CN101667638B - Preparation method of lithium silicon alloy membrane electrode used for lithium ion battery - Google Patents
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Abstract
The invention discloses a preparation method of lithium silicon alloy membrane electrode used for lithium ion battery. The lithium silicon alloy membrane electrode used for lithium ion battery is obtained by the steps of adopting electrolytic deposition method and multiple current step technology under argon protection, taking anhydrous organic solvent or ionic liquid containing silicon compound and lithium salt as electrolyte and realizing the co-deposition of silicon and lithium through electrochemical reduction on a metal current collector. By changing the composition of the electrolyte and the parameters of the multiple current step technology, the cycle capacity and primary cycle efficiency of the lithium silicon alloy membrane electrode can be effectively regulated and controlled. The obtained lithium silicon alloy membrane electrode is used as the negative electrode of a lithium ion battery, the primary cycle efficiency is 45.0 percent -150.0 percent, the charge and discharge capacity is 50.0-1000.0MumAh cm<-2> and the cycle stability is good.
Description
Technical field
The present invention relates to a kind of preparation method's of battery electrode material, particularly a kind of lithium silicon alloy membrane electrode used for lithium ion battery preparation method.
Background technology
At present, the commercial li-ion battery extensively adopts graphite and modified graphite as negative material, and lower (graphite is 372mAh g but there is theoretical lithium storage content
-1), shortcomings such as organic solvent embeds altogether easily take place, so the research of cathode material for high capacity lithium ion battery has become the key that improves battery performance with application.In known lithium storage materials, silicon has the highest theoretical capacity and (is about 4200mAh g
-1) and comparatively moderate doff lithium current potential (about 0.1-0.5V vs.Li/Li
+), be highly suitable for doing lithium ion battery negative material (J.O.Besenhard, J.Yang et.al., J Power Sources, 1997,68:87).But shortcoming be silica-base material under high level doff lithium condition, have serious bulk effect, cause the electrode material structural breakdown easily or peel off and electrode material is lost electrically contacting, thereby cause the cycle performance of electrode sharply to descend from collector.
In recent years, domestic and international many scholars are devoted to improve the research of aspects such as silicon-based anode performance, mainly concentrate on to improve cycle efficieny, inhibition electrode material volumetric expansion first and improve cycle performance etc.For example adopt submicron order thickness of silicon base film electrode, reduced the absolute volume of silicon in the doff lithium process and expanded, can improve the cyclical stability of electrode to a certain extent.Therefore, a large amount of research is conceived to the exploitation of silica-base film electrode.
2003 the 150th volumes of Journal of the Electrochemical Society magazine A121 page or leaf has been reported by pulsed laser deposition and prepared unbodied Mg on Copper Foil
2Si film, thickness are 30～380nm; Thickness is that the membrane electrode cycle performance of 30nm is better, and 100 circulation back specific capacities are still at 2000mAh g
-1More than, but along with the increase of film thickness, the irreversible capacity that circulates first increases and the capacity attenuation aggravation, Mg
2There is serious self-discharge phenomenon in the Si film at circulation time first.
2008 the 53rd volumes of Electrochimica Acta magazine have reported and have adopted vacuum vapor deposition method to prepare the thick silicon thin film electrode of 6 μ m that the specific capacity after 20 circulations is 960mAh g for 5660 pages on the Copper Foil after the surface treatment
-1, but cycle efficieny is 42% only first, awaits further raising; 2004 the 129th volumes of Journal ofPower Sources magazine have then been reported for 96 pages and have been adopted vacuum vapor deposition method to prepare the n type silicon thin film electrode of phosphorus doping on nickel foil, result of study shows that thickness is that membrane electrode specific capacity under the 12C charge-discharge magnification of 50nm reaches 3000mAh g
-1, 1000 times capable of circulation, but increase capacity and all significantly decline of cycle performance with thickness.
2008 the 53rd volumes of ElectrochimicaActa magazine have reported that the employing magnetron sputtering method prepares the thick amorphous Si of 300nm-Al film for 8149 pages, and the mass percent of Al is 18.08%, and preceding 10 recycle ratio capacity reach 2100mAh g under the 0.5C multiplying power
-1, the cycle performance excellence, 350 times circulation back capability retention is 80.2%; SANYO GS company adopts several micron thickness amorphous si film electrode reversible capacities of RF magnetron sputtering technique preparation to reach 3000mAh g
-1More than, efficient is near 100%, electrode energy stable circulation tens times, but the pattern of membrane electrode and performance are subjected to all multifactor impacts such as roughness, Si/Cu interfacial property and silicon thin film thickness of copper substrate, big (the M.Shima of the reproducible technique controlling difficulty of result, H.Yagi, et.al., US patent 6887511B1 (2005)).
Though adopt the silica-base film material of method for preparing to have higher capacity and excellent cycle performance, material preparation needs special installation, and complex process, cost are higher, are difficult to rapid large-scale production.Advantages such as and electro-deposition method is low because of having equipment cost, and is easy and simple to handle have been widely used in preparing lithium ion battery tin base alloy anode material (K.Ui, S.Kikuchi et.al., J.Power Sources, 2009,189:224; L.Huang, Y.Yang et.al., Electrochem.Commun., 2009,11:6).Early (A.K.Agrawal, A.E.Austin, J.Electrochem.Soc.1981,128:2292 are carried out in the research work of relevant silicon electro-deposition; G.M.Rao, D.Elwell, et.al., Solar Energy Materials, 1982,7:15), and low and be easy to reasons such as hydrolysis owing to sedimentation potential, can only do plating bath with organic solvent or fuse salt and could implement the electro-deposition of silicon (Y.Nishimura, Y.Fukunaka, Electrochim.Acta, 2007,53:111; S.Zein El Abedin, N.Borissenko et.al., Electrochem.Commun., 2004,6:510; J.Mallet, M.Molinari, et.al., Nano Lett., 2008,8:3468).
Summary of the invention
The object of the invention is to propose a kind of preparation method of lithium silicon alloy membrane electrode used for lithium ion battery; adopt electrodeposition process; under argon shield, pass through multiple current step technology; with the anhydrous organic solvent or the ionic liquid that contain silicon compound and lithium salts is electrolyte; on metal collector, implement the codeposition of silicon and lithium; the taking-up that continues is also removed remaining electrolyte with anhydrous organic solvent flushing; to obtain a kind of lithium silicon alloy membrane electrode used for lithium ion battery; electrolyte is formed and the parameter of multiple current step technology by changing, and can effectively regulate and control the circulation volume of lithium silicon alloy membrane electrode and cycle efficieny first.
The preparation method of a kind of lithium silicon alloy membrane electrode used for lithium ion battery of the present invention is as follows:
(1) under argon shield, lithium salts and silicon compound are joined in anhydrous organic solvent or the ionic liquid, stirring and dissolving obtains the electrolyte of certain volume, and the molar concentration of silicon compound is 0.1～1.0mol L in the electrolyte
-1, the molar concentration of lithium salts is 0.1～1.0mol L
-1
(2) above-mentioned electrolyte is placed two Room electrolytic cells, in 20～30 ℃ of temperature ranges, carry out the electro-deposition of lithium silicon alloy under argon shield: negative electrode is foam-metal current collector body or planar metal collector; Multiple current step technology is adopted in electro-deposition, and first step step apparent area current density is 1.5～8.0mA cm
-2, first step snap time is 600～1800 seconds, second step apparent area current density that jumps is 1.0～8.0mA cm
-2, the second step time of jumping was 3600～14400 seconds; After electro-deposition finishes,, obtain a kind of lithium silicon alloy membrane electrode used for lithium ion battery with the anhydrous organic solvent flushing.
The lithium salts that the present invention uses is lithium perchlorate, lithium hexafluoro phosphate, two fluoroform sulfimide lithium or trifluoromethyl sulfonic acid lithium.
The anhydrous organic solvent that the present invention uses is 1: 1 ethylene carbonate and dimethyl carbonate mixed solvent as oxolane, pyridine, propene carbonate, diethyl carbonate, dimethyl carbonate or volume ratio; Ionic liquid is the two fluoroform sulfimide salt of 1-butyl-1 methylpyrrole, the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole or the two fluoroform sulfimide salt of trimethyl n-hexyl ammonium.
The silicon compound that the present invention uses is trichlorosilane or silicon tetrachloride.
The foam-metal current collector body that the present invention uses is foam copper or nickel foam, and thickness is 0.4～3.0mm; The planar metal collector is Copper Foil, copper sheet, nickel foil or nickel sheet, and thickness is 0.02～1.00mm.
The preparation method of a kind of lithium silicon alloy membrane electrode used for lithium ion battery of the present invention has following advantage:
(1) among the preparation method of a kind of lithium silicon alloy membrane electrode used for lithium ion battery of the present invention, adopt electrodeposition process, under argon shield, pass through multiple current step technology, make in the electrolyte silicon compound and lithium salts on the metal collector negative electrode electrochemical reduction takes place and codeposition makes the lithium silicon alloy membrane electrode; Electrolyte is formed and the parameter of multiple current step technology by changing, and can effectively regulate and control the circulation volume of lithium silicon alloy membrane electrode and cycle efficieny first;
(2) adhesion of electrodeposited film and metal collector is better in the lithium silicon alloy membrane electrode, compares with conventional lithium ion cell electrode, need not to add conductive agent and binding agent in this lithium silicon alloy membrane electrode, has reduced the influence of binding agent to electrode performance;
(3) lithium silicon alloy membrane electrode surface is more coarse, wherein has some irregular pore structures, can alleviate the bulk effect of silicon in the doff lithium process to a certain extent, improves the cycle performance of electrode material; The lithium silicon alloy membrane electrode is as lithium ion battery negative, and cycle efficieny is 45.0%～150.0% first, and charge/discharge capacity is 50.0～1000.0 μ Ah cm
-2, cyclical stability is better.
Description of drawings
The XRD figure of a kind of lithium silicon alloy membrane electrode used for lithium ion battery that Fig. 1 obtains for embodiment 1.
The SEM figure of a kind of lithium silicon alloy membrane electrode used for lithium ion battery that Fig. 2 obtains for embodiment 1.
The capacity of the charging and discharging curve of the 1st, 2,3 and 22 circulations of the lithium ion battery of a kind of lithium silicon alloy membrane electrode used for lithium ion battery that Fig. 3 obtains for embodiment 1 and preceding 22 circulations of battery is with the variation diagram of cycle-index.
The capacity of preceding 32 circulations of the lithium ion battery of a kind of lithium silicon alloy membrane electrode used for lithium ion battery that Fig. 4 obtains for embodiment 2 is with the variation diagram of cycle-index.
The charging and discharging curve of preceding 2 circulations of the lithium ion battery of a kind of lithium silicon alloy membrane electrode used for lithium ion battery that Fig. 5 obtains for embodiment 3.
Embodiment
Following examples further specify the present invention, but the present invention is not limited to following examples.
The method of testing that the lithium silicon alloy membrane electrode that makes in following examples is applied in the lithium ion battery is as follows:
In being full of the argon gas glove box, be positive pole with the lithium silicon alloy membrane electrode for preparing, metal lithium sheet is a negative pole, ENTEK ET20-26 is a barrier film, 1.0mol L
-1The ethylene carbonate of lithium hexafluoro phosphate and dimethyl carbonate (volume ratio 1: 1) mixed solution is an electrolyte, is assembled into the CR2016 button cell; Carry out the constant current charge-discharge performance test on LAND battery test system (the blue electric Electronics Co., Ltd. in Wuhan provides), charging and discharging currents density is 12.7 μ Acm
-2Or 25.5 μ Acm
-2, discharge and recharge cut-ff voltage with respect to Li/Li
+Be 0.01～1.4V.
Embodiment 1
(1) under argon shield, 1.8618g lithium perchlorate and 1.44ml silicon tetrachloride are joined in the propene carbonate, stirring and dissolving obtains 25.0ml electrolyte, and the molar concentration of silicon tetrachloride is 0.5mol L in the electrolyte
-1, the molar concentration of lithium perchlorate is 0.7mol L
-1
(2) above-mentioned electrolyte is placed two Room electrolytic cells, under 25 ℃, carry out the electro-deposition of lithium silicon alloy under argon shield: negative electrode is a Copper Foil, and thickness is 0.02mm; Multiple current step technology is adopted in electro-deposition, and first step step apparent area current density is 3.8mA cm
-2, first step snap time is 600 seconds, second step apparent area current density that jumps is 1.3mA cm
-2, the second step time of jumping was 7200 seconds, after electro-deposition finished, the Copper Foil with after the propene carbonate flushing electro-deposition obtained a kind of lithium silicon alloy membrane electrode used for lithium ion battery.
The XRD figure of a kind of lithium silicon alloy membrane electrode used for lithium ion battery that Fig. 1 obtains for embodiment 1, the result shows: the lithium silicon alloy is mainly by Li in the lithium silicon alloy membrane electrode
21Si
5, Li
21Si
8And Li
7Si
3Phase composition.
The SEM figure of a kind of lithium silicon alloy membrane electrode used for lithium ion battery that Fig. 2 obtains for embodiment 1, as seen from the figure, lithium silicon alloy film and Copper Foil adhere to better; And the surface of electrode is more coarse, wherein has some irregular pore structures, can alleviate the bulk effect of silicon in the doff lithium process to a certain extent.
The capacity of the charging and discharging curve of the 1st, 2,3 and 22 circulations of the lithium ion battery of a kind of lithium silicon alloy membrane electrode used for lithium ion battery that Fig. 3 obtains for embodiment 1 and preceding 22 circulations of battery is with the variation diagram of cycle-index.The charging and discharging currents density of preceding twice circulation is 12.7 μ Acm
-2, the first charge-discharge capacity is respectively 259.4 μ Ah cm
-2With 267.1 μ Ah cm
-2, cycle efficieny is up to 97.1% first.Begin twice circulation to take off the lithium charging curve overlapping fully, show good electrochemical reversibility.After activating two circulations, charging and discharging currents density changes 25.5 μ Acm into
-2, charging capacity is 240.6 μ Ah cm
-2(seeing the 3rd circulation among Fig. 3), 20 times circulation back charging capacity is 215.3 μ Ah cm
-2, promptly capability retention is 89.5%.
(1) under argon shield, 1.8988g lithium hexafluoro phosphate and 1.44ml silicon tetrachloride are joined in the propene carbonate, stirring and dissolving obtains 25.0ml electrolyte, and the molar concentration of silicon tetrachloride is 0.5mol L in the electrolyte
-1, the molar concentration of lithium hexafluoro phosphate is 0.5mol L
-1
(2) above-mentioned electrolyte is placed two Room electrolytic cells, under 30 ℃, carry out the electro-deposition of lithium silicon alloy under argon shield: negative electrode is a copper sheet, and thickness is 0.50mm; Multiple current step technology is adopted in electro-deposition, and first step step apparent area current density is 3.8mA cm
-2, first step snap time is 600 seconds, second step apparent area current density that jumps is 1.3mA cm
-2, the second step time of jumping was 7200 seconds, after electro-deposition finished, the copper sheet with after the propene carbonate flushing electro-deposition obtained a kind of lithium silicon alloy membrane electrode used for lithium ion battery.
The capacity of preceding 32 circulations of the lithium ion battery of a kind of lithium silicon alloy membrane electrode used for lithium ion battery that Fig. 4 obtains for embodiment 2 is with the variation diagram of cycle-index.The charging and discharging currents density of preceding twice circulation is 12.7 μ A cm
-2, activate two circulations after, charging and discharging currents density changes 25.5 μ A cm into
-2At 25.5 μ A cm
-2Condition under, 30 times the circulation after the charging capacity conservation rate up to 95.0%, cycle efficieny is 47.5% first, good cycling stability.
Embodiment 3
(1) under argon shield, 1.8618g lithium perchlorate and 1.44ml silicon tetrachloride are joined in the propene carbonate, stirring and dissolving obtains 25.0ml electrolyte, and the molar concentration of silicon tetrachloride is 0.5mol L in the electrolyte
-1, the molar concentration of lithium perchlorate is 0.7mol L
-1
(2) above-mentioned electrolyte is placed two Room electrolytic cells, under 25 ℃, carry out the electro-deposition of lithium silicon alloy under argon shield: negative electrode is a Copper Foil, and thickness is 0.02mm; Multiple current step technology is adopted in electro-deposition, and first step step apparent area current density is 3.8mA cm
-2, first step snap time is 600 seconds, second step apparent area current density that jumps is 1.3mA cm
-2, the second step time of jumping was 10800 seconds, after electro-deposition finished, the Copper Foil with after the propene carbonate flushing electro-deposition obtained a kind of lithium silicon alloy membrane electrode used for lithium ion battery.
The charging and discharging curve of preceding 2 circulations of the lithium ion battery of a kind of lithium silicon alloy membrane electrode used for lithium ion battery that Fig. 5 obtains for embodiment 3.Charging and discharging currents density is 12.7 μ Acm
-2As seen from the figure, the first charge-discharge capacity is respectively 502.2 μ Ahcm
-2With 412.5 μ Ahcm
-2, cycle efficieny is up to 121.7% first.
Embodiment 4
(1) under argon shield, 0.7800g trifluoromethyl sulfonic acid lithium and 2.53ml trichlorosilane are joined in the oxolane, stirring and dissolving obtains 25.0ml electrolyte, and the molar concentration of trichlorosilane is 1.0mol L in the electrolyte
-1, the molar concentration of trifluoromethyl sulfonic acid lithium is 0.2mol L
-1
(2) above-mentioned electrolyte is placed two Room electrolytic cells, under 20 ℃, carry out the electro-deposition of lithium silicon alloy under argon shield: negative electrode is a nickel foam, and thickness is 2.0mm; Multiple current step technology is adopted in electro-deposition, and first step step apparent area current density is 6.0mAcm
-2, first step snap time is 1800 seconds, second step apparent area current density that jumps is 4.0mAcm
-2, the second step time of jumping was 3600 seconds, after electro-deposition finished, the nickel foam with after the dimethyl carbonate flushing electro-deposition obtained a kind of lithium silicon alloy membrane electrode used for lithium ion battery.
(1) under argon shield; two fluoroform sulfimide lithiums of 3.5885g and 1.52ml trichlorosilane are joined in the two fluoroform sulfimide salt of 1-butyl-1 methylpyrrole; stirring and dissolving obtains 25.0ml electrolyte, and the molar concentration of trichlorosilane is 0.6mol L in the electrolyte
-1, the molar concentration of two fluoroform sulfimide lithiums is 0.5mol L
-1
(2) above-mentioned electrolyte is placed two Room electrolytic cells, under 20 ℃, carry out the electro-deposition of lithium silicon alloy under argon shield: negative electrode is a foam copper, and thickness is 0.5mm; Multiple current step technology is adopted in electro-deposition, and first step step apparent area current density is 8.0mAcm
-2, first step snap time is 1000 seconds, second step apparent area current density that jumps is 3.5mAcm
-2, the second step time of jumping was 10000 seconds, after electro-deposition finished, the foam copper with after the propene carbonate flushing electro-deposition obtained a kind of lithium silicon alloy membrane electrode used for lithium ion battery.
Embodiment 6
(1) under argon shield; two fluoroform sulfimide lithiums of 0.7177g and 0.29ml silicon tetrachloride are joined in the two fluoroform sulfimide salt of trimethyl n-hexyl ammonium; stirring and dissolving obtains 25.0ml electrolyte, and the molar concentration of silicon tetrachloride is 0.1mol L in the electrolyte
-1, the molar concentration of two fluoroform sulfimide lithiums is 0.1mol L
-1
(2) above-mentioned electrolyte is placed two Room electrolytic cells, under 20 ℃, carry out the electro-deposition of lithium silicon alloy under argon shield: negative electrode is the nickel sheet, and thickness is 0.40mm; Multiple current step technology is adopted in electro-deposition, and first step step apparent area current density is 1.5mAcm
-2, first step snap time is 1200 seconds, second step apparent area current density that jumps is 8.0mA cm
-2, the second step time of jumping was 14400 seconds, after electro-deposition finished, the nickel sheet with after the dimethyl carbonate flushing electro-deposition obtained a kind of lithium silicon alloy membrane electrode used for lithium ion battery.
Claims (2)
1. the preparation method of a lithium silicon alloy membrane electrode used for lithium ion battery is characterized in that, the preparation method is as follows:
(1) under argon shield, lithium salts and silicon compound are joined in anhydrous organic solvent or the ionic liquid, stirring and dissolving obtains the electrolyte of certain volume, and the molar concentration of silicon compound is 0.1～1.0mol L in the electrolyte
-1, the molar concentration of lithium salts is 0.1～1.0mol L
-1
(2) above-mentioned electrolyte is placed two Room electrolytic cells, in 20～30 ℃ of temperature ranges, carry out the electro-deposition of lithium silicon alloy under argon shield: negative electrode is foam-metal current collector body or planar metal collector; Multiple current step technology is adopted in electro-deposition, and first step step apparent area current density is 1.5～8.0mA cm
-2, first step snap time is 600～1800 seconds, second step apparent area current density that jumps is 1.0～8.0mA cm
-2, the second step time of jumping was 3600～14400 seconds; After electro-deposition finishes,, obtain a kind of lithium silicon alloy membrane electrode used for lithium ion battery with the anhydrous organic solvent flushing; Wherein, lithium salts is lithium perchlorate, lithium hexafluoro phosphate, two fluoroform sulfimide lithium or trifluoromethyl sulfonic acid lithium; Silicon compound is trichlorosilane or silicon tetrachloride; Anhydrous organic solvent is that oxolane, pyridine, propene carbonate, diethyl carbonate, dimethyl carbonate or volume ratio are 1: 1 ethylene carbonate and dimethyl carbonate mixed solvent; Ionic liquid is the two fluoroform sulfimide salt of 1-butyl-1 methylpyrrole, the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole or the two fluoroform sulfimide salt of trimethyl n-hexyl ammonium.
2. the preparation method of a kind of lithium silicon alloy membrane electrode used for lithium ion battery according to claim 1 is characterized in that the foam-metal current collector body is foam copper or nickel foam, and thickness is 0.4～3.0mm; The planar metal collector is Copper Foil, copper sheet, nickel foil or nickel sheet, and thickness is 0.02～1.00mm.
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| CN107134577A (en) * | 2017-05-09 | 2017-09-05 | 东北大学 | A kind of preparation method of nanoscale lithium manganese phosphate |
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| CN107134577A (en) * | 2017-05-09 | 2017-09-05 | 东北大学 | A kind of preparation method of nanoscale lithium manganese phosphate |
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