-sized porous silicon by taking the silicon-aluminum alloy, the potassium hydroxide, the zinc oxide, the copper sulfate pentahydrate and the sodium citrate as raw materials comprises the following specific steps:
(1) weighing silicon-aluminum alloy (wherein the weight percentage of Si is 12%) powder (1.0g), potassium hydroxide (56mmol), zinc oxide (1.6mmol), copper sulfate pentahydrate (1mmol) and sodium citrate (2 mmol);
(2) potassium hydroxide and zinc oxide were dispersed in 40mL H2In the presence of oxygen in the atmosphere of O,
(3) dispersing copper sulfate pentahydrate and sodium citrate in 20mLH2In O, forming a blue transparent solution B;
(4) adding 1.0g of silicon-aluminum powder into the solution A, controlling the reaction time for 5min, then centrifuging for 5min at 5000r/min by using a centrifuge, and usingWashed to neutrality with deionized water and absolute ethanol, and redispersed in 20mL of H2Obtaining solution C in O;
(5) adding the obtained zinc nanoparticle modified porous silicon mixed solution C into the solution B, controlling the reaction time for 5min, centrifuging for 5min at 5000r/min by using a centrifuge, washing to be neutral by using deionized water and absolute ethyl alcohol, and drying at 60 ℃ to obtain porous silicon with copper nanoparticles introduced;
(6) taking the porous silicon composite material obtained in the step (5) as a precursor, and performing Ar/H2(5％H2) Heating to 300 ℃ at a speed of 3 ℃/min in a tube furnace under the atmosphere and keeping for 2h for heat treatment;
(7) and (4) adding the powder material obtained in the step (6) into 0.5M hydrochloric acid for etching for 12h, washing to be neutral, and drying to obtain the micron-sized porous silicon composite material modified by the copper nanoparticles.
Claims (8)
1. A preparation method of a nano-copper particle modified micron-sized porous silicon composite structure material is characterized by comprising the following steps:
(1) dispersing alkali and zinc oxide in deionized water to obtain a solution A;
(2) dispersing a copper salt and a copper salt complexing agent in deionized water to obtain a solution B;
(3) adding silicon-aluminum alloy powder into the solution A for reaction to obtain a porous silicon material modified by zinc nanoparticles after the reaction is finished;
(4) adding the obtained porous silicon material modified by the zinc nanoparticles into the solution B, and obtaining a porous silicon composite material modified by the introduced nano-copper particles after the reaction is finished;
(5) taking the porous silicon composite material obtained in the step (4) as a precursor, and carrying out heat treatment in the atmosphere of mixing hydrogen and inert gas;
(6) and (5) performing acid etching on the powder material obtained in the step (5), and washing and drying to obtain the nano-copper particle in-situ modified micron-sized porous silicon composite material.
2. The process according to claim 1, whereinCharacterized in that the molar ratio of the base to the zinc oxide is in the range of 2:1 to 7: 1; in the step (1), the base is added in an amount such that OH in the solution A is present at the beginning of the reaction-The concentration of (A) is in the range of 1.0-7.0M.
3. The method according to claim 1, wherein the copper salt is one or more selected from copper chloride, copper sulfate and copper nitrate; the copper salt complexing agent is selected from one or more of disodium ethylene diamine tetraacetate, potassium sodium tartrate and sodium citrate; the molar ratio of the copper salt to the copper salt complexing agent is 1:1 to 1: 5.
4. The method according to claim 1, wherein the silicon-aluminum alloy powder contains silicon in an amount ranging from 5 to 50% by mass; the grain diameter of the silicon-aluminum alloy powder is 0.5-10 microns, and the shape is spherical; the ratio of the amount of aluminum component in the silicon aluminum alloy powder to the amount of hydroxide ion species in solution a ranges from 1/3 to 2/3; the reaction temperature of the step (3) is room temperature, and the reaction time is 5-10 min.
5. The preparation method according to claim 1, wherein the reaction temperature in the step (4) is normal temperature, and the reaction time is 10-60 min; the mass ratio of the porous silicon material modified by the zinc nanoparticles to the solution B is 1:800-1: 200.
6. The method as set forth in claim 1, wherein in the step (5), the volume percentage of hydrogen in the mixed atmosphere of hydrogen and inert gas is 5-10%, and the temperature range of the heat treatment is 250-oC, the time is 2.0 to 10.0 hours, and the heating rate is 2 to 3oC min-1。
7. The micron-sized porous silicon composite structure material modified by the nano-copper particles prepared by the method in claim 1.
8. The nano-copper particle modified micron-sized porous silicon composite structure material according to claim 7, wherein in the composite structure material, nano-copper particles are uniformly distributed on the surface and inside of a micron-sized porous silicon skeleton, and the particle size of the nano-copper particles is 5-20 nm.
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