CN103579585B - A kind of anode composite material of lithium sulfur battery and Synthesis and applications thereof - Google Patents
A kind of anode composite material of lithium sulfur battery and Synthesis and applications thereof Download PDFInfo
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Abstract
The present invention relates to a kind of lithium-sulfur cell anode composite material and preparation method thereof, described anode composite material is that be surrounded by the core-shell structure of sulphur in shell, wherein the mass fraction of sulphur is 10-90% with the conducting polymer containing Si-O key for shell.During as lithium sulfur battery anode material, the Si-O key contained because of material itself has the function of " storage capsule ", to the many lithium sulfides formed in battery discharge procedure, there is stronger absorption and releasability, effectively can suppress " effect of shuttling back and forth " of many lithium sulfides, improve cyclical stability and the coulombic efficiency of battery.
Description
Technical field
The present invention relates to electrode material and preparation method thereof, particularly a kind of positive material for lithium-sulfur battery and preparation method thereof.
Background technology
The secondary cell that lithium-sulfur cell is a kind of take lithium metal as negative pole, elemental sulfur is positive pole, its specific energy can reach 2600Wh/kg in theory, actual energy density can reach 300Wh/kg at present, very likely about 600Wh/kg is brought up in the coming years, elemental sulfur positive electrode has abundance, low price, advantages of environment protection simultaneously, is considered to one of secondary cell system of current most research attraction.
But also there is a lot of problem in the development of lithium-sulfur cell.The utilance of positive active material sulphur is not high, and Capacity fading is serious, and (room-temperature conductivity is 5 × 10 to the electrical insulating property of have its source in elemental sulfur and discharging product thereof
-30and " effect of shuttling back and forth " of discharging product S/cm).Therefore, the key improving the performance of lithium-sulfur cell is the conductivity improving elemental sulfur, the dissolving of inhibit activities material, Simultaneous Stabilization metallic lithium surface.Domestic and international worker is mainly studied from aspects such as positive electrode, electrolyte and negative poles.
Domestic Nankai University openly reports a kind of microporous carbon, by hot melt, elemental sulfur is filled in the micropore of material with carbon element, not only solve the insulating properties problem of elemental sulfur, and the cyclical stability of battery is improve by the pore structure utilizing material with carbon element special, circulate 500 times, capability retention still has 650mAh/g-S.But the material with carbon element pore volume prepared due to it is too small, fills sulfur content on the low side, limits its application process.
Chinese patent (application number 200910241977.1) discloses a kind of anode composite material of lithium sulfur battery and preparation method thereof; by the mechanical high-energy ball milling under inert gas shielding and the hot composite algorithm of anoxybiotic; make sulfur-bearing conducting polymer, sulphur positive-active composition and catalysis conductive oxide Homogeneous phase mixing or coated; prepare new sulfur composite positive pole, effectively improve the cycle life performance of lithium-sulfur cell.But because its preparation technology is loaded down with trivial details, limit its development.
External Canadian University of Waterloo (CA) Waterloo, Ontario, N2L3GI Canada has openly reported for work a kind of method improving the cyclical stability of lithium-sulfur cell.Namely in the carbon-sulfur compound prepared, add the material containing silica group, by the weakly stable ability of silicon oxygen bond, suppress shuttling back and forth of many lithium sulfides, improve the cyclical stability of lithium-sulfur cell.But due to the mode that it adopts rear interpolation, make the material containing silica group not be scattered in around carbon-sulfur compound uniformly, limit its development.
To sum up, improve material with carbon element structure to make it to form novel carbon-sulfur compound with sulphur or on the basis of existing carbon-sulfur compound, add adsorbent all can effectively suppress shuttling back and forth of polysulfide, improve the cyclical stability of lithium-sulfur cell, but no matter existing lithium sulfur battery anode material is in the preparation method of product or in commercial value, all have palpus improvements.
The present invention is directed to above-mentioned shortcoming, a kind of novel anode composite material of lithium-sulfur cell is provided, it is to contain the conducting polymer of Si-O key for reaction precursor, under initator effect, while polymerization reaction take place, original position adds elemental sulfur, the compound of obtained carbon bag sulphur, then through protonated processing procedure, positive pole carbon sulphur composite material is finally obtained.It is used as lithium sulfur battery anode material time, its first discharge capacity be greater than 1000mAh/g-S, circulate 50 times, discharge capacitance is greater than 94%.
Summary of the invention
The object of the present invention is to provide anode composite material of a kind of lithium-sulfur cell and preparation method thereof, can effectively suppress the dissolving of polysulfide to be shuttled back and forth, improve the starting point of the cyclical stability of battery,
For achieving the above object, the technical solution used in the present invention is:
A kind of for lithium-sulphur cell positive electrode conducting polymer-sulphur composite material and preparation method thereof, described anode composite material is for shell with the conducting polymer containing Si-O key, be surrounded by the core-shell structure of sulphur in shell, wherein the mass fraction of sulphur is 10-90%, is obtained by following preparation process:
(1) will containing-CH
2five yuan of OH group or hexa-atomic aromatic compound mix with the ratio that esters of silicon acis is greater than 0 to≤1 in molar ratio, form clear solution A after fully dissolving;
(2) in solution A, add aqueous slkali, adjustment pH value 7-9, makes it to generate product B;
(3) by product B decompression distillation 30s-5h under 100-150 DEG C of condition, product C is obtained;
(4) product C is joined in the mixed solution of substituted benzene and linear paraffin, recrystallization under-10 ~-20 DEG C of conditions, obtain product D, wherein the mixed solution of the preferred toluene of the mixed solution of substituted benzene and linear paraffin and n-hexane, its volume ratio (0.01-1): 1;
(5) product D is obtained the conducting polymer monomer of product E containing Si-O key after linear paraffin washing, drying;
(6) be dissolved in solvent by product E, mix under 0 DEG C-room temperature condition, forming solution F(concentration is 1% ~ 80%), wherein solvent is one or more mixtures in water, ethanol, chloroform, toluene;
(7) get elemental sulfur, surfactant, initator be dissolved in the solvent in step (6), form solution G after stirring 10-60min, concentration is 0.1-90%;
(8) solution F is slowly added in solution G, stir 5-24h under 0 DEG C-room temperature condition, filtration drying, obtain pressed powder H;
Wherein the mass ratio of product E, elemental sulfur, surfactant, initator is 1:(1 ~ 5): (0.1-1): (0.1 ~ 5);
(9), after powder H being soaked 10-48h in acid solution, filtration drying, obtains described anode composite material.
Described containing-CH
2the conducting polymer monomer of OH is containing 1 ~ 2-CH on aromatic ring
2five yuan or the hexa-atomic aromatic compound of OH.Described the best containing-CH
2the conducting polymer monomer of OH is the one in thenyl alcohol, aniline alcohol, pyrroles's alcohol and acetylene alcohol.Described esters of silicon acis is one in tetraethoxysilane or methyl silicate or two kinds of mixtures; Described alkali lye is NaOH solution, KOH solution, Na
2cO
3solution, NaHCO
3solution, NH
3water, (NH
4)
2cO
3one in solution; Described diluted acid is the one in sulfuric acid, nitric acid, phosphoric acid or hydrochloric acid.Described initator is one in hydrogen peroxide, ferric trichloride, sodium thiosulfate or two kinds of mixtures.Described surfactant to be described surfactant be styrene (PS)/butadiene (PB)/styrene (PS), poly(ethylene oxide)-PPOX-poly(ethylene oxide), cetyl amine bromide one or two or more kinds.
The application of described composite material is lithium-sulphur cell positive electrode.
Compared with prior art, tool of the present invention has the following advantages:
(1) employ cheap reaction monomers, product cost is low;
(2) namely Si-O key is contained in reaction monomers, avoid the problems such as the skewness that rear interpolation brings, " storage capsule " function itself had, to the many lithium sulfides formed in battery discharge procedure, there is stronger absorption and releasability, can effectively suppress " effect of shuttling back and forth " of many lithium sulfides, improve cyclical stability and the coulombic efficiency of battery, for the cyclical stability improving battery provides guarantee;
(3) add elemental sulfur at the process situ preparing electric conducting material, make it evenly be coated on the inside of electric conducting material.Not only effectively achieve the high degree of dispersion of elemental sulfur, improve the discharge capacity of battery, discharging product can also be made effectively to be fixed in the skeleton of electric conducting material, suppress the self-discharge phenomenon of battery, improve the cyclical stability of battery.
(4) conducting polymer-sulphur nano material that prepared by the present invention has higher utilization efficiency and good cyclical stability.Discharge capacity is greater than 1000mAh/g-S, and after circulation 50 circle, discharge capacitance is greater than 94%.
(5) preparation process of the present invention is simple, low in raw material price, and therefore prepared conducting polymer-sulphur composite material is conducive to large-scale application in lithium-sulfur rechargeable battery anode material.
Accompanying drawing and explanation thereof
Fig. 1 is the first circle charging and discharging curve (discharge-rate 0.1C) of conducting polymer-sulfur compound prepared by embodiment 1.
Fig. 2 is the stability test curve of anode composite material circulation 50 circle prepared by embodiment 1, and discharge electric close 0.1C.
Embodiment
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
The ratio being 10:1 in molar ratio by thenyl alcohol and tetraethoxysilane mixes, and stirring at room temperature, makes it fully dissolve, and forms clear solution A; In solution A, add the sodium hydroxide solution of 2M, continue to stir, adjustment pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B-0.1MPa decompression distillation 5h under 100 DEG C of conditions, obtain product C; Product C joined in the mixed solution (V: V=10:1) of toluene and n-hexane, recrystallization under-10 DEG C of conditions, obtains product D; By product D through n-hexane 3 times, after vacuumize, obtain product E; Pressed powder E is dissolved in ethanol (solution concentration is 1%), mixes under 0 DEG C of condition, form solution F; Get elemental sulfur, cetyl amine bromide (CTAB), ferric trichloride in mass ratio for the ratio of 1:1:0.1:1 is dissolved in ethanol (solution concentration is 0.1%), after stirring 10min, form solution G; Slowly added by solution F in solution G, stir 5h under 0 DEG C of condition, filtration, cleaning, drying, obtain pressed powder H; After powder H is soaked 10h in the hydrochloric acid solution of 2M, filtration, cleaning, drying, obtain conducting polymer-sulphur composite material prepared by the present invention.Be that 90:10 is at N in mass ratio by the anode composite material obtained, PVDF, in dinethylformamide (NMP) solution (solid content is 10%) ultrasonic mix after, blade coating is on aluminium foil, obtain homemade lithium sulfur battery anode material (1#C-S), this material has higher utilization efficiency and excellent cyclical stability.By the positive electrode assembling button cell prepared, under room temperature condition, 0.1C electric discharge, is 1.5V-2.8V by voltage, test battery chemical property.As seen from Figure 1, conducting polymer prepared by the present invention-sulfur compound first circle discharge capacity can reach 1042mAh/g-S, and the utilance of elemental sulfur is 62%.Therefore, the lithium sulfur battery anode material prepared by the present invention has higher utilization efficiency.As seen from Figure 2, conducting polymer prepared by the present invention-sulphur composite material is after 50 circle circulations, and the capability retention of battery is 94%, and substantially remains unchanged.Therefore, the lithium sulfur battery anode material prepared by the present invention has excellent cyclical stability.
Embodiment 2
The ratio being 1:1 in molar ratio by aniline alcohol and methyl silicate mixes, and stirring at room temperature, makes it fully dissolve, and forms clear solution A; In solution A, add 0.2M sodium hydroxide solution, continue to stir, adjustment pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B-0.1MPa decompression distillation 5h under 150 DEG C of conditions, obtain product C; Product C joined in the mixed solution (V: V=1:1) of toluene and n-hexane, recrystallization under-10 DEG C of conditions, obtains product D; By product D through n-hexane 5 times, after vacuumize, obtain product E; By soluble in water for pressed powder E, mix under 0 DEG C of condition, forming solution F(solution concentration is 80%); Get elemental sulfur, poly(ethylene oxide)-PPOX-poly(ethylene oxide), ammonium persulfate in mass ratio for the ratio of 1:5:1:5 is dissolved in the solvent in step (6), after stirring 10min, form solution G; Slowly added by solution F (solution concentration is 90%) in solution G, stir 5h under 0 DEG C of condition, filtration, cleaning, drying, obtain pressed powder H; After powder H is soaked 10h in dilute hydrochloric acid solution, filtration, cleaning, drying, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtained, PVDF in mass ratio for 90:10 in nmp solution, (solid content is 8%) is ultrasonic mix after, blade coating, on aluminium foil, obtains homemade lithium sulfur battery anode material (2#C-S).
Embodiment 3
The ratio being 10:1 in molar ratio by aniline alcohol and tetraethoxysilane mixes, and stirring at room temperature, makes it fully dissolve, and forms clear solution A; In solution A, add 0.1M sodium bicarbonate solution, continue to stir, adjustment pH value is 9, makes it to generate the liquid-solid product B of yellowish orange; By product B-0.1MPa decompression distillation 5h under 150 DEG C of conditions, obtain product C; Product C joined in the mixed solution (V: V=1:1) of toluene and n-hexane, recrystallization under-10 DEG C of conditions, obtains product D; By product D through n-hexane 5 times, after vacuumize, obtain product E; By soluble in water for pressed powder E, mix under 0 DEG C of condition, forming solution F(solution concentration is 10%); Get elemental sulfur, poly(ethylene oxide)-PPOX-poly(ethylene oxide), hydrogen peroxide in mass ratio for the ratio of 1:5:1:8 is dissolved in the solvent in step (6), after stirring 30min, form solution G; Slowly added by solution F (solution concentration is 10%) in solution G, stir 5h under 0 DEG C of condition, filtration, cleaning, drying, obtain pressed powder H; After powder H is soaked 10h in dilute hydrochloric acid solution, filtration, cleaning, drying, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtained, PVDF in mass ratio for 90:10 in nmp solution, (solid content is 8%) is ultrasonic mix after, blade coating, on aluminium foil, obtains homemade lithium sulfur battery anode material (3#C-S).
Embodiment 4
The ratio being 10:1 in molar ratio by pyrroles's alcohol and tetraethoxysilane mixes, and stirring at room temperature, makes it fully dissolve, and forms clear solution A; In solution A, add 1M sodium bicarbonate solution, continue to stir, adjustment pH value is 9, makes it to generate the liquid-solid product B of yellowish orange; By product B-0.1MPa decompression distillation 5h under 150 DEG C of conditions, obtain product C; Product C joined in the mixed solution (V: V=1:1) of toluene and n-hexane, recrystallization under-10 DEG C of conditions, obtains product D; By product D through n-hexane 5 times, after vacuumize, obtain product E; By soluble in water for pressed powder E, mix under 0 DEG C of condition, forming solution F(solution concentration is 50%); Get elemental sulfur, poly(ethylene oxide)-PPOX-poly(ethylene oxide), hydrogen peroxide in mass ratio for the ratio of 1:5:1:0.1 is dissolved in the solvent in step (6), after stirring 30min, form solution G; Slowly added by solution F (solution concentration is 30%) in solution G, stir 5h under 0 DEG C of condition, filtration, cleaning, drying, obtain pressed powder H; After powder H is soaked 10h in dilute hydrochloric acid solution, filtration, cleaning, drying, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtained, PVDF in mass ratio for 90:10 in nmp solution, (solid content is 5%) is ultrasonic mix after, blade coating, on aluminium foil, obtains homemade lithium sulfur battery anode material (4#C-S).
Embodiment 5
The ratio being 1:1 in molar ratio by aniline alcohol and tetraethoxysilane mixes, and stirring at room temperature, makes it fully dissolve, and forms clear solution A; In solution A, add 0.1M sodium hydroxide solution, continue to stir, adjustment pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B-0.1MPa decompression distillation 5h under 100 DEG C of conditions, obtain product C; Product C joined in the mixed solution (V:V=10:1) of toluene and n-hexane, recrystallization under-10 DEG C of conditions, obtains product D; By product D through n-hexane 3 times, after vacuumize, obtain product E; Be dissolved in ethanol by pressed powder E, mix under 0 DEG C of condition, forming solution F(solution concentration is 5%); Get elemental sulfur, cetyl amine bromide (CTAB), hydrogen peroxide in mass ratio for the ratio of 1:1:0.1:1 is dissolved in the solvent in step (6), forming solution G(solution concentration after stirring 10min is 10%); Slowly added by solution F in solution G, stir 5h under 0 DEG C of condition, filtration, cleaning, drying, obtain pressed powder H; After powder H is soaked 10h in dilute hydrochloric acid solution, filtration, cleaning, drying, obtain conducting polymer-sulphur composite material prepared by the present invention.Be that 80:20 is at N in mass ratio by the anode composite material obtained, PVDF, in dinethylformamide (NMP) solution, (solid content is 10%) is ultrasonic mix after, blade coating, on aluminium foil, obtains homemade lithium sulfur battery anode material (5#C-S).
Embodiment 6
The ratio being 1:1 in molar ratio by pyrroles's alcohol and methyl silicate mixes, and stirring at room temperature, makes it fully dissolve, and forms clear solution A; In solution A, add 0.5M potassium hydroxide solution, continue to stir, adjustment pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B-0.1MPa decompression distillation 5h under 100 DEG C of conditions, obtain product C; Product C joined in the mixed solution (V: V=1:1) of toluene and n-hexane, recrystallization under-10 DEG C of conditions, obtains product D; By product D through n-hexane 5 times, after vacuumize, obtain product E; By soluble in water for pressed powder E, mix under room temperature condition, forming solution F(solution concentration is 10%); Get elemental sulfur, poly(ethylene oxide)-PPOX-poly(ethylene oxide), hydrogen peroxide in mass ratio for the ratio of 1:1:0.1:1 is dissolved in the solvent in step (6), forming solution G(solution concentration after stirring 30min is 20%); Slowly added by solution F in solution G, stir 24h under 0 DEG C of condition, filtration, cleaning, drying, obtain pressed powder H; After powder H is soaked 48h in dilute hydrochloric acid solution, filtration, cleaning, drying, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtained, PVDF in mass ratio for 90:10 in nmp solution, (solid content is 15%) is ultrasonic mix after, blade coating, on aluminium foil, obtains homemade lithium sulfur battery anode material (6#C-S).
Embodiment 7
The ratio being 1:1 in molar ratio by acetylene alcohol and methyl silicate mixes, and stirring at room temperature, makes it fully dissolve, and forms clear solution A; In solution A, add 0.1M potassium hydroxide solution, continue to stir, adjustment pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B-0.1MPa decompression distillation 5h under 100 DEG C of conditions, obtain product C; Product C joined in the mixed solution (V: V=1:1) of toluene and n-hexane, recrystallization under-10 DEG C of conditions, obtains product D; By product D through n-hexane 5 times, after vacuumize, obtain product E; By soluble in water for pressed powder E, mix under room temperature condition, forming solution F(solution concentration is 5%); Get elemental sulfur, poly(ethylene oxide)-PPOX-poly(ethylene oxide), hydrogen peroxide in mass ratio for the ratio of 1:1:0.1:1 is dissolved in the solvent in step (6), forming solution G(solution concentration after stirring 30min is 5%); Slowly added by solution F in solution G, stir 24h under 0 DEG C of condition, filtration, cleaning, drying, obtain pressed powder H; After powder H is soaked 48h in dilute hydrochloric acid solution, filtration, cleaning, drying, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtained, PVDF in mass ratio for 90:10 in nmp solution, (solid content is 10%) is ultrasonic mix after, blade coating, on aluminium foil, obtains homemade lithium sulfur battery anode material (7#C-S).
Embodiment 8
The ratio being 1:1 in molar ratio by aniline alcohol and tetraethoxysilane mixes, and stirring at room temperature, makes it fully dissolve, and forms clear solution A; In solution A, add 0.5M sodium hydroxide solution, continue to stir, adjustment pH value is 9, makes it to generate the liquid-solid product B of yellowish orange; By product B-0.1MPa decompression distillation 5h under 100 DEG C of conditions, obtain product C; Product C joined in the mixed solution (V:V=10:1) of toluene and n-hexane, recrystallization under-20 DEG C of conditions, obtains product D; By product D through n-hexane 3 times, after vacuumize, obtain product E; Be dissolved in ethanol by pressed powder E, mix under 0 DEG C of condition, forming solution F(solution concentration is 10%); Get elemental sulfur, cetyl amine bromide (CTAB), ammonium persulfate in mass ratio for the ratio of 1:1:0.1:1 is dissolved in the solvent in step (6), forming solution G(solution concentration after stirring 60min is 10%); Slowly added by solution F in solution G, stir 5h under 0 DEG C of condition, filtration, cleaning, drying, obtain pressed powder H; After powder H is soaked 48h in dilute hydrochloric acid solution, filtration, cleaning, drying, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtained, PVDF in mass ratio for 90:10 in DMF (NMP) solution, (solid content is 10%) is ultrasonic mix after, blade coating, on aluminium foil, obtains homemade lithium sulfur battery anode material (8#C-S).
Embodiment 9
The ratio being 10:1 in molar ratio by acetylene alcohol and methyl silicate mixes, and stirring at room temperature, makes it fully dissolve, and forms clear solution A; In solution A, add 0.1M sodium hydroxide solution, continue to stir, adjustment pH value is 9, makes it to generate the liquid-solid product B of yellowish orange; By product B-0.1MPa decompression distillation 5h under 100 DEG C of conditions, obtain product C; Product C joined in the mixed solution (V:V=10:1) of toluene and n-hexane, recrystallization under-20 DEG C of conditions, obtains product D; By product D through n-hexane 3 times, after vacuumize, obtain product E; Be dissolved in ethanol by pressed powder E, mix under 0 DEG C of condition, forming solution F((solution concentration is 10%); Get elemental sulfur, ratio that styrene (PS)/butadiene (PB)/styrene (PS), hydrogen peroxide mass ratio are 1:1:0.1:1 is dissolved in the solvent in step (6), forming solution G(solution concentration after stirring 60min is 10%); Slowly added by solution F in solution G, stir 5h under 0 DEG C of condition, filtration, cleaning, drying, obtain pressed powder H; After powder H is soaked 48h in dilute hydrochloric acid solution, filtration, cleaning, drying, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtained, PVDF in mass ratio for 80:20 in DMF (NMP) solution, (solid content is 10%) is ultrasonic mix after, blade coating, on aluminium foil, obtains homemade lithium sulfur battery anode material (9#C-S).
Embodiment 10
The ratio being 10:1 in molar ratio by thenyl alcohol and methyl silicate mixes, and stirring at room temperature, makes it fully dissolve, and forms clear solution A; In solution A, add 0.5M sodium hydroxide solution, continue to stir, adjustment pH value is 9, makes it to generate the liquid-solid product B of yellowish orange; By product B-0.1MPa decompression distillation 5h under 100 DEG C of conditions, obtain product C; Product C joined in the mixed solution (V:V=10:1) of benzene and normal heptane, recrystallization under-20 DEG C of conditions, obtains product D; By product D through n-hexane 3 times, after vacuumize, obtain product E; Be dissolved in ethanol by pressed powder E, mix under 0 DEG C of condition, forming solution F(solution concentration is 60%); Get elemental sulfur, ratio that styrene (PS)/butadiene (PB)/styrene (PS), ferric trichloride mass ratio are 1:1:0.1:1 is dissolved in the solvent in step (6), forming solution G(solution concentration after stirring 60min is 50%); Slowly added by solution F in solution G, stir 5h under 0 DEG C of condition, filtration, cleaning, drying, obtain pressed powder H; After powder H is soaked 48h in dilute hydrochloric acid solution, filtration, cleaning, drying, obtain conducting polymer-sulphur composite material prepared by the present invention.Be that 80:20 is at N in mass ratio by the anode composite material obtained, PVDF, in dinethylformamide (NMP) solution, (solid content is 10%) is ultrasonic mix after, blade coating, on aluminium foil, obtains homemade lithium sulfur battery anode material (10#C-S).
Embodiment 11
The ratio being 1:1 in molar ratio by thenyl alcohol and tetraethoxysilane mixes, and stirring at room temperature, makes it fully dissolve, and forms clear solution A; In solution A, add 1M sodium hydroxide solution, continue to stir, adjustment pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B-0.09MPa decompression distillation 30s under 100 DEG C of conditions, obtain product C; Product C joined in the mixed solution (V: V=1:1) of toluene and n-hexane, recrystallization under-10 DEG C of conditions, obtains product D; By product D through n-hexane 5 times, after vacuumize, obtain product E; By soluble in water for pressed powder E, mix under 0 DEG C of condition, forming solution F(solution concentration is 50%); Get elemental sulfur, CTAB, ferric trichloride in mass ratio for the ratio of 1:5:1:8 is dissolved in the solvent in step (6), after stirring 10min, form solution G; Slowly added by solution F (solution concentration is 70%) in solution G, stir 5h under 0 DEG C of condition, filtration, cleaning, drying, obtain pressed powder H; After powder H is soaked 10h in dilute hydrochloric acid solution, filtration, cleaning, drying, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtained, PVDF in mass ratio for 90:10 in nmp solution, (solid content is 10%) is ultrasonic mix after, blade coating, on aluminium foil, obtains homemade lithium sulfur battery anode material (11#C-S).
Claims (9)
1. lithium-sulfur cell anode composite material, is characterized in that:
Described anode composite material is that be surrounded by the core-shell structure of sulphur in shell, wherein the mass fraction of sulphur is 10-90% with the conducting polymer containing Si-O key for shell;
The described conducting polymer containing Si-O key is to contain CH
2five yuan or hexa-atomic aromatic compound thenyl alcohols, aniline alcohol, pyrroles's alcohol or acetylene alcohols of OH group are that monomer polymerization forms.
2. according to anode composite material described in claim 1, it is characterized in that: described anode composite material is prepared from according to the following procedure,
(1) will containing-CH
2five yuan of OH group or hexa-atomic aromatic compound mix with the ratio that esters of silicon acis is greater than 0 to≤1 in molar ratio, form clear solution A after fully dissolving;
(2) in solution A, add aqueous slkali, adjustment pH value 7-9, makes it to generate product B;
(3) by product B decompression distillation 30s-5h under 100-150 DEG C of condition, product C is obtained;
(4) product C joined in the mixed solution of substituted benzene and linear paraffin, recrystallization under-10 ~-20 DEG C of conditions, obtains product D, wherein the mixed solution of substituted benzene and linear paraffin, and its volume ratio is (0.01-1): 1;
(5) product D is obtained the conducting polymer monomer of product E containing Si-O key after linear paraffin washing, drying;
(6) be dissolved in solvent by product E, mix under 0 DEG C-room temperature condition, form solution F, the mass concentration of its solute is 1% ~ 80%, and wherein solvent is one or more mixtures in water, ethanol, chloroform, toluene;
(7) get elemental sulfur, surfactant, initator be dissolved in the solvent in step (6), form solution G after stirring 10-60min, the mass concentration of solute is 0.1-90%;
(8) solution F is slowly added in solution G, stir 5-24h under 0 DEG C-room temperature condition, filtration drying, obtain pressed powder H;
Wherein the mass ratio of product E, elemental sulfur, surfactant, initator is 1:(1 ~ 5): (0.1-1): (0.1 ~ 5);
(9), after powder H being soaked 10-48h in acid solution, filtration drying, obtains described anode composite material.
3. according to anode composite material described in claim 2, it is characterized in that: the mixed solution of substituted benzene and linear paraffin described in step (4) is the mixed solution of toluene and n-hexane.
4. according to anode composite material described in claim 2, it is characterized in that: described containing-CH
2five yuan or the preferred thenyl alcohol of hexa-atomic aromatic compound, aniline alcohol, pyrroles's alcohol or acetylene alcohol of OH group.
5., according to anode composite material according to claim 2, it is characterized in that:
Described esters of silicon acis is one in tetraethoxysilane or methyl silicate or two kinds of mixtures;
Described aqueous slkali is NaOH solution, KOH solution, Na
2cO
3solution, NaHCO
3solution, NH
3water, (NH
4)
2cO
3one in solution;
To be concentration be is less than the sulfuric acid of 2M, nitric acid, phosphoric acid or hydrochloric acid solution in described acid.
6., according to anode composite material according to claim 2, it is characterized in that:
Described initator is one or two or more kinds in hydrogen peroxide, ferric trichloride, sodium thiosulfate;
Described surfactant be styrene (PS)/butadiene (PB)/styrene (PS), poly(ethylene oxide)-PPOX-poly(ethylene oxide), cetyl amine bromide one or two or more kinds.
7. a preparation method for anode composite material described in claim 1, is characterized in that: described preparation method is with the conducting polymer containing Si-O key for precursors, and the composite material of obtained polymer bag sulphur, is then prepared from through protonated processing procedure;
Its concrete preparation process is:
(1) will containing-CH
2five yuan of OH group or hexa-atomic aromatic compound mix with the ratio that esters of silicon acis is greater than 0 to≤1 in molar ratio, form clear solution A after fully dissolving;
(2) in solution A, add aqueous slkali, adjustment pH value 7-9, makes it to generate product B;
(3) by product B decompression distillation 30s-5h under 100-150 DEG C of condition, product C is obtained;
(4) product C joined in the mixed solution of substituted benzene and linear paraffin, recrystallization under-10 ~-20 DEG C of conditions, obtains product D, wherein the mixed solution of substituted benzene and linear paraffin, its volume ratio (0.01-1): 1;
(5) product D is obtained the conducting polymer monomer of product E containing Si-O key after linear paraffin washing, drying;
(6) be dissolved in solvent by product E, mix under 0 DEG C-room temperature condition, form solution F, its mass concentration is 1% ~ 80%, and wherein solvent is one or more mixtures in water, ethanol, chloroform, toluene;
(7) get elemental sulfur, surfactant, initator be dissolved in the solvent in step (6), form solution G after stirring 10-60min, mass concentration is 0.1-90%;
(8) solution F is slowly added in solution G, stir 5-24h under 0 DEG C-room temperature condition, filtration drying, obtain pressed powder H;
Wherein the mass ratio of product E, elemental sulfur, surfactant, initator is 1:(1 ~ 5): (0.1-1): (0.1 ~ 5);
(9), after powder H being soaked 10-48h in acid solution, filtration drying, obtains described anode composite material.
8. preparation method according to claim 7, is characterized in that: the mixed solution of substituted benzene and linear paraffin described in step (4) is the mixed solution of toluene and n-hexane.
9. an application for anode composite material described in claim 1, is characterized in that: described composite material is applied to lithium-sulphur cell positive electrode.
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| CN106374095B (en) * | 2016-11-08 | 2019-02-22 | 太原理工大学 | A kind of preparation method of the composite material as lithium sulfur battery anode material |
| CN110993902B (en) * | 2019-11-12 | 2023-02-14 | 东北师范大学 | Lithium-sulfur battery with positively charged organic small molecule positive electrode additive |
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| CN101740754A (en) * | 2009-12-16 | 2010-06-16 | 北京理工大学 | Preparation method of composite anode material for lithium element sulphur secondary battery |
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| CN101740754A (en) * | 2009-12-16 | 2010-06-16 | 北京理工大学 | Preparation method of composite anode material for lithium element sulphur secondary battery |
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| "Stabilizing lithium-sulphur cathodes using polysulphide reservoirs";Xiulei Ji et al;《Nature cammunications》;20110524;第2卷;第326页左栏第1段至右栏第1段，第328页右栏第1段至第330页左栏第1段 * |
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