CN104157851A - Lithium sulfur battery adopting stannous sulfide as anchoring center and preparation method of positive electrode of lithium sulfur battery - Google Patents
Lithium sulfur battery adopting stannous sulfide as anchoring center and preparation method of positive electrode of lithium sulfur battery Download PDFInfo
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- CN104157851A CN104157851A CN201410333198.5A CN201410333198A CN104157851A CN 104157851 A CN104157851 A CN 104157851A CN 201410333198 A CN201410333198 A CN 201410333198A CN 104157851 A CN104157851 A CN 104157851A
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- lithium
- sulphur
- sulfide
- positive electrode
- stannous sulfide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of a lithium sulfur battery, and aims at providing a lithium sulfur battery adopting stannous sulfide as an anchoring center and a preparation method of a positive electrode of the lithium sulfur battery. The preparation method of the lithium sulfur battery adopting the stannous sulfide as the anchoring center specifically comprises the following steps: preparing a macroporous carbon material with nano stannous sulfide being dispersed on the inner wall and a macroporous carbon material with supported sulfur, preparing an anode material of the lithium sulfur battery by utilizing the macroporous carbon material with supported sulfur, preparing the positive electrode by utilizing the positive electrode material, and assembling the positive electrode, a diaphragm, a negative electrode and electrolyte to form the lithium sulfur battery. The prepared high-capacity lithium ion battery positive electrode material is good in conductivity, low in internal resistance, good in electrode reaction reversibility, good in chemical stability and thermal stability, low in price, easy to prepare and pollution-free, so that the electrochemical dynamics performance of the lithium sulfur battery positive electrode can be improved, the electrode polarization can be alleviated, and the speed capacity of the lithium battery can be improved.
Description
Technical field
The invention relates to lithium-sulfur cell field, particularly taking stannous sulfide as the lithium-sulfur cell at grappling center and anodal preparation method.
Background technology
Lithium-sulfur cell is the one of lithium ion battery, the advantages such as that a kind of lithium ion battery using element sulphur as anode has is lightweight, capacity large, memory-less effect.The specific capacity of lithium-sulfur cell is up to 1675mAh g
-1, far away higher than capacity (the <150mAh g of the cobalt acid lithium battery of commercial extensive use
-1), and sulphur is a kind of environmental friendliness element, and environment is not polluted substantially.Lithium-sulfur cell is the very promising lithium ion battery of one.
Lithium-sulfur cell taking lithium as negative pole is example, and when electric discharge, negative reaction is that lithium loses electronics and becomes lithium ion, and anodal reaction generates sulfide for sulphur and lithium ion and electron reaction, and the electrical potential difference of positive pole and negative reaction is the discharge voltage that lithium-sulfur cell provides.Under applied voltage effect, the positive pole of lithium-sulfur cell and negative reaction counter movement, be charging process.Become S completely according to the elemental sulfur of unit mass
2-the electric weight that can provide can show that the theory electric discharge specific discharge capacity of sulphur is 1675mAh g
-1, in like manner can show that the theory electric discharge specific discharge capacity of simple substance lithium is 3860mAh g
-1.The theoretical discharge voltage of lithium-sulfur cell is 2.287V, as sulphur and lithium complete reaction generation lithium sulfide (Li
2s) time.The theory electric discharge specific energy of corresponding lithium-sulfur cell is 2600Wh kg
-1.
The charging and discharging reaction of sulfur electrode is more complicated, and the intermediate product that sulfur electrode is produced in charging and discharging reaction does not also have clear and definite understanding.The discharge process of sulfur electrode mainly comprises two steps, respectively corresponding two discharge platforms: (1) corresponding S
8circulus become S
n 2-the chain structure of (3≤n≤7) ion, and and Li
+in conjunction with generating poly-lithium sulfide (Li
2s
n), this reaction is near the discharge platform corresponding 2.4～2.1V on discharge curve; (2) corresponding S
n 2-the chain structure of ion becomes S
2-and S
2 2-and and Li
+in conjunction with generating Li
2s
2and Li
2s, near longer discharge platform 2.1～1.8V in the corresponding discharge curve of this reaction, this platform is the main region of discharge of lithium-sulfur cell.In the time of electric discharge, be positioned at the further reduction that the corresponding elemental sulfur reduction of 2.5～2.05V potential region generates soluble polysulfide and polysulfide, be positioned at the corresponding soluble polysulfide reduction of 2.05～1.5V potential region and generate lithium sulfide solid film, it covers conductive carbon based surface.When charging, Li in sulfur electrode
2s and Li
2s
2oxidized S
8and S
m 2-(6≤m≤7), can not be completely oxidized to S
8, near this charging reaction charging platform corresponding 2.5～2.4V in charging curve.The problem of lithium-sulfur cell maximum is at present: in charge and discharge process, form the poly-lithium sulfide that is dissolved in electrolyte, the poly-lithium sulfide of dissolving reacts with negative pole lithium metal, causes capacitance loss, causes lithium-sulfur cell capacity to fail fast, shows the cycle life of extreme difference.
Summary of the invention
Main purpose of the present invention is to overcome deficiency of the prior art, provides a kind of taking stannous sulfide as grappling center, then by the lithium-sulfur cell of sulphur particle and the preparation method of positive electrode thereof in the coated macropore carbon of stannous sulfide.For solving the problems of the technologies described above, solution of the present invention is:
Preparation method taking stannous sulfide as the lithium-sulphur cell positive electrode at grappling center is provided, specifically comprises the steps:
(1) take hydrophilic nano CaCO
3, carbon source material and tin salt, be added in 100mL deionized water, ultrasonic vibration (supersonic frequency 40kHz) mixes 30 minutes, carbon source material and tin salt are dissolved and with nanometer CaCO
3be uniformly dispersed; Then after heating evaporates the water, at 160 DEG C, solidify 6 hours, then cured product is warming up to 700～900 DEG C, constant temperature carbonization 2 hours under nitrogen atmosphere protection; Be cooled to 500 DEG C, pass into hydrogen sulfide gas, react 1 hour, after reaction finishes, obtain product; Then product is used successively to hydrochloric acid and the deionized water washing and filtering of 1wt% concentration, then freeze-day with constant temperature, after 4 hours, obtains inwall and contains disperse distribution nanometer stannous sulfide macropore material with carbon element at 120 DEG C;
Wherein, hydrophilic nano CaCO
3, carbon source material, tin salt mass ratio be 1: 1: 0.1～0.5, and hydrophilic nano CaCO
3addition is 10g, and carbon source material addition is 10g, and tin salt addition is 1～5g;
Described carbon source material is any one material in glucose, sucrose, starch, cyclodextrin, polyvinyl alcohol, polyethylene glycol, polyacrylic acid or water soluble fiber element;
Described tin salt is any one material in the nitrate of the sulfate of sub-tin, sub-tin or the chloride of sub-tin;
(2) using in elemental sulfur and step (1), make for as storage sulfur materials containing nanometer stannous sulfide macropore material with carbon element, 10: 1 in mass ratio～25 ground and mixed, be placed in reactor (reactors of 316 stainless steels), after being vacuumized, reactor is heated to 60 DEG C, react and complete supporting of sulphur after 5～10 hours, product is cooled to room temperature (10～30 DEG C), has been supported the macropore material with carbon element of sulphur;
(3) by the macropore material with carbon element that supports sulphur making in step (2), impregnated in the stannous chloride solution that concentration is 5wt%, product filtration drying is placed in reactor (reactors of 316 stainless steels), in reactor, pass into hydrogen sulfide gas again, react after 1 hour, on sulfur granules, cover one deck stannous sulfide, realize the comprehensive grappling to sulphur particle in macropore, make the carbon-sulphur-stannous sulfide composite material taking stannous sulfide as poly-lithium sulfide grappling center, for the positive electrode as lithium-sulfur cell.
As further improvement, described hydrophilic nano CaCO
3particle diameter be 15～40nm.
The lithium-sulfur cell taking stannous sulfide as the lithium-sulphur cell positive electrode at grappling center based on described is provided, comprise barrier film, positive pole, negative pole and electrolyte, described barrier film adopts microporous polypropylene membrane, anodal and negative pole is arranged on respectively barrier film both sides in opposite directions, form sandwich structure, electrolyte is built in sandwich structure;
Described electrolyte refers to: with LiClO
4for solute, dioxolanes (C
3h
6o
2) and EGME (C
4h
10o
2) mixture be solvent, and the volume ratio of dioxolanes and EGME is 1:1, in one liter of electrolyte containing 1 mole of (106.4g) LiClO
4;
The described anodal positive electrode preparation that adopts, positive electrode comprises the carbon-sulphur-stannous sulfide composite material taking stannous sulfide as poly-lithium sulfide grappling center;
Described negative pole adopts lithium metal, or adopts negative material preparation, negative material to comprise lithium titanate.
As further improvement, the preparation method of described positive pole is: get carbon-sulphur-stannous sulfide composite material, acetylene black and Kynoar (PVDF) taking stannous sulfide as poly-lithium sulfide grappling center, after being 80: 10: 10 ground and mixed in mass ratio, add 1-METHYLPYRROLIDONE mechanical mixture 30 minutes, be modulated into paste and be coated on aluminium film, dry in the shade; Then under the pressure of 100Kg cm-2, by compressing the aluminium film after drying in the shade, make positive pole.
As further improvement, the method that described employing negative material is prepared negative pole is: get lithium titanate, acetylene black and Kynoar (PVDF), after being 80: 10: 10 ground and mixed in mass ratio, add solvent 1-METHYLPYRROLIDONE mechanical mixture 30 minutes, be modulated into paste and be coated on copper film, dry in the shade; Then at 100Kg cm
-2pressure under, by compressing the copper film after drying in the shade, make negative pole.
The present invention prepares the principle of positive electrode: the carbon monoxide reduction tin salt that when 700～900 DEG C of constant temperature carbonizations, carbon source material cracking produces, form nano metal tin, and be present in form after carbon source material carbonization mesoporous, nano-calcium carbonate is decomposed to form calcium oxide.Be cooled to 500 DEG C and be filled with hydrogen sulfide gas, in the material with carbon element of carbonized product is mesoporous, metallic tin reacts with hydrogen sulfide and generates stannous sulfide.Calcium oxide reacts with hydrogen sulfide and generates calcium sulfide.The hydrochloric acid of 1wt% concentration and deionized water washing can be removed the calcium sulfide in product, form macropore in material with carbon element.Because stannous sulfide is water insoluble and watery hydrochloric acid, the hydrochloric acid of 1wt% concentration and the washing of deionized water can not exert an influence to stannous sulfide.
The operation principle of lithium-sulfur cell prepared by the present invention: stannous sulfide is acid sulphide, discharge process, the Li in electrolyte
+under the effect of stannous sulfide, embed sulphur particle (sulphur is reduced): SnS+2Li
++ S+2e → Li
2[SnS
2]; Li
2[SnS
2] further act on sulphur particle and make sulphur reduction, form trithio lithium stannate: Li
2[SnS
2]+S+2e → Li
2[SnS
3]; Li
2[SnS
3] continue to make sulphur embedding lithium, form four sulphur lithium stannate Li
4[SnS
4]: Li
2[SnS
3]+2Li
++ S+2e → Li
4[SnS
4].
Because four sulphur lithium stannates have very strong affinity to polysulfide ion, the poly-lithium sulfide forming in sulphur embedding lithium process is subsequently adsorbed on four sulphur lithium stannates firmly, has greatly suppressed the dissolving of poly-lithium sulfide in electrolyte.The further embedding lithium of poly-lithium sulfide forms Li
2s
2and Li
2s.
Charging process is the back reaction of said process, first Li
2s takes off lithium (S
2-oxidized) formation Li
2s
2, Li
2s
2further formed poly-lithium sulfide by electrochemical oxidation.Equally, poly-lithium sulfide is adsorbed on four sulphur lithium stannates firmly, cannot be dissolved in electrolyte.Thereby effectively prevent reacting of poly-lithium sulfide and negative pole lithium metal, suppressed the inducing capacity fading of lithium-sulfur cell, improved the cycle life of lithium-sulfur cell.
The structure of macropore material with carbon element makes sulphur be present in material macropore inside, and stannous sulfide is present in hole wall mesoporous, in first embedding lithium process, forms four sulphur lithium stannate grappling centers to adsorb poly-lithium sulfide.And, lithium ion battery is in charge and discharge process, take off/the change in volume that embedding causes of the lithium ion in sulphur is all in the inner generation of material macropore, eliminated sulphur de-/impact on electrode structure of change in volume that embedding lithium causes, having stablized anodal structure, is also the key factor that improves the lithium-sulfur cell life-span.Macropore material with carbon element has higher conductivity, effectively improves the high power charging-discharging cycle life of lithium ion battery.
The stannous sulfide that covers sulphur particle surface is finally also forming four sulphur lithium stannate layers in embedding lithium process first, and thoroughly isolated sulphur contacts with the direct of electrolyte, effectively prevents the dissolving in electrolyte of the poly-lithium sulfide that forms in charge and discharge process.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention utilizes sulphur to have the characteristic of high storage lithium specific capacity, form a kind of anode material for lithium-ion batteries of high power capacity, have at the mesoporous interior formation disperse distribution stannous sulfide of macropore material with carbon element inwall, and taking stannous sulfide as poly-lithium sulfide grappling center, effectively prevent poly-lithium sulfide stripping from macropore material with carbon element in charge and discharge process, be conducive to the stable of electrode material performance.
Carbon-sulphur-stannous sulfide composite material (being positive electrode) of macroporous structure of the present invention has: good conductivity, very low internal resistance; Well electrode reaction invertibity; Good chemical stability and thermal stability; Cheap and be easy to preparation; Pollution-free.Thereby the electrochemical kinetics performance that improves lithium-sulphur cell positive electrode, reduces electrode polarization, improve the speed capabilities of lithium battery, can be applicable to the electrokinetic cell of electric automobile, improve reliability and the fail safe of power lithium-ion battery.
Brief description of the drawings
Fig. 1 is the comparison schematic diagram in the life-span of the lithium-sulphur cell positive electrode prepared of the present invention and traditional sulfur electrode.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail:
Embodiment mono-: nanometer stannous sulfide supports the preparation of macropore material with carbon element
Taking in mass ratio particle diameter at 1: 1: 0.1 is the commercially available hydrophilic nano CaCO of 15～40nm
3(10g), glucose (10g) and stannous chloride (1g), be added in 100mL deionized water, ultrasonic vibration (supersonic frequency 40kHz) mix within 30 minutes, make glucose and stannous chloride dissolve and with nanometer CaCO
3be uniformly dispersed; Heating evaporates the water, and then at 160 DEG C, solidifies 6 hours; Cured product is warming up to 700 under nitrogen atmosphere protection, DEG C constant temperature carbonization 2 hours; Be cooled to 500 DEG C, pass into hydrogen sulfide gas, react 1 hour.Product is used hydrochloric acid and the deionized water washing and filtering of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains inwall and contains disperse distribution nanometer stannous sulfide macropore material with carbon element at 120 DEG C.
Embodiment bis-: support sulphur in macropore carbon
Taking in mass ratio particle diameter at 1: 1: 0.3 is the commercially available hydrophilic nano CaCO of 15～40nm
3(10g), the sub-tin of sucrose (10g) and nitric acid (3g), be added in 100mL deionized water, ultrasonic vibration (supersonic frequency 40kHz) mix within 30 minutes, make sucrose and the sub-tin of nitric acid dissolve and with nanometer CaCO
3be uniformly dispersed; Heating evaporates the water, and then at 160 DEG C, solidifies 6 hours; Cured product is warming up to 850 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Be cooled to 500 DEG C, pass into hydrogen sulfide gas, react 1 hour.Product is used hydrochloric acid and the deionized water washing and filtering of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains inwall and contains disperse distribution nanometer stannous sulfide macropore material with carbon element at 120 DEG C.
Be placed in the reactor of 316 stainless steels containing nanometer stannous sulfide macropore material with carbon element 10: 1 ground and mixed in mass ratio using elemental sulfur and as the above-mentioned of storage sulfur materials, after vacuumizing, be heated to 60 DEG C, after 5 hours, complete supporting of sulphur.
Embodiment tri-: stannous sulfide is coated
Taking in mass ratio particle diameter at 1: 1: 0.5 is the commercially available hydrophilic nano CaCO of 15～40nm
3(10g), starch (10g) and stannous sulfate (5g), be added in 100mL deionized water, ultrasonic vibration mix (supersonic frequency 40kHz) within 30 minutes, make starch and stannous sulfate dissolve and with nanometer CaCO
3be uniformly dispersed; Heating evaporates the water, and then at 160 DEG C, solidifies 6 hours; Cured product is warming up to 900 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Be cooled to 500 DEG C, pass into hydrogen sulfide gas, react 1 hour.Product is used hydrochloric acid and the deionized water washing and filtering of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains inwall and contains disperse distribution nanometer stannous sulfide macropore material with carbon element at 120 DEG C.
Be placed in the reactor of 316 stainless steels containing nanometer stannous sulfide macropore material with carbon element 1: 1 ground and mixed in mass ratio using elemental sulfur and as the above-mentioned of storage sulfur materials, after vacuumizing, be heated to 60 DEG C, after 8 hours, complete supporting of sulphur, be cooled to 30 DEG C.
The above-mentioned macropore material with carbon element that has supported sulphur be impregnated in to the stannous chloride solution that concentration is 5wt%, and product filtration drying is placed on the reactor of 316 stainless steels, passes into hydrogen sulfide gas, reacts and on sulfur granules, covers one deck stannous sulfide after 1 hour.
Embodiment tetra-: lithium sulfur battery anode material preparation
Taking in mass ratio particle diameter at 1: 1: 0.5 is the commercially available hydrophilic nano CaCO of 15～40nm
3(10g), polyvinyl alcohol, polyethylene glycol, polyacrylic acid or water soluble fiber element (each 10g) and stannous chloride (5g), be added to respectively in 100mL deionized water, ultrasonic vibration mix (supersonic frequency 40kHz) within 30 minutes, make polyvinyl alcohol, polyethylene glycol, polyacrylic acid or water soluble fiber element and stannous chloride dissolve and with nanometer CaCO
3be uniformly dispersed; Heating evaporates the water, and then at 160 DEG C, solidifies 6 hours; Obtain respectively the cured product taking polyvinyl alcohol, polyethylene glycol, polyacrylic acid or water soluble fiber element as carbon source, these cured products are warming up to 900 DEG C respectively under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Be cooled to 500 DEG C, pass into hydrogen sulfide gas, react 1 hour.Product is used hydrochloric acid and the deionized water washing and filtering of 1wt% concentration successively, at 120 DEG C, freeze-day with constant temperature, after 4 hours, is able to respectively the inwall that polyvinyl alcohol, polyethylene glycol, polyacrylic acid or water soluble fiber element are forerunner's material with carbon element and contains disperse distribution nanometer stannous sulfide macropore material with carbon element again.
Be placed in reactor containing nanometer stannous sulfide macropore material with carbon element 10: 1 ground and mixed in mass ratio using elemental sulfur and as the above-mentioned of storage sulfur materials, after vacuumizing, be heated to 60 DEG C, after 8 hours, complete supporting of sulphur, be cooled to 20 DEG C.
The above-mentioned macropore material with carbon element that has supported sulphur be impregnated in to the stannous chloride solution that concentration is 5wt%, product filtration drying is placed on the reactor of 316 stainless steels, pass into hydrogen sulfide gas, react and on sulfur granules, cover one deck stannous sulfide after 1 hour, realize the comprehensive grappling to sulphur particle in macropore carbon, obtain carbon-sulphur-stannous sulfide composite material, as the positive electrode (sulfur electrode material) of lithium-sulfur cell.
Embodiment five: the lithium-sulfur cell that is negative material with lithium titanate
Taking in mass ratio particle diameter at 1: 1: 0.5 is the commercially available hydrophilic nano CaCO of 15～40nm
3(10g), cyclodextrin (10g) and stannous sulfate (5g), be added in 100mL deionized water, ultrasonic vibration (supersonic frequency 40kHz) mix within 30 minutes, make cyclodextrin and stannous sulfate dissolve and with nanometer CaCO
3be uniformly dispersed; Heating evaporates the water, and then at 160 DEG C, solidifies 6 hours; Cured product is warming up to 900 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Be cooled to 500 DEG C, pass into hydrogen sulfide gas, react 1 hour.Product is used hydrochloric acid and the deionized water washing and filtering of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains inwall and contains disperse distribution nanometer stannous sulfide macropore material with carbon element at 120 DEG C.
Be placed in reactor containing nanometer stannous sulfide macropore material with carbon element 10: 25 ground and mixed in mass ratio using elemental sulfur and as the above-mentioned of storage sulfur materials, after vacuumizing, be heated to 60 DEG C, after 10 hours, complete supporting of sulphur, be cooled to 10 DEG C.
The above-mentioned macropore material with carbon element that has supported sulphur be impregnated in to the stannous chloride solution that concentration is 5wt%, product filtration drying is placed on the reactor of 316 stainless steels, pass into hydrogen sulfide gas, react and on sulfur granules, cover one deck stannous sulfide after 1 hour, realize the comprehensive grappling to sulphur particle in macropore carbon, obtain sulfur electrode material.
Be 80: 10: 10 in mass ratio by above-mentioned sulfur electrode material, acetylene black and PVDF, add 1-METHYLPYRROLIDONE to be adjusted to certain viscosity after grinding, mechanical mixture 30 minutes, is modulated into paste, is coated on aluminium film, dries in the shade; At 100Kg cm
-2pressure under compressing, obtain lithium-sulphur cell positive electrode.
Be 80: 10: 10 in mass ratio by lithium titanate, acetylene black and Kynoar (PVDF), add solvent 1-METHYLPYRROLIDONE to be adjusted to certain viscosity after grinding, mechanical mixture 30 minutes, is modulated into paste, is coated on copper film, dries in the shade; At 100Kg cm
-2pressure under compressing, obtain lithium-sulfur cell negative pole.
Taking microporous polypropylene membrane as barrier film, electrode material side anodal and negative pole forms sandwich structure, built-in electrolyte: LiClO with barrier film in opposite directions
4be dissolved in dioxolanes (C
3h
6o
2) and EGME (C
4h
10o
2) mixed solvent obtain electrolyte, the volume ratio of dioxolanes and EGME is 1:1, in one liter of electrolyte containing one mole of (106.4g) LiClO
4.Obtain the lithium-sulfur cell taking lithium titanate as negative material.
Embodiment six: the lithium-sulfur cell taking lithium metal as negative material
Taking in mass ratio particle diameter at 1: 1: 0.1 is the commercially available hydrophilic nano CaCO of 15～40nm
3(10g), cyclodextrin (10g) and stannous sulfate (5g), be added in 100mL deionized water, ultrasonic vibration (supersonic frequency 40kHz) mix within 30 minutes, make cyclodextrin and stannous sulfate dissolve and with nanometer CaCO
3be uniformly dispersed; Heating evaporates the water, and then at 160 DEG C, solidifies 6 hours; Cured product is warming up to 900 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Be cooled to 500 DEG C, pass into hydrogen sulfide gas, react 1 hour.Product is used hydrochloric acid and the deionized water washing and filtering of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains inwall and contains disperse distribution nanometer stannous sulfide macropore material with carbon element at 120 DEG C.
Be placed in reactor containing nanometer stannous sulfide macropore material with carbon element 10: 25 ground and mixed in mass ratio using elemental sulfur and as the above-mentioned of storage sulfur materials, after vacuumizing, be heated to 60 DEG C, after 10 hours, complete supporting of sulphur, be cooled to 25 DEG C.
The above-mentioned macropore material with carbon element that has supported sulphur be impregnated in to the stannous chloride solution that concentration is 5wt%, product filtration drying is placed on the reactor of 316 stainless steels, pass into hydrogen sulfide gas, react and on sulfur granules, cover one deck stannous sulfide after 1 hour, realize the comprehensive grappling to sulphur particle in macropore carbon, obtain sulfur electrode material.
Be 80: 10: 10 in mass ratio by above-mentioned sulfur electrode material, acetylene black and PVDF, add 1-METHYLPYRROLIDONE to be adjusted to certain viscosity after grinding, mechanical mixture 30 minutes, is modulated into paste, is coated on aluminium film, dries in the shade; At 100Kg cm
-2pressure under compressing, obtain lithium-sulphur cell positive electrode.
Taking microporous polypropylene membrane as barrier film, the electrode material side of sulfur electrode and barrier film in opposite directions with metal lithium sheet sandwich structure, built-in electrolyte: LiClO
4be dissolved in dioxolanes (C
3h
6o
2) and EGME (C
4h
10o
2) mixed solvent obtain electrolyte, the volume ratio of dioxolanes and EGME is 1:1, in one liter of electrolyte containing one mole of (106.4g) LiClO
4.Obtain the lithium-sulfur cell taking lithium metal as negative material.
Embodiment seven: the life test of lithium-sulfur cell
Taking in mass ratio particle diameter at 1: 1: 0.1 is the commercially available hydrophilic nano CaCO of 15～40nm
3(10g), polyethylene glycol (10g) and stannous chloride (5g), be added to respectively in 100mL deionized water, ultrasonic vibration (supersonic frequency 40kHz) mix within 30 minutes, make polyethylene glycol and stannous chloride dissolve and with nanometer CaCO
3be uniformly dispersed; Heating evaporates the water, and then at 160 DEG C, solidifies 6 hours; Cured product is warming up to 800 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Be cooled to 500 DEG C, pass into hydrogen sulfide gas, react 1 hour.Product is used hydrochloric acid and the deionized water washing and filtering of 1wt% concentration successively, then freeze-day with constant temperature, after 4 hours, obtains containing taking polyethylene glycol as the inwall of forerunner's material with carbon element disperse distribution nanometer stannous sulfide macropore material with carbon element at 120 DEG C.
Be placed in reactor containing nanometer stannous sulfide macropore material with carbon element 1: 1 ground and mixed in mass ratio using elemental sulfur and as the above-mentioned of storage sulfur materials, after vacuumizing, be heated to 60 DEG C, after 10 hours, complete supporting of sulphur, be cooled to 20 DEG C.
The above-mentioned macropore material with carbon element that has supported sulphur be impregnated in to the stannous chloride solution that concentration is 5wt%, product filtration drying is placed on the reactor of 316 stainless steels, pass into hydrogen sulfide gas, react and on sulfur granules, cover one deck stannous sulfide after 1 hour, realize the comprehensive grappling to sulphur particle in macropore carbon, obtain sulfur electrode material.
Be 80: 10: 10 in mass ratio by above-mentioned positive electrode, acetylene black and PVDF, add 1-METHYLPYRROLIDONE to be adjusted to certain viscosity after grinding, mechanical mixture 30 minutes, is modulated into paste, is coated on aluminium film, dries in the shade; At 100Kg cm
-2pressure under compressing, obtain lithium-sulphur cell positive electrode.
Taking microporous polypropylene membrane as barrier film, anodal electrode material side and barrier film in opposite directions with metal lithium sheet sandwich structure, built-in electrolyte: LiClO
4be dissolved in dioxolanes (C
3h
6o
2) and EGME (C
4h
10o
2) mixed solvent obtain electrolyte, the volume ratio of dioxolanes and EGME is 1:1, in one liter of electrolyte containing one mole of (106.4g) LiClO
4.Be assembled into the lithium sulphur button cell taking lithium metal as negative material.
Fig. 1 is the mesoporous interior formation disperse distribution stannous sulfide of macropore material with carbon element inwall, and carries out the comparison in coated sulfur electrode and traditional sulfur electrode (electrode only has elemental sulfur and conductive agent acetylene black) life-span with stannous sulfide.The electric weight that ordinate unit discharges for every gram of sulphur.In figure, curve 1: the lithium-sulfur cell of common sulfur electrode, curve 2: it is storage sulfur-donor the lithium-sulfur cell that carries out the coated sulfur electrode obtaining of stannous sulfide that stannous sulfide supports macropore carbon.Charging and discharging currents density: 168mA/g, temperature: 25 DEG C.
Finally, it should be noted that above what enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, can also have a lot of distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (5)
1. the preparation method taking stannous sulfide as the lithium-sulphur cell positive electrode at grappling center, is characterized in that, specifically comprises the steps:
(1) take hydrophilic nano CaCO
3, carbon source material and tin salt, be added in 100mL deionized water, ultrasonic vibration mixes 30 minutes, carbon source material and tin salt are dissolved and with nanometer CaCO
3be uniformly dispersed; Then after heating evaporates the water, at 160 DEG C, solidify 6 hours, then cured product is warming up to 700～900 DEG C, constant temperature carbonization 2 hours under nitrogen atmosphere protection; Be cooled to 500 DEG C, pass into hydrogen sulfide gas, react 1 hour, after reaction finishes, obtain product; Then product is used successively to hydrochloric acid and the deionized water washing and filtering of 1wt% concentration, then freeze-day with constant temperature, after 4 hours, obtains inwall and contains disperse distribution nanometer stannous sulfide macropore material with carbon element at 120 DEG C;
Wherein, hydrophilic nano CaCO
3, carbon source material, tin salt mass ratio be 1: 1: 0.1～0.5, and hydrophilic nano CaCO
3addition is 10g, and carbon source material addition is 10g, and tin salt addition is 1～5g;
Described carbon source material is any one material in glucose, sucrose, starch, cyclodextrin, polyvinyl alcohol, polyethylene glycol, polyacrylic acid or water soluble fiber element;
Described tin salt is any one material in the nitrate of the sulfate of sub-tin, sub-tin or the chloride of sub-tin;
(2) using in elemental sulfur and step (1), make for as storage sulfur materials containing nanometer stannous sulfide macropore material with carbon element, 10: 1 in mass ratio～25 ground and mixed, be placed in reactor, after being vacuumized, reactor is heated to 60 DEG C, react and complete supporting of sulphur after 5～10 hours, product is cooled to room temperature (10～30 DEG C), has been supported the macropore material with carbon element of sulphur;
(3) by the macropore material with carbon element that supports sulphur making in step (2), impregnated in the stannous chloride solution that concentration is 5wt%, product filtration drying is placed in reactor, in reactor, pass into hydrogen sulfide gas again, react after 1 hour, on sulfur granules, cover one deck stannous sulfide, realize the comprehensive grappling to sulphur particle in macropore, make the carbon-sulphur-stannous sulfide composite material taking stannous sulfide as poly-lithium sulfide grappling center, for the positive electrode as lithium-sulfur cell.
2. the preparation method taking stannous sulfide as the lithium-sulphur cell positive electrode at grappling center according to claim 1, is characterized in that, described hydrophilic nano CaCO
3particle diameter be 15～40nm.
3. based on the lithium-sulfur cell taking stannous sulfide as the lithium-sulphur cell positive electrode at grappling center claimed in claim 1, comprise barrier film, positive pole, negative pole and electrolyte, it is characterized in that, described barrier film adopts microporous polypropylene membrane, anodal and negative pole is arranged on respectively barrier film both sides in opposite directions, form sandwich structure, electrolyte is built in sandwich structure;
Described electrolyte refers to: with LiClO
4for solute, dioxolanes (C
3h
6o
2) and EGME (C
4h
10o
2) mixture be solvent, and the volume ratio of dioxolanes and EGME is 1:1, in one liter of electrolyte containing 1 mole of (106.4g) LiClO
4;
The described anodal positive electrode preparation that adopts, positive electrode comprises the carbon-sulphur-stannous sulfide composite material taking stannous sulfide as poly-lithium sulfide grappling center;
Described negative pole adopts lithium metal, or adopts negative material preparation, negative material to comprise lithium titanate.
4. lithium-sulfur cell according to claim 3, it is characterized in that, the preparation method of described positive pole is: get carbon-sulphur-stannous sulfide composite material, acetylene black and Kynoar (PVDF) taking stannous sulfide as poly-lithium sulfide grappling center, after being 80: 10: 10 ground and mixed in mass ratio, add 1-METHYLPYRROLIDONE mechanical mixture 30 minutes, be modulated into paste and be coated on aluminium film, dry in the shade; Then under the pressure of 100Kg cm-2, by compressing the aluminium film after drying in the shade, make positive pole.
5. lithium-sulfur cell according to claim 3, it is characterized in that, the method that described employing negative material is prepared negative pole is: get lithium titanate, acetylene black and Kynoar (PVDF), after being 80: 10: 10 ground and mixed in mass ratio, add solvent 1-METHYLPYRROLIDONE mechanical mixture 30 minutes, be modulated into paste and be coated on copper film, dry in the shade; Then at 100Kg cm
-2pressure under, by compressing the copper film after drying in the shade, make negative pole.
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| CN111446439A (en) * | 2020-05-20 | 2020-07-24 | 中南大学 | S@MxSnSy@ C composite positive electrode active material, preparation method thereof and application of active material in lithium-sulfur battery |
| CN112234184A (en) * | 2020-10-14 | 2021-01-15 | 桑顿新能源科技有限公司 | SnS/CNTs/S composite material and preparation method and application thereof |
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| CN104577083A (en) * | 2015-01-20 | 2015-04-29 | 浙江大学 | Positive electrode sulfur-carrying material of lithium-sulfur battery and preparation method of lithium-sulfur battery |
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| CN109411737A (en) * | 2018-12-06 | 2019-03-01 | 中国地质大学（北京） | A kind of polarity sulfide-sulphur/porous carbon composite anode material and preparation method thereof with three-dimensional structure |
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| CN111446439A (en) * | 2020-05-20 | 2020-07-24 | 中南大学 | S@MxSnSy@ C composite positive electrode active material, preparation method thereof and application of active material in lithium-sulfur battery |
| CN111446439B (en) * | 2020-05-20 | 2021-04-13 | 中南大学 | S@MxSnSy@ C composite positive electrode active material, preparation method thereof and application of active material in lithium-sulfur battery |
| CN112234184A (en) * | 2020-10-14 | 2021-01-15 | 桑顿新能源科技有限公司 | SnS/CNTs/S composite material and preparation method and application thereof |
| CN113880130A (en) * | 2021-12-06 | 2022-01-04 | 中博龙辉装备集团股份有限公司 | Stannous sulfide carbon composite material and preparation method and application thereof |
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