CN103579585A - Lithium-sulfur cell anode composite material and its preparation method and use - Google Patents
Lithium-sulfur cell anode composite material and its preparation method and use Download PDFInfo
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Abstract
The invention relates to a lithium-sulfur cell anode composite material and a preparation method thereof. The lithium-sulfur cell anode composite material is a shell-core structure comprising a Si-O bond-containing conducting polymer as a shell and sulfur in the shell, and the sulfur content is in a range of 10-90wt%. Through the Si-O bond having reception bag functions, the lithium-sulfur cell anode composite material has a strong capability of adsorption and release of lithium polysulfide produced by in cell charging and discharging, can effectively inhibit tunneling effects of lithium polysulfide and can improve cell cycling stability and coulombic efficiency.
Description
Technical field
The present invention relates to electrode material and preparation method thereof, particularly positive electrode and preparation method thereof for a kind of lithium-sulfur cell.
Background technology
Lithium-sulfur cell be a kind of take lithium metal as negative pole, elemental sulfur be anodal secondary cell, its specific energy can reach 2600Wh/kg in theory, actual energy density can reach 300Wh/kg at present, in the coming years, very likely bring up to 600Wh/kg left and right, simultaneously elemental sulfur positive electrode have that source is abundant, low price, advantages of environment protection, be considered to one of secondary cell system of current tool research attraction.
Yet also there are a lot of problems 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
-30s/cm) and " effect of shuttling back and forth " of discharging product.Therefore, the key that improves the performance of lithium-sulfur cell is to improve the conductivity of elemental sulfur, suppresses the dissolving of active material, Simultaneous Stabilization lithium metal surface.Worker is mainly studied from aspects such as positive electrode, electrolyte and negative poles both at home and abroad.
Domestic Nankai University has openly reported a kind of microporous carbon, by hot melt, elemental sulfur is filled in the micropore of material with carbon element, not only solved the insulating properties problem of elemental sulfur, and by the special pore structure of utilizing material with carbon element, improved the cyclical stability of battery, circulate 500 times, capability retention still has 650mAh/g-S.But because its material with carbon element pore volume of preparing is too small, fill sulfur content on the low side, limited 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, the anodal active component of sulphur and catalysis conductive oxide evenly mix or be coated; prepare novel sulphur composite positive pole, effectively improved the cycle life performance of lithium-sulfur cell.But because its preparation technology is loaded down with trivial details, limited its development.
External Canadian University of Waterloo (CA) Waterloo, Ontario, N2L3GI Canada a kind of method that improves the cyclical stability of lithium-sulfur cell of openly having reported for work.In the carbon-sulfur compound preparing, add the material that contains silica group, the weak adsorption capacity by silicon oxygen bond, suppresses shuttling back and forth of many lithium sulfides, improves the cyclical stability of lithium-sulfur cell.But due to its mode that adopts rear interpolation, make the material that contains silica group not be scattered in uniformly carbon-sulfur compound around, limited its development.
To sum up, improving material with carbon element structure makes it form novel carbon-sulfur compound with sulphur or on the basis of existing carbon-sulfur compound, add adsorbent and 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 aspect commercial value, all there are 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 take containing the conducting polymer of Si-O key is reaction precursor, under initator effect, in polymerization reaction take place, original position is added elemental sulfur, make the compound of carbon bag sulphur, then through protonated processing procedure, finally obtain anodal carbon sulphur composite material.Its when the lithium sulfur battery anode material, 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 and shuttle 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 that the conducting polymer of take containing Si-O key is shell, in shell, be surrounded by the core-shell structure of sulphur, wherein the mass fraction of sulphur is 10-90%, by being prepared as follows process, obtains:
(1) will be containing-CH
2five yuan of OH group or hexa-atomic aromatic compound and esters of silicon acis are greater than 0 to≤1 ratio in molar ratio to be mixed, and after fully dissolving, forms clear solution A;
(2) in solution A, add aqueous slkali, adjust pH value 7-9, make it to generate product B;
(3) by product B decompression distillation 30s-5h under 100-150 ℃ of condition, obtain product C;
(4) product C is joined in the mixed solution of substituted benzene and linear paraffin, recrystallization under-10 ~-20 ℃ of conditions, obtain product D, the mixed solution of the preferred toluene of the mixed solution of substituted benzene and linear paraffin and n-hexane wherein, its volume ratio (0.01-1): 1;
(5) product D after washing, be dried, linear paraffin is obtained to product E containing the conducting polymer monomer of Si-O key;
(6) product E is dissolved in solvent, under 0 ℃-room temperature condition, mixes, 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 and 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, under 0 ℃-room temperature condition, stir 5-24h, filtration drying, obtains 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) powder H is soaked after 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.Contain-the CH of described the best
2the conducting polymer monomer of OH is a kind of in thenyl alcohol, aniline alcohol, pyrroles's alcohol and acetylene alcohol.Described esters of silicon acis is a kind of or two kinds of mixtures in tetraethoxysilane or methyl silicate; Described alkali lye is NaOH solution, KOH solution, Na
2cO
3solution, NaHCO
3solution, NH
3water, (NH
4)
2cO
3a kind of in solution; Described diluted acid is a kind of in sulfuric acid, nitric acid, phosphoric acid or hydrochloric acid.Described initator is a kind of or two kinds of mixtures in hydrogen peroxide, ferric trichloride, sodium thiosulfate.Described surfactant 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) used cheap reaction monomers, product cost is low;
(2) in reaction monomers, contain Si-O key, the problems such as skewness of having avoided rear interpolation to bring, " taking in capsule " function itself having, the many lithium sulfides that form in battery discharge procedure are had to stronger absorption and releasability, " effect of shuttling back and forth " that can effectively suppress many lithium sulfides, improve cyclical stability and coulomb efficiency of battery, for improving the cyclical stability of battery, provide guarantee;
(3) at the process situ of preparing electric conducting material, add elemental sulfur, make it evenly be coated on the inside of electric conducting material.Not only effectively realize the high degree of dispersion of elemental sulfur, improved the discharge capacity of battery, can also make discharging product effectively be fixed in the skeleton of electric conducting material, suppressed the self-discharge phenomenon of battery, improved 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, circulates after 50 circles, and discharge capacitance is greater than 94%.
(5) preparation process of the present invention is simple, and cost of material is cheap, 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 the conducting polymer-sulfur compound of embodiment 1 preparation.
Fig. 2 is the stability test curve of anode composite material circulation 50 circles of embodiment 1 preparation, and electric close 0.1C discharges.
Embodiment
Below by embodiment, the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
By thenyl alcohol with tetraethoxysilane in molar ratio for the ratio of 10:1 is mixed, stirring at room, fully dissolves it, forms clear solution A; To the sodium hydroxide solution that adds 2M in solution A, continue to stir, adjusting pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B under 100 ℃ of conditions-0.1MPa decompression distillation 5h, obtain product C; Product C is joined to the mixed solution (V: V=10:1), recrystallization under-10 ℃ of conditions, obtains product D of toluene and n-hexane; Product D, through n-hexane washing 3 times, is obtained to product E after vacuumize; Pressed powder E is dissolved in ethanol (solution concentration is 1%), under 0 ℃ of condition, mixes, 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; Solution F is slowly added in solution G, under 0 ℃ of condition, stir 5h, filter, clean, be dried, obtain pressed powder H; Powder H is soaked after 10h in the hydrochloric acid solution of 2M, filter, clean, be dried, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtaining, PVDF, be that 90:10 is at N in mass ratio, in dinethylformamide (NMP) solution (solid content is 10%) after ultrasonic mixing, blade coating is to 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 preparing, 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-sulfur compound first circle discharge capacity prepared by the present invention can reach 1042mAh/g-S, and the utilance of elemental sulfur is 62%.Therefore the lithium sulfur battery anode material of, preparing by the present invention has higher utilization efficiency.As seen from Figure 2, conducting polymer-sulphur composite material prepared by the present invention is after 50 circle circulations, and the capability retention of battery is 94%, and substantially remains unchanged.Therefore the lithium sulfur battery anode material of, preparing by the present invention has excellent cyclical stability.
Embodiment 2
By aniline alcohol with methyl silicate in molar ratio for the ratio of 1:1 is mixed, stirring at room, fully dissolves it, forms clear solution A; In solution A, add 0.2M sodium hydroxide solution, continue to stir, adjusting pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B under 150 ℃ of conditions-0.1MPa decompression distillation 5h, obtain product C; Product C is joined to the mixed solution (V: V=1:1), recrystallization under-10 ℃ of conditions, obtains product D of toluene and n-hexane; Product D, through n-hexane washing 5 times, is obtained to product E after vacuumize; Pressed powder E is soluble in water, under 0 ℃ of condition, mix, 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; Solution F is slowly added to (solution concentration is 90%) in solution G, under 0 ℃ of condition, stir 5h, filter, clean, be dried, obtain pressed powder H; Powder H is soaked after 10h in dilute hydrochloric acid solution, filter, clean, be dried, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtaining, PVDF, in mass ratio for 90:10 is in nmp solution after (solid content is 8%) ultrasonic mixing, blade coating, to aluminium foil, obtains homemade lithium sulfur battery anode material (2#C-S).
Embodiment 3
By aniline alcohol with tetraethoxysilane in molar ratio for the ratio of 10:1 is mixed, stirring at room, fully dissolves it, forms clear solution A; In solution A, add 0.1M sodium bicarbonate solution, continue to stir, adjusting pH value is 9, makes it to generate the liquid-solid product B of yellowish orange; By product B under 150 ℃ of conditions-0.1MPa decompression distillation 5h, obtain product C; Product C is joined to the mixed solution (V: V=1:1), recrystallization under-10 ℃ of conditions, obtains product D of toluene and n-hexane; Product D, through n-hexane washing 5 times, is obtained to product E after vacuumize; Pressed powder E is soluble in water, under 0 ℃ of condition, mix, 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; Solution F is slowly added to (solution concentration is 10%) in solution G, under 0 ℃ of condition, stir 5h, filter, clean, be dried, obtain pressed powder H; Powder H is soaked after 10h in dilute hydrochloric acid solution, filter, clean, be dried, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtaining, PVDF, in mass ratio for 90:10 is in nmp solution after (solid content is 8%) ultrasonic mixing, blade coating, to aluminium foil, obtains homemade lithium sulfur battery anode material (3#C-S).
Embodiment 4
By pyrroles's alcohol with tetraethoxysilane in molar ratio for the ratio of 10:1 is mixed, stirring at room, fully dissolves it, forms clear solution A; In solution A, add 1M sodium bicarbonate solution, continue to stir, adjusting pH value is 9, makes it to generate the liquid-solid product B of yellowish orange; By product B under 150 ℃ of conditions-0.1MPa decompression distillation 5h, obtain product C; Product C is joined to the mixed solution (V: V=1:1), recrystallization under-10 ℃ of conditions, obtains product D of toluene and n-hexane; Product D, through n-hexane washing 5 times, is obtained to product E after vacuumize; Pressed powder E is soluble in water, under 0 ℃ of condition, mix, 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; Solution F is slowly added to (solution concentration is 30%) in solution G, under 0 ℃ of condition, stir 5h, filter, clean, be dried, obtain pressed powder H; Powder H is soaked after 10h in dilute hydrochloric acid solution, filter, clean, be dried, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtaining, PVDF, in mass ratio for 90:10 is in nmp solution after (solid content is 5%) ultrasonic mixing, blade coating, to aluminium foil, obtains homemade lithium sulfur battery anode material (4#C-S).
Embodiment 5
By aniline alcohol with tetraethoxysilane in molar ratio for the ratio of 1:1 is mixed, stirring at room, fully dissolves it, forms clear solution A; In solution A, add 0.1M sodium hydroxide solution, continue to stir, adjusting pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B under 100 ℃ of conditions-0.1MPa decompression distillation 5h, obtain product C; Product C is joined in the mixed solution (V:V=10:1) of toluene and n-hexane, recrystallization under-10 ℃ of conditions, obtains product D; Product D, through n-hexane washing 3 times, is obtained to product E after vacuumize; Pressed powder E is dissolved in ethanol, under 0 ℃ of condition, mixes, forming solution F(solution concentration is 5%); Get elemental sulfur, cetyl amine bromide (CTAB), hydrogen peroxide and for the ratio of 1:1:0.1:1, be dissolved in the solvent in step (6) in mass ratio, stirring and forming solution G(solution concentration after 10min is 10%); Solution F is slowly added in solution G, under 0 ℃ of condition, stir 5h, filter, clean, be dried, obtain pressed powder H; Powder H is soaked after 10h in dilute hydrochloric acid solution, filter, clean, be dried, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtaining, PVDF, in mass ratio for 80:20 is in DMF (NMP) solution after (solid content is 10%) ultrasonic mixing, blade coating, to aluminium foil, obtains homemade lithium sulfur battery anode material (5#C-S).
Embodiment 6
By pyrroles's alcohol with methyl silicate in molar ratio for the ratio of 1:1 is mixed, stirring at room, fully dissolves it, forms clear solution A; In solution A, add 0.5M potassium hydroxide solution, continue to stir, adjusting pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B under 100 ℃ of conditions-0.1MPa decompression distillation 5h, obtain product C; Product C is joined to the mixed solution (V: V=1:1), recrystallization under-10 ℃ of conditions, obtains product D of toluene and n-hexane; Product D, through n-hexane washing 5 times, is obtained to product E after vacuumize; Pressed powder E is soluble in water, under room temperature condition, mix, 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), after stirring 30min, forming solution G(solution concentration is 20%); Solution F is slowly added in solution G, under 0 ℃ of condition, stir 24h, filter, clean, be dried, obtain pressed powder H; Powder H is soaked after 48h in dilute hydrochloric acid solution, filter, clean, be dried, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtaining, PVDF, in mass ratio for 90:10 is in nmp solution after (solid content is 15%) ultrasonic mixing, blade coating, to aluminium foil, obtains homemade lithium sulfur battery anode material (6#C-S).
Embodiment 7
By acetylene alcohol with methyl silicate in molar ratio for the ratio of 1:1 is mixed, stirring at room, fully dissolves it, forms clear solution A; In solution A, add 0.1M potassium hydroxide solution, continue to stir, adjusting pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B under 100 ℃ of conditions-0.1MPa decompression distillation 5h, obtain product C; Product C is joined to the mixed solution (V: V=1:1), recrystallization under-10 ℃ of conditions, obtains product D of toluene and n-hexane; Product D, through n-hexane washing 5 times, is obtained to product E after vacuumize; Pressed powder E is soluble in water, under room temperature condition, mix, 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), after stirring 30min, forming solution G(solution concentration is 5%); Solution F is slowly added in solution G, under 0 ℃ of condition, stir 24h, filter, clean, be dried, obtain pressed powder H; Powder H is soaked after 48h in dilute hydrochloric acid solution, filter, clean, be dried, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtaining, PVDF, in mass ratio for 90:10 is in nmp solution after (solid content is 10%) ultrasonic mixing, blade coating, to aluminium foil, obtains homemade lithium sulfur battery anode material (7#C-S).
Embodiment 8
By aniline alcohol with tetraethoxysilane in molar ratio for the ratio of 1:1 is mixed, stirring at room, fully dissolves it, forms clear solution A; In solution A, add 0.5M sodium hydroxide solution, continue to stir, adjusting pH value is 9, makes it to generate the liquid-solid product B of yellowish orange; By product B under 100 ℃ of conditions-0.1MPa decompression distillation 5h, obtain product C; Product C is joined in the mixed solution (V:V=10:1) of toluene and n-hexane, recrystallization under-20 ℃ of conditions, obtains product D; Product D, through n-hexane washing 3 times, is obtained to product E after vacuumize; Pressed powder E is dissolved in ethanol, under 0 ℃ of condition, mixes, forming solution F(solution concentration is 10%); Get elemental sulfur, cetyl amine bromide (CTAB), ammonium persulfate and for the ratio of 1:1:0.1:1, be dissolved in the solvent in step (6) in mass ratio, stirring and forming solution G(solution concentration after 60min is 10%); Solution F is slowly added in solution G, under 0 ℃ of condition, stir 5h, filter, clean, be dried, obtain pressed powder H; Powder H is soaked after 48h in dilute hydrochloric acid solution, filter, clean, be dried, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtaining, PVDF, in mass ratio for 90:10 is in DMF (NMP) solution after (solid content is 10%) ultrasonic mixing, blade coating, to aluminium foil, obtains homemade lithium sulfur battery anode material (8#C-S).
Embodiment 9
By acetylene alcohol with methyl silicate in molar ratio for the ratio of 10:1 is mixed, stirring at room, fully dissolves it, forms clear solution A; In solution A, add 0.1M sodium hydroxide solution, continue to stir, adjusting pH value is 9, makes it to generate the liquid-solid product B of yellowish orange; By product B under 100 ℃ of conditions-0.1MPa decompression distillation 5h, obtain product C; Product C is joined in the mixed solution (V:V=10:1) of toluene and n-hexane, recrystallization under-20 ℃ of conditions, obtains product D; Product D, through n-hexane washing 3 times, is obtained to product E after vacuumize; Pressed powder E is dissolved in ethanol, under 0 ℃ of condition, mixes, forming solution F((solution concentration is 10%); The ratio that to get elemental sulfur, styrene (PS)/butadiene (PB)/styrene (PS), hydrogen peroxide mass ratio be 1:1:0.1:1 is dissolved in the solvent in step (6), and stirring and forming solution G(solution concentration after 60min is 10%); Solution F is slowly added in solution G, under 0 ℃ of condition, stir 5h, filter, clean, be dried, obtain pressed powder H; Powder H is soaked after 48h in dilute hydrochloric acid solution, filter, clean, be dried, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtaining, PVDF, in mass ratio for 80:20 is in DMF (NMP) solution after (solid content is 10%) ultrasonic mixing, blade coating, to aluminium foil, obtains homemade lithium sulfur battery anode material (9#C-S).
By thenyl alcohol with methyl silicate in molar ratio for the ratio of 10:1 is mixed, stirring at room, fully dissolves it, forms clear solution A; In solution A, add 0.5M sodium hydroxide solution, continue to stir, adjusting pH value is 9, makes it to generate the liquid-solid product B of yellowish orange; By product B under 100 ℃ of conditions-0.1MPa decompression distillation 5h, obtain product C; Product C is joined in the mixed solution (V:V=10:1) of benzene and normal heptane, recrystallization under-20 ℃ of conditions, obtains product D; Product D, through n-hexane washing 3 times, is obtained to product E after vacuumize; Pressed powder E is dissolved in ethanol, under 0 ℃ of condition, mixes, forming solution F(solution concentration is 60%); The ratio that to get elemental sulfur, styrene (PS)/butadiene (PB)/styrene (PS), ferric trichloride mass ratio be 1:1:0.1:1 is dissolved in the solvent in step (6), and stirring and forming solution G(solution concentration after 60min is 50%); Solution F is slowly added in solution G, under 0 ℃ of condition, stir 5h, filter, clean, be dried, obtain pressed powder H; Powder H is soaked after 48h in dilute hydrochloric acid solution, filter, clean, be dried, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtaining, PVDF, in mass ratio for 80:20 is in DMF (NMP) solution after (solid content is 10%) ultrasonic mixing, blade coating, to aluminium foil, obtains homemade lithium sulfur battery anode material (10#C-S).
Embodiment 11
By thenyl alcohol with tetraethoxysilane in molar ratio for the ratio of 1:1 is mixed, stirring at room, fully dissolves it, forms clear solution A; In solution A, add 1M sodium hydroxide solution, continue to stir, adjusting pH value is 7, makes it to generate the liquid-solid product B of yellowish orange; By product B under 100 ℃ of conditions-0.09MPa decompression distillation 30s, obtain product C; Product C is joined to the mixed solution (V: V=1:1), recrystallization under-10 ℃ of conditions, obtains product D of toluene and n-hexane; Product D, through n-hexane washing 5 times, is obtained to product E after vacuumize; Pressed powder E is soluble in water, under 0 ℃ of condition, mix, 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; Solution F is slowly added to (solution concentration is 70%) in solution G, under 0 ℃ of condition, stir 5h, filter, clean, be dried, obtain pressed powder H; Powder H is soaked after 10h in dilute hydrochloric acid solution, filter, clean, be dried, obtain conducting polymer-sulphur composite material prepared by the present invention.By the anode composite material obtaining, PVDF, in mass ratio for 90:10 is in nmp solution after (solid content is 10%) ultrasonic mixing, blade coating, to aluminium foil, obtains homemade lithium sulfur battery anode material (11#C-S).
Claims (8)
1. lithium-sulfur cell anode composite material, is characterized in that:
Described anode composite material is that the conducting polymer of take containing Si-O key is shell, is surrounded by the core-shell structure of sulphur in shell, and wherein the mass fraction of sulphur is 10-90%.
2. according to anode composite material described in claim 1, it is characterized in that: the described conducting polymer containing Si-O key is to contain CH
2five yuan of OH group or hexa-atomic aromatic compound thenyl alcohol, aniline alcohol, pyrroles's alcohol or acetylene alcohol are that monomer polymerization forms.
3. according to anode composite material described in claim 1 or 2, it is characterized in that: described anode composite material is prepared from according to the following procedure,
(1) will be containing-CH
2five yuan of OH group or hexa-atomic aromatic compound and esters of silicon acis are greater than 0 to≤1 ratio in molar ratio to be mixed, and after fully dissolving, forms clear solution A;
(2) in solution A, add aqueous slkali, adjust pH value 7-9, make it to generate product B;
(3) by product B decompression distillation 30s-5h under 100-150 ℃ of condition, obtain product C;
(4) product C is joined in the mixed solution of substituted benzene and linear paraffin, recrystallization under-10 ~-20 ℃ of conditions, obtain product D, the mixed solution of the preferred toluene of the mixed solution of substituted benzene and linear paraffin and n-hexane wherein, its volume ratio is (0.01-1): 1;
(5) product D after washing, be dried, linear paraffin is obtained to product E containing the conducting polymer monomer of Si-O key;
(6) product E is dissolved in solvent, under 0 ℃-room temperature condition, mixes, the mass concentration that forms solution F(solute is 1% ~ 80%), wherein solvent is one or more mixtures in water, ethanol, chloroform, toluene;
(7) get elemental sulfur, surfactant, initator and 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, under 0 ℃-room temperature condition, stir 5-24h, filtration drying, obtains 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) powder H is soaked after 10-48h in acid solution, filtration drying, obtains described anode composite material.
4. according to anode composite material described in claim 3, it is characterized in that: described contain-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 claimed in claim 3, it is characterized in that:
Described esters of silicon acis is a kind of or two kinds of mixtures in tetraethoxysilane or methyl silicate;
Described aqueous slkali is NaOH solution, KOH solution, Na
2cO
3solution, NaHCO
3solution, NH
3water, (NH
4)
2cO
3a kind of in solution;
Described acid is that concentration is sulfuric acid, nitric acid, phosphoric acid or the hydrochloric acid solution that is less than 2M.
6. according to anode composite material claimed in claim 3, 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. the preparation method of anode composite material described in a claim 1 or 2, it is characterized in that: described preparation method is that the conducting polymer of take containing Si-O key is precursors, make the composite material of polymer bag sulphur, then through protonated processing procedure, be prepared from;
Its concrete preparation process is:
(1) will be containing-CH
2five yuan of OH group or hexa-atomic aromatic compound and esters of silicon acis are greater than 0 to≤1 ratio in molar ratio to be mixed, and after fully dissolving, forms clear solution A;
(2) in solution A, add aqueous slkali, adjust pH value 7-9, make it to generate product B;
(3) by product B decompression distillation 30s-5h under 100-150 ℃ of condition, obtain product C;
(4) product C is joined in the mixed solution of substituted benzene and linear paraffin, recrystallization under-10 ~-20 ℃ of conditions, obtain product D, the mixed solution of the preferred toluene of the mixed solution of substituted benzene and linear paraffin and n-hexane wherein, its volume ratio (0.01-1): 1;
(5) product D after washing, be dried, linear paraffin is obtained to product E containing the conducting polymer monomer of Si-O key;
(6) product E is dissolved in solvent, under 0 ℃-room temperature condition, mixes, 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 and 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, under 0 ℃-room temperature condition, stir 5-24h, filtration drying, obtains 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) powder H is soaked after 10-48h in acid solution, filtration drying, obtains described anode composite material.
8. an application for anode composite material described in claim 1 or 2, is characterized in that: described composite material is applied to lithium-sulphur cell positive electrode.
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| CN103985913A (en) * | 2014-05-16 | 2014-08-13 | 宋大余 | Process for manufacturing lithium sulfur battery |
| CN106374095A (en) * | 2016-11-08 | 2017-02-01 | 太原理工大学 | Preparation method of composite material used as lithium-sulfur battery cathode material |
| CN106663788A (en) * | 2014-06-06 | 2017-05-10 | 罗伯特·博世有限公司 | Polymer electrlyte for a lithium sulfur cell |
| CN110993902A (en) * | 2019-11-12 | 2020-04-10 | 东北师范大学 | Lithium-sulfur battery with positively charged organic small molecule positive electrode additive |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985913A (en) * | 2014-05-16 | 2014-08-13 | 宋大余 | Process for manufacturing lithium sulfur battery |
| CN106663788A (en) * | 2014-06-06 | 2017-05-10 | 罗伯特·博世有限公司 | Polymer electrlyte for a lithium sulfur cell |
| CN106663788B (en) * | 2014-06-06 | 2021-04-30 | 罗伯特·博世有限公司 | Polymer electrolyte for lithium-sulfur batteries |
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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 |
| CN110993902A (en) * | 2019-11-12 | 2020-04-10 | 东北师范大学 | Lithium-sulfur battery with positively charged organic small molecule positive electrode additive |
| 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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| CN103579585B (en) | 2015-09-09 |
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