CN102703748B - Preparation method of nanometer porous copper tin alloy - Google Patents
Preparation method of nanometer porous copper tin alloy Download PDFInfo
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- CN102703748B CN102703748B CN 201210233788 CN201210233788A CN102703748B CN 102703748 B CN102703748 B CN 102703748B CN 201210233788 CN201210233788 CN 201210233788 CN 201210233788 A CN201210233788 A CN 201210233788A CN 102703748 B CN102703748 B CN 102703748B
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Abstract
The invention belongs to the field of nanometer metal material preparation and particularly relates to a preparation method of nanometer porous copper tin alloy. The method includes the following steps: first weighing pure magnesium, copper and tin according to proportion, heating the metals to the molten state under the protection of a covering agent and casting the metals into an alloy ingot; then preparing an alloy strip belt through the belt throwing process; and finally conducting corrosion processing in acid solution and selectively removing magnesium in the strip belt to obtain the nanometer porous copper tin alloy material. The method is simple, controllable, low in cost and capable of being produced in batch. Prepared nanometer porous copper tin alloy has a three-dimensional double-continuous nanometer-size hole structure. The size of a hole is 20-150 nanometers, and the alloy is a potential lithium ion battery cathode material.
Description
Technical field
The invention belongs to the nano metal material preparation field, relate in particular to a kind of preparation method of nano porous copper tin alloy material.
Background technology
Along with the development of electronic industry, seek and to have high-energy-density, the fast charging and discharging ability, high security and cheaply electrochemical cell become the main flow of research.In numerous electrochemical cells, lithium ion battery because of its high-voltage, heavy body, have extended cycle life, distinguishing feature that safety performance is good, showed wide application prospect and potential great economic benefit in many-sides such as portable electric appts, electromobile, space technology, national defense industry.Since lithium ion battery was born, the relevant negative material of research mainly contained following several: graphitized carbon material, amorphous carbon material, nitride, silica-base material, tin-based material, novel alloy, nano-oxide etc.Wherein tin-based material is a kind of very promising lithium ion battery negative material.
Tin and oxide compound thereof as negative material because of its high building coverage, high-energy-density and preferably electroconductibility obtained extensive concern, but in the charge and discharge process of battery, what the serious mechanical stress that the expansion of tin negative pole and shrinkage phenomenon cause had greatly limited battery discharges and recharges number of times and stability.For solving this drawback, mainly proposed at present following three kinds of ways: (1) uses Cu
6Sn
5Deng tin-based alloy; (2) tin-based material with nano-scale is dispersed on the carbon base body; (3) make up core-shell nano structure tin-based material or adopt hollow carbon covered stannum rice grain.Under comparing, first method is the most simple and feasible, has obtained a large amount of research and practices.
In recent years, the preparation method about gunmetal is in the news in a large number, relates generally to chemical reduction method (W.J.Cui, F.Wang, J.Wang, H.J.Liu, C.X.Wang, Y.Y Xia, J.Power Sources, 2001,196:3633-3639), sputtering method (Y.S.Lina, J.G.Duh, H.S.Sheu, J.Alloy.Compd, 2011,509:123-127), electrodip process (X.Y.Fan, Q.C.Zhuang, G.Z.Wei, L.Huang, Q.F.Dong, S.G.Sun, JAppl.Electrochem, 2009,39:1323-1330), means of electron beam deposition (R.Z.Hu, M.Q.Zeng, M.Zhu, Electrochim.Acta, 2009,54:2843-2850) etc., above method is all prepared gunmetal or the gunmetal/tin composite material of nanoscale, but equal complicated operations, can't volume production, and wayward alloy proportion, be unfavorable for industrial applying.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, the preparation method of the nanoporous gunmetal that a kind of cost is low, technique simple, be produced on a large scale is provided.
The present invention is achieved in the following ways:
A kind of preparation method of nanoporous gunmetal is characterized in that may further comprise the steps:
(1) press magnesium 50-90%, copper 5-35%, all the other take by weighing starting material for the atomic percent of tin;
(2) load weighted magnesium is put into quartz crucible, and at magnesium covering last layer magnesium alloy covering agent, then resistance furnace temperature is adjusted to 750-800 ℃, treat that magnesium is melted into molten state, take out crucible, again add an amount of magnesium alloy covering agent, add simultaneously the copper of load weighted certain proportioning, crucible is put back to resistance furnace; Through 15-20 minute, treat that copper incorporates after the magnesium molten metal fully, take out crucible, add one deck magnesium alloy covering agent, put into simultaneously load weighted tin, again crucible is put into resistance furnace; After alloy melted evenly fully, the regulating resistance temperature was treated to take out crucible when temperature is down to 700-750 ℃, and aluminium alloy is poured into ingot; Behind the polishing alloy pig surface, be cut to the sample that gets rid of with usefulness;
(3) get a bottom and drive foraminate silica tube, hole diameter is 0.8 ~ 1.2mm, and step (2) gained ingot intercepting fritter is put into silica tube, adopts the ratio-frequency heating remelting to get rid of carry sample; Treat that melt temperature reaches 750 ~ 800 ℃, then get rid of band, get rid of band and under argon shield, carry out;
(4) carry out corrosion treatment getting rid of with the gained alloy strip in the hydrochloric acid soln of 0.1-5mol/L, treatment temp is 10-50 ℃, and the reaction times is 0.5-2.5 hour; After the processing sample is washed till neutrality and places vacuum vessel to preserve, namely obtain the nanoporous gunmetal, this material has the pore space structure of three-dimensional, co-continuous and nano-scale, and the hole is of a size of the 20-150 nanometer.
The present invention after the hydrochloric acid soln corrosion, obtains the nanoporous gunmetal by the reasonable component proportioning, and through scanning electron microscope analysis, gained nano-porous structure mesopore is of a size of 20 ~ 150 nanometers, and microhomogeneity is better.
The present invention has the following advantages: (1) is by the standby magnesium copper tin presoma alloy of melting-get rid of band legal system, and is simply controlled, can realize batch production.(2) it is less to get rid of band gained alloy strip thickness, has greatly shortened the corrosion required time, and can realize corroding fully with general lower concentration acid.(3) composition of the nanoporous gunmetal of the method preparation can be regulated by the component proportions of control magnesium copper tin presoma alloy.(4) this nanoporous gunmetal hole has the structure of three-dimensional, co-continuous, and size is less, be 20 ~ 150 nanometers, copper wherein is on the one hand because comparatively tiny yardstick can provide good conductivity, stable porous framework structure is provided on the other hand, has weakened the volume change that causes when lithium inserts.It is a kind of potential lithium ion battery negative material.
Embodiment
The invention will be further described below in conjunction with specific embodiment, should be understood that, following explanation only is in order to explain the present invention, its content not to be limited.
Embodiment one
(1) according to atomic percent 50% magnesium, 35% bronze medal, all the other take by weighing starting material for the proportioning of tin;
(2) load weighted magnesium is put into quartz crucible, and at magnesium covering last layer RJ-2 magnesium alloy covering agent, then resistance furnace temperature is adjusted to 750-800 ℃, treat that magnesium is melted into molten state, take out crucible, again add an amount of RJ-2 magnesium alloy covering agent, add simultaneously the copper of load weighted certain proportioning, crucible is put back to resistance furnace; Through 15-20 minute, treat that copper incorporates after the magnesium molten metal fully, take out crucible, add one deck RJ-2 magnesium alloy covering agent, put into simultaneously load weighted tin, again crucible is put into resistance furnace; After alloy melted evenly fully, the regulating resistance temperature was treated to take out crucible when temperature is down to 700-750 ℃, and aluminium alloy is poured into ingot.Behind the polishing alloy pig surface, be cut to the sample that gets rid of with usefulness;
(3) getting a length is 400mm, diameter 10mm, and foraminate silica tube is driven in the bottom, and hole diameter is 0.8mm, and step (2) gained ingot intercepting fritter is put into silica tube, adopts the ratio-frequency heating remelting to get rid of carry sample; Treat that melt temperature reaches 750 ~ 800 ℃, be incubated 1 minute, then get rid of band, get rid of band and under argon shield, carry out;
(4) carry out corrosion treatment getting rid of with the gained alloy strip in the hydrochloric acid soln of 5mol/L, treatment temp is 10 ℃, and the reaction times is 1 hour; After the processing sample is washed till neutrality and places vacuum vessel to preserve, namely obtain the nanoporous gunmetal, this material has the pore space structure of three-dimensional, co-continuous and nano-scale, and the hole is of a size of the 20-50 nanometer.
Embodiment two
(1) according to atomic percent 70% magnesium, 20% bronze medal, all the other take by weighing starting material for the proportioning of tin;
(2) load weighted magnesium is put into quartz crucible, and at magnesium covering last layer RJ-2 magnesium alloy covering agent, then resistance furnace temperature is adjusted to 750-800 ℃, treat that magnesium is melted into molten state, take out crucible, again add an amount of RJ-2 magnesium alloy covering agent, add simultaneously the copper of load weighted certain proportioning, crucible is put back to resistance furnace; Through 15-20 minute, treat that copper incorporates after the magnesium molten metal fully, take out crucible, add one deck RJ-2 magnesium alloy covering agent, put into simultaneously load weighted tin, again crucible is put into resistance furnace; After alloy melted evenly fully, the regulating resistance temperature was treated to take out crucible when temperature is down to 700-750 ℃, and aluminium alloy is poured into ingot.Behind the polishing alloy pig surface, be cut to the sample that gets rid of with usefulness;
(3) getting a length is 300mm, diameter 8mm, and foraminate silica tube is driven in the bottom, and hole diameter is 1mm, and step (2) gained ingot intercepting fritter is put into silica tube, adopts the ratio-frequency heating remelting to get rid of carry sample; Treat that melt temperature reaches 750 ~ 800 ℃, be incubated 2 minutes, then get rid of band, get rid of band and under argon shield, carry out;
(4) carry out corrosion treatment getting rid of with the gained alloy strip in the hydrochloric acid soln of 0.1mol/L, treatment temp is 50 ℃, and the reaction times is 2 hours; After the processing sample is washed till neutrality and places vacuum vessel to preserve, namely obtain the nanoporous gunmetal, this material has the pore space structure of three-dimensional, co-continuous and nano-scale, and the hole is of a size of the 70-150 nanometer.
Embodiment three
(1) according to atomic percent 90% magnesium, 5% bronze medal, all the other take by weighing starting material for the proportioning of tin;
(2) load weighted magnesium is put into quartz crucible, and at magnesium covering last layer RJ-2 magnesium alloy covering agent, then resistance furnace temperature is adjusted to 750-800 ℃, treat that magnesium is melted into molten state, take out crucible, again add an amount of RJ-2 magnesium alloy covering agent, add simultaneously the copper of load weighted certain proportioning, crucible is put back to resistance furnace; Through 15-20 minute, treat that copper incorporates after the magnesium molten metal fully, take out crucible, add one deck RJ-5 magnesium alloy covering agent, put into simultaneously load weighted tin, again crucible is put into resistance furnace; After alloy melted evenly fully, the regulating resistance temperature was treated to take out crucible when temperature is down to 700-750 ℃, and aluminium alloy is poured into ingot.Behind the polishing alloy pig surface, be cut to the sample that gets rid of with usefulness;
(3) getting a length is 450mm, diameter 15mm, and foraminate silica tube is driven in the bottom, and hole diameter is 1.2mm, and step (2) gained ingot intercepting fritter is put into silica tube, adopts the ratio-frequency heating remelting to get rid of carry sample; Treat that melt temperature reaches 750 ~ 800 ℃, be incubated 0.5 minute, then get rid of band, get rid of band and under argon shield, carry out;
(4) carry out corrosion treatment getting rid of with the gained alloy strip in the hydrochloric acid soln of 3mol/L, treatment temp is 25 ℃, and the reaction times is 1.5 hours; After the processing sample is washed till neutrality and places vacuum vessel to preserve, namely obtain the nanoporous gunmetal, this material has the pore space structure of three-dimensional, co-continuous and nano-scale, and the hole is of a size of the 40-80 nanometer.
Claims (1)
1. the preparation method of a nano porous copper tin alloy material is characterized in that may further comprise the steps:
(1) press magnesium 50-90%, copper 5-35%, all the other take by weighing starting material for the atomic percent of tin;
(2) load weighted magnesium is put into quartz crucible, and at magnesium covering last layer magnesium alloy covering agent, then resistance furnace temperature is adjusted to 750-800 ℃, treat that magnesium is fused into molten state, take out crucible, again add an amount of magnesium alloy covering agent, add simultaneously the copper of load weighted certain proportioning, crucible is put back to resistance furnace; Through 15-20 minute, treat that copper incorporates after the magnesium molten metal fully, take out crucible, add one deck magnesium alloy covering agent, put into simultaneously load weighted tin, again crucible is put into resistance furnace; After alloy melted evenly fully, the regulating resistance temperature was treated to take out crucible when temperature is down to 700-750 ℃, and aluminium alloy is cast into ingot; Behind the polishing alloy pig surface, be cut to the sample that gets rid of with usefulness;
(3) get a bottom and drive foraminate silica tube, hole diameter is 0.8 ~ 1.2mm, and step (2) gained ingot intercepting fritter is put into silica tube, adopts the ratio-frequency heating remelting to get rid of carry sample; Treat that melt temperature reaches 750 ~ 800 ℃, then get rid of band, get rid of band and under argon shield, carry out;
(4) carry out corrosion treatment getting rid of with the gained alloy strip in the hydrochloric acid soln of 0.1-5mol/L, treatment temp is 10-50 ℃, and the reaction times is 0.5-2.5 hour; After the processing sample is washed till neutrality and places vacuum vessel to preserve, namely obtain the nanoporous gunmetal.
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| CN104953104B (en) * | 2015-06-16 | 2017-03-22 | 华南理工大学 | Nano-porous and nano-porous flower shape copper-tin alloy and preparation method thereof |
| CN106935864B (en) * | 2017-03-09 | 2020-04-28 | 华南理工大学 | Nano porous copper-zinc-aluminum shape memory alloy and preparation method and application thereof |
| CN111621784B (en) * | 2019-02-28 | 2022-08-05 | 华中科技大学 | Controllable synthesis method of nano material |
Citations (3)
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|---|---|---|---|---|
| CN101590528A (en) * | 2009-06-19 | 2009-12-02 | 山东大学 | A kind of preparation method of nano porous copper |
| CN102337420A (en) * | 2011-09-15 | 2012-02-01 | 北京航空航天大学 | Method for preparing porous Mg2Cu compound based on Mg-Cu one-step dealloying |
| CN102352496A (en) * | 2011-09-30 | 2012-02-15 | 浙江工业大学 | Method for preparing tin-copper alloy materials and carbon covered tin-copper alloy materials |
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| RU2482204C2 (en) * | 2008-10-31 | 2013-05-20 | Зундвигер Мессингверк Гмбх Унд Ко.Кг | Copper-tin alloy, composite material and their application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101590528A (en) * | 2009-06-19 | 2009-12-02 | 山东大学 | A kind of preparation method of nano porous copper |
| CN102337420A (en) * | 2011-09-15 | 2012-02-01 | 北京航空航天大学 | Method for preparing porous Mg2Cu compound based on Mg-Cu one-step dealloying |
| CN102352496A (en) * | 2011-09-30 | 2012-02-15 | 浙江工业大学 | Method for preparing tin-copper alloy materials and carbon covered tin-copper alloy materials |
Non-Patent Citations (6)
| Title |
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| Changchun Zhao et al..Fabrication and characterization of monolithic nanoporous copper through chemical dealloying of Mg-Cu alloys.《Corrosion Science》.2009,第51卷第2120-2125页. |
| Changchun Zhao et al..On the electrochemical dealloying of Mg-Cu alloys in a NaCl aqueous solution.《Corrosion Science》.2010,第52卷第3962-3972页. |
| Fabrication and characterization of monolithic nanoporous copper through chemical dealloying of Mg-Cu alloys;Changchun Zhao et al.;《Corrosion Science》;20090609;第51卷;第2120-2125页 * |
| On the electrochemical dealloying of Mg-Cu alloys in a NaCl aqueous solution;Changchun Zhao et al.;《Corrosion Science》;20100811;第52卷;第3962-3972页 * |
| Preparation and characterization of nanoporous Cu6Sn5/Cu composite by chemical dealloying of Al-Cu-Sn ternary alloy;Yefei Feng et al.;《J Mater Sci》;20120516;第47卷;第5911-5917页 * |
| Yefei Feng et al..Preparation and characterization of nanoporous Cu6Sn5/Cu composite by chemical dealloying of Al-Cu-Sn ternary alloy.《J Mater Sci》.2012,第47卷第5911-5917页. |
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