CN103996834A - Silicon-base negative material with silane coupling agent and conductive polymer two-layer cladding structure as well as preparation method and application of material - Google Patents
Silicon-base negative material with silane coupling agent and conductive polymer two-layer cladding structure as well as preparation method and application of material Download PDFInfo
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Abstract
The invention discloses a silicon-base negative material with a silane coupling agent and conductive polymer two-layer cladding structure as well as a preparation method and application of the material. The silicon-base negative material is characterized in that monomer silicon is adopted as a substrate, the substrate is coated with a silane coupling agent decorative layer, and the silane coupling agent decorative layer is coated with protonic acid doping-state conductive polyaniline. The preparation method comprises the following steps: (1) ultrasonically blending a silane coupling agent and silicon powder, and refluxing the mixture of the silane coupling agent and the silicon powder at a given temperature so as to decorate the silicon powder; (2) ultrasonically blending aniline monomer and decorated silicon powder in an acid solution system, and performing in-situ polymerizing on the aniline monomer and the decorated silicon powder to obtain a silicon-base composite material which is coated with the conductive polymer; (3) washing, suction-filtering and vacuum-drying the mixed solution to obtain the silicon-base negative material with the silane coupling agent and conductive polymer two-layer cladding structure. When being doped in graphite, the silicon-base negative material can be used for preparing a negative material of a lithium ion battery. The preparation method is simple and easy, low in manufacturing cost, good in repeatability and convenient for industrialized mass production.
Description
Technical field
The invention belongs to lithium ion battery negative material and technical field of electrochemistry, relate to a kind of silicon based anode material with silane coupler and conducting polymer double-coated structure and preparation method thereof and application.
Background technology
In the last few years, lithium ion battery with respect to the secondary cells such as traditional lead-acid battery, iron cell, Ni-MH battery have high-energy-density, high output voltage, low self-discharge, memory effect is little and advantages of environment protection, and be widely used and study.The performance of lithium ion battery critical material is the important deciding factor of battery performance, and it is global scientific research focus that the exploitation of negative material improves.The negative materials such as silicon materials, material with carbon element, tin material, lithium titanate, metal oxide are studied widely.But there is the defects such as cycle performance is poor, specific energy density is low, cost is high, poor stability, consistency problem in the lithium-ion battery system of these negative material assemblings, is difficult to meet the requirement of power energy-storage battery.
silicon based anode material is because its theoretical specific capacity surpasses 4200 mAh/g, embedding lithium current potential is low, actual specific capacity is greater than 3000 mAh/g, at natural rich content, the advantages such as cost of material is relatively cheap are the study hotspots of lithium ion battery negative material always.The shortcoming severe inhibition such as but coulomb efficiency first of silicon materials is low, high rate performance is poor, cycle performance is poor the large-scale application of silicon based anode material in lithium ion battery.
For the silicon based anode material of development cycle excellent performance, researcher has developed multiple technologies means silicon materials has been carried out to modification raising.Graphite, hard carbon, pitch, carbon nano-tube, carbon nano-fiber, metal nano-tube etc. have been used to coated silicon based anode material.As N. Kurita etc. makes the Si with regular texture
2c
52h
18, this material is with respect to C
54h
18can embed in a large number lithium ion, and its structure also can reduce the irreversible reaction that lithium ion is deviate from, there is good cycle performance.N. the employing hot gas sedimentation such as Dimov has been coated one deck material with carbon element on elementary silicon surface, obtain the particle that average-size is 18 μ m, specific capacity is more than 600mAh/g, than the theoretical specific capacity of material with carbon element (372 mAh/g) height, cycle performance and material with carbon element are suitable, with elemental silicon, compare and improve a lot.Z. S. Wen etc., by carrying out pyrolysis to inserting the resin of graphite and elemental silicon, obtains silicon-carbon compound, and its specific capacity reaches 800～900 mAh/g, circulates after 20 times, and its specific capacity is stabilized in 600 mAh/g.B.J. Neudecker etc. makes SiSn
0.87o
1.20n
1.72, specific capacity approaches 800 mAh/g, after discharging and recharging for 10000 times, still can remain on 600 mAh/g, and discharge voltage 4.1～2.7V circulates irreversible capacity loss in 0.002% at every turn, but too high cost has hindered its business-like process.
Silane coupler is that people study the earliest, apply coupling agent the earliest, has advantages of that consumption is few, cost is low.Owing to having X and R two class chemical groups in silane coupled agent molecule simultaneously, wherein R is the organo-functional group that can be combined with high molecular polymer; X be can with silicon surface oxidation layer in the hydrolyzable groups of hydroxyl reaction.Therefore the effect of coupling is played in the interaction of silane coupler between high molecular polymer and inorganic system.
Therefore, need at present the modification method and the preparation method that find a kind of simple silicon based anode material badly, make silicon based anode material have both higher coulomb efficiency first and good cyclical stability simultaneously, thereby can meet the requirement of electrokinetic cell.
Summary of the invention
The object of the present invention is to provide a kind of silicon based anode material with silane coupler and conducting polymer double-coated structure and preparation method thereof and application, use silane coupler to modify silica flour, silane coupler has played function served as bridge between the inorganic system substrate of conducting polymer organic coating layer and silica flour, the method is simple, low cost of manufacture, favorable reproducibility, is convenient to large-scale industrial production.
The object of the invention is to be achieved through the following technical solutions:
Have a silicon based anode material for silane coupler and conducting polymer double-coated structure, take elemental silicon as substrate, in substrate, be coated with silane coupler decorative layer, silane coupler decorative layer is coated with protonic acid doping state electrically conductive polyaniline.
An above-mentioned silicon based anode material preparation method with silane coupler and conducting polymer double-coated structure, its step is as follows:
(1) silane coupler and silica flour are carried out to ultrasonic blend, reflux at a certain temperature, silica flour is modified; Wherein: the preparation method of silica flour is a kind of of vapor phase method, sol-gel processing, the precipitation method, microemulsion method, ball-milling method; The particle size interval scope of silica flour is between 20 to 2000 nm; Silane coupler is a kind of of γ-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, octyltri-ethoxysilane, dimethyldimethoxysil,ne, methyl tributanoximo silane, isocyanic acid propyl-triethoxysilicane; The addition of silane coupler is the 0.01-10% of silica flour mass fraction; Reflux temperature is 40-120 ℃, and return time is 1-24 h;
(2) silica flour by aniline monomer and after modifying carries out ultrasonic blend in the acid solution system of Bronsted acid, then adds ammonium persulfate, carries out in-situ polymerization, obtains being coated with the silicon based composite material of conducting polymer; Wherein: Bronsted acid is one or more the mixture in hydrochloric acid, DBSA, camphorsulfonic acid, p-methyl benzenesulfonic acid, pyrovinic acid, normal-butyl/ethyl phosphonic acid, n-decane base phosphoric acid, benzyl phosphoric acid, benzoic acid; Polymeric reaction temperature is 0-10 ℃, and the ratio that adds quality of ammonium persulfate and aniline is 1:2-1:4, and the silica flour after modification and the mass ratio of aniline are 4:1-1:1, and polymerization reaction time is 4-10 h.
(3), by described mixed solution washing, suction filtration, vacuumize, obtain having the silicon based anode material of silane coupler and conducting polymer double-coated structure; Wherein: vacuumize temperature is 45-55 ℃, the vacuumize time is 10-12 h.
The silicon based anode material with silane coupler and conducting polymer double-coated structure prepared by said method, can be entrained in graphite, and the silicon based anode material with silane coupler and conducting polymer double-coated structure accounts for 1 ~ 98% of content of graphite.
The silane coupler modified silica flour of the present invention, on silicon base surface, form decorative layer, then at its Surface Creation conducting polymer coating layer, function served as bridge due to silane coupler, silicon base and outermost conducting polymer are in conjunction with tight, the expansion efflorescence effect that can effectively stop silicon, makes silicon based anode material have higher coulomb efficiency first and good cyclical stability, to meet the requirement of electrokinetic cell.
Advantage of the present invention is as follows:
(1) with silane coupler, modify elemental silicon and form the first coating layer, surface in situ generates the conducting polymer coating layer of combining closely outside, has improved coulomb efficiency and the cyclical stability first of silicon based anode material, can meet the requirement of electrokinetic cell.
(2) this modified technique is applicable to all silicon based anode materials, simple, low cost of manufacture, and favorable reproducibility, is convenient to large-scale industrial production.
(3) silicon-based anode of the present invention has higher specific capacity with respect to the silicon-based anode of prior art, particularly the cycle performance of existing silicium cathode has been carried out significantly improving, after being entrained in graphite, the performance of graphite cathode material is had significantly and promoted.
(4) the prepared silicon based anode material of the present invention has infrared spectrum as shown in Figure 5, and its characteristic peak is 2972cm
-1, 2926cm
-1and 1735cm
-1.
Accompanying drawing explanation
Fig. 1 is the reaction principle figure of silane coupler and elemental silicon substrate;
Fig. 2 is the reaction unit schematic diagram of in-situ polymerization;
Fig. 3 is the SEM figure of silane coupler modified front silicon based anode material;
Fig. 4 is the SEM figure of the silicon based anode material (embodiment 1) of silane coupler and conducting polymer double-coated structure;
Fig. 5 is the infrared spectrum with the silicon based anode material of silane coupler coating layer;
Fig. 6 is the cycle performance curve with the silicon based anode material (embodiment 4) of silane coupler and conducting polymer double-coated structure;
Fig. 7 is the cycle performance diagram with the silicon based anode material of conducting polymer double-coated structure.
Embodiment
Below by embodiment and comparative example, further illustrate the present invention, these embodiment, just for the present invention is described, the invention is not restricted to following examples.Every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
embodiment 1:
1,0.1g γ-(methacryloxypropyl) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 4.9g silica flour ultrasonic mixing 0.5h; At air velocity, be that 200mL/min, temperature are the vacuumize 12h at 10 h, 55 ℃ that refluxes under 80 ℃, magnetic agitation condition, finally obtain mass concentration and be the silicon based anode material of γ-(methacryloxypropyl) propyl trimethoxy silicane surface modification of 2%.As shown in Figure 1, from elemental silicon substrate, the first coating layer is silane coupler decorative layer to the reaction principle figure of silane coupler and elemental silicon substrate, and the second coating layer is protonic acid doping state electrically conductive polyaniline.There is the infrared spectrum of silane coupler coating layer as shown in Figure 5, at 2972 and 2926 cm
-1there is absworption peak in place, this absworption peak correspondence the stretching vibration of c h bond.
2, ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.045g aniline monomer and 0.2g modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 ℃, drip sulfuric acid solution 30 mL of 1.5% percentage by volume that contains 0.0216g ammonium persulfate, in reaction unit shown in Fig. 2, carry out in-situ polymerization, polymerization reaction time is 10 h.
3, mixed solution in step 2 is used distilled water and ethanol alternately wash 2-3 time, suction filtration, vacuumize, obtain having the silicon based anode material of silane coupler and conducting polymer double-coated structure, dry with circulating water pump suction filtration final vacuum, vacuumize temperature is 60 ℃, and the vacuumize time is 12 h.
In comparative example, silica flour reunion is serious (as Fig. 3) comparatively, and the spheroid (as Fig. 4) that the silicon based anode material with silane coupler and conducting polymer double-coated structure of preparation is particle integrity, reunion situation has obtained alleviation, and granular size is about 20-8000 nm.
Silicon based anode material cycle performance curve from Fig. 7 silane coupler coating layer structure, initial charge capacity 2271.2 mAh/g of material, first charge-discharge efficiency is 69.8%, after 200 circulations, charging capacity is 1441.48 mAh/g, Capacitance reserve, in 1400 mAh/g left and right, has excellent performance.
embodiment 2:
1,0.25g γ-(methacryloxypropyl) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 4.75g silica flour ultrasonic mixing 0.5h; At air velocity, be that 200mL/min, temperature are the vacuumize 12h at 10 h, 55 ℃ that refluxes under 80 ℃, magnetic agitation condition, finally obtain mass concentration and be the silicon based anode material of γ-(methacryloxypropyl) propyl trimethoxy silicane surface modification of 5%.
2, ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.045 g aniline monomer and 0.2g modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 ℃, drip hydrochloric acid solution 30 mL of 3.1% percentage by volume that contains 0.0216g ammonium persulfate, carry out in-situ polymerization, polymerization reaction time is 10 h.
3, mixed solution in step 2 is used distilled water and ethanol alternately wash 2-3 time, suction filtration, vacuumize, obtain having the silicon based anode material of silane coupler and conducting polymer double-coated structure, dry with circulating water pump suction filtration final vacuum, vacuumize temperature is 60 ℃, and the vacuumize time is 12 h.
Silicon based anode material cycle performance curve from Fig. 7 silane coupler coating layer structure, initial charge capacity 2156.14 mAh/g of material, first charge-discharge efficiency is 70.2%, after 200 circulations, charging capacity is 1553.28 mAh/g, Capacitance reserve, in 1550 mAh/g left and right, has excellent performance.
embodiment 3:
1,0.1g γ-(methacryloxypropyl) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 4.9g silica flour ultrasonic mixing 0.5h; At air velocity, be that 200mL/min, temperature are the vacuumize 12h at 10 h, 55 ℃ that refluxes under 80 ℃, magnetic agitation condition, finally obtain mass concentration and be the silicon based anode material of γ-(methacryloxypropyl) propyl trimethoxy silicane surface modification of 2%.
2, ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.09g aniline monomer and 0.2g modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 ℃, drip hydrochloric acid solution 30 mL of 3.1% percentage by volume that contains 0.0432g ammonium persulfate, carry out in-situ polymerization, polymerization reaction time is 10 h.
3, mixed solution in step 2 is used distilled water and ethanol alternately wash 2-3 time, suction filtration, vacuumize, obtain having the silicon based anode material of silane coupler and conducting polymer double-coated structure, dry with circulating water pump suction filtration final vacuum, vacuumize temperature is 60 ℃, and the vacuumize time is 12 h.
Silicon based anode material cycle performance curve from Fig. 7 silane coupler coating layer structure, initial charge capacity 1893.61 mAh/g of material, first charge-discharge efficiency is 71.7%, after 200 circulations, charging capacity is 1201.83 mAh/g, Capacitance reserve, in 1200 mAh/g left and right, has excellent performance.
embodiment 4:
1,0.25g γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 4.75g silica flour ultrasonic mixing 0.5h; At air velocity, be that 200mL/min, temperature are the vacuumize 12h at 10 h, 55 ℃ that refluxes under 80 ℃, magnetic agitation condition, finally obtain mass concentration and be the silicon based anode material of γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane surface modification of 5%.
2, ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.09g aniline monomer and 0.2g modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 ℃, drip hydrochloric acid solution 30 mL of 3.1% percentage by volume that contains 0.0432g ammonium persulfate, carry out in-situ polymerization, polymerization reaction time is 10 h.
3, mixed solution in step 2 is used distilled water and ethanol alternately wash 2-3 time, suction filtration, vacuumize, obtain having the silicon based anode material of silane coupler and conducting polymer double-coated structure, dry with circulating water pump suction filtration final vacuum, vacuumize temperature is 60 ℃, and the vacuumize time is 12 h.
Silicon based anode material cycle performance curve from Fig. 7 silane coupler coating layer structure, initial charge capacity 1797.67 mAh/g of material, first charge-discharge efficiency is 68.9%, after 200 circulations, charging capacity is 1295.05 mAh/g, Capacitance reserve, in 1300 mAh/g left and right, has excellent performance.
embodiment 5:
1,0.25g γ-(methacryloxypropyl) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 4.75g silica flour ultrasonic mixing 0.5h; At air velocity, be that 200mL/min, temperature are the vacuumize 12h at 10 h, 55 ℃ that refluxes under 80 ℃, magnetic agitation condition, finally obtain mass concentration and be the silicon based anode material of γ-(methacryloxypropyl) propyl trimethoxy silicane surface modification of 5%.
2, ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.045 g aniline monomer and 0.2g modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 ℃, drip hydrochloric acid solution 30 mL of 3.1% percentage by volume that contains 0.0216g ammonium persulfate, carry out in-situ polymerization, polymerization reaction time is 10 h.
3, mixed solution in step 2 is used distilled water and ethanol alternately wash 2-3 time, suction filtration, vacuumize, obtain having the silicon based anode material of silane coupler and conducting polymer double-coated structure, dry with circulating water pump suction filtration final vacuum, vacuumize temperature is 60 ℃, and the vacuumize time is 12 h.
4, the silicon based anode material with silane coupler and conducting polymer double-coated structure making in step (3) is added with graphite and mixed with 20% mass fraction ratio, obtain thering is high power capacity, the negative material for lithium ion battery of good circulation performance.
The silicon based anode material cycle performance curve from Fig. 7 with silane coupler and conducting polymer double-coated structure, the initial charge capacity 728.83mAh/g of material, first charge-discharge efficiency is 87.00%, after 200 circulations, charging capacity is 648.43 mAh/g, Capacitance reserve, in 650mAh/g left and right, has excellent performance.
embodiment 6:
1,0.25g γ-(methacryloxypropyl) propyl trimethoxy silicane is mixed in the there-necked flask of 45mL ethanol and 5mL water and is hydrolyzed, add after 4.75g silica flour ultrasonic mixing 0.5h; At air velocity, be that 200mL/min, temperature are the vacuumize 12h at 10 h, 55 ℃ that refluxes under 80 ℃, magnetic agitation condition, finally obtain mass concentration and be the silicon based anode material of γ-(methacryloxypropyl) propyl trimethoxy silicane surface modification of 5%.
2, ultrasonic blend 0.5 h in the hydrochloric acid system of 30mL 3.1% percentage by volume by 0.045 g aniline monomer and 0.2g modification silica flour, ultrasonic power is 1.5w/cm, supersonic frequency is 30kHz, then at 0-5 ℃, drip hydrochloric acid solution 30 mL of 3.1% percentage by volume that contains 0.0216g ammonium persulfate, carry out in-situ polymerization, polymerization reaction time is 10 h.
3, mixed solution in step 2 is used distilled water and ethanol alternately wash 2-3 time, suction filtration, vacuumize, obtain having the silicon based anode material of silane coupler and conducting polymer double-coated structure, dry with circulating water pump suction filtration final vacuum, vacuumize temperature is 60 ℃, and the vacuumize time is 12 h.The mass ratio of copper modification silica flour and aniline is 4:1.
4, the silicon based anode material with silane coupler and conducting polymer double-coated structure making in step (3) is mixed with 50% additional proportion and graphite.
The silicon based anode material cycle performance curve from Fig. 7 with silane coupler and conducting polymer double-coated structure, initial charge capacity 1264.07 mAh/g of material, first charge-discharge efficiency is 77.2%, after 200 circulations, charging capacity is 1083.66 mAh/g, Capacitance reserve, in 1080 mAh/g left and right, has excellent performance.
Comparative example is undressed elemental silicon material.
The test case contrast of each embodiment and comparative example is as shown in table 1.
Table 1
Claims (10)
1. a silicon based anode material with silane coupler and conducting polymer double-coated structure, it is characterized in that described silicon based anode material take elemental silicon as substrate, in substrate, be coated with silane coupler decorative layer, silane coupler decorative layer is coated with protonic acid doping state electrically conductive polyaniline.
2. a preparation method with the silicon based anode material of silane coupler and conducting polymer double-coated structure claimed in claim 1, is characterized in that described method step is as follows:
(1) silane coupler and silica flour are carried out to ultrasonic blend, at 40-120 ℃ of temperature, reflux, silica flour is modified; Wherein: the addition of silane coupler is the 0.01-10% of silica flour mass fraction;
(2) silica flour by aniline monomer and after modifying carries out ultrasonic blend in the acid solution system of Bronsted acid, then adds ammonium persulfate, carries out in-situ polymerization, obtains being coated with the silicon based composite material of conducting polymer; Wherein: the ratio that adds quality of ammonium persulfate and aniline is 1:2-1:4, the silica flour after modification and the mass ratio of aniline are 4:1-1:1;
(3), by described mixed solution washing, suction filtration, vacuumize, obtain having the silicon based anode material of silane coupler and conducting polymer double-coated structure.
3. the preparation method with the silicon based anode material of silane coupler and conducting polymer double-coated structure according to claim 2, the preparation method who it is characterized in that described silica flour is a kind of of vapor phase method, sol-gel processing, the precipitation method, microemulsion method, ball-milling method.
4. according to the preparation method of the silicon based anode material with silane coupler and conducting polymer double-coated structure described in claim 2 or 3, it is characterized in that the particle size interval scope of described silica flour is between 20 to 2000 nm.
5. the preparation method with the silicon based anode material of silane coupler and conducting polymer double-coated structure according to claim 2, it is characterized in that described silane coupler is a kind of of γ-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane, octyltri-ethoxysilane, dimethyldimethoxysil,ne, methyl tributanoximo silane, isocyanic acid propyl-triethoxysilicane.
6. the preparation method with the silicon based anode material of silane coupler and conducting polymer double-coated structure according to claim 2, is characterized in that described return time is 1-24 h.
7. the preparation method with the silicon based anode material of silane coupler and conducting polymer double-coated structure according to claim 2, is characterized in that described Bronsted acid is one or more the mixture in hydrochloric acid, DBSA, camphorsulfonic acid, p-methyl benzenesulfonic acid, pyrovinic acid, normal-butyl/ethyl phosphonic acid, n-decane base phosphoric acid, benzyl phosphoric acid, benzoic acid.
8. the preparation method with the silicon based anode material of silane coupler and conducting polymer double-coated structure according to claim 2, is characterized in that described polymeric reaction temperature is 0-10 ℃, and polymerization reaction time is 4-10 h.
9. the preparation method with the silicon based anode material of silane coupler and conducting polymer double-coated structure according to claim 2, is characterized in that described vacuumize temperature is 45-55 ℃, and the vacuumize time is 10-12 h.
10. the silicon based anode material with silane coupler and conducting polymer double-coated structure claimed in claim 1 is entrained in the application of preparing the negative material of lithium ion battery in graphite.
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