CN104835948A - Composite material for anodes of lithium sulfur batteries, method for manufacturing composite material and anodes and batteries which are made of composite material - Google Patents
Composite material for anodes of lithium sulfur batteries, method for manufacturing composite material and anodes and batteries which are made of composite material Download PDFInfo
- Publication number
- CN104835948A CN104835948A CN201510292305.9A CN201510292305A CN104835948A CN 104835948 A CN104835948 A CN 104835948A CN 201510292305 A CN201510292305 A CN 201510292305A CN 104835948 A CN104835948 A CN 104835948A
- Authority
- CN
- China
- Prior art keywords
- composite material
- naphthalene
- poly
- lithium
- sulphur
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M4/362—Composites
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a composite material for anodes of lithium sulfur batteries. The composite material comprises polynaphthylene/sulfur composite materials and porous titanium dioxide. The porous titanium dioxide wraps the surfaces of the polynaphthylene/sulfur composite materials. The invention further provides a method for manufacturing the composite material for the anodes of the lithium sulfur batteries, and the anodes and the batteries which are made of the composite material for the anodes of the lithium sulfur batteries. The composite material for the anodes of the lithium sulfur batteries, the method, the anodes and the batteries have the advantages that the porous titanium dioxide wraps the surfaces of the polynaphthylene/sulfur composite materials, so that lithium polysulfide generated by the anodes when electricity of the batteries is discharged is difficult to dissolve in electrolyte; the S (sulfur) capacity of electrode materials can be greatly improved by the aid of the composite material for the anodes of the lithium sulfur batteries, and the high contents of sulfur in the polynaphthylene/sulfur composite materials can reach 65%-80%; polynaphthylene and the titanium dioxide are elastic to a certain extent and are combined with each other, so that double relief effects can be realized for volume expansion of the anodes.
Description
Technical field
The present invention relates to sulphur technical field of lithium batteries, in particular to lithium-sulphur cell positive electrode composite material, preparation method and positive pole, the battery be made up of it.
Background technology
Lithium ion battery is widely used in the various mobile electronic devices such as notebook computer, camera, mobile phone, panel computer.Due to the fast development of mobile electronic device, require more and more higher to the specific capacity of battery and specific energy.Current commercial Li-ion battery can not meet due to the restriction of self theoretical capacity, so the secondary cell in the urgent need to developing height ratio capacity high-energy-density, and lithium-sulfur cell (theoretical specific capacity is 1675.0mAh/g, specific energy is 2500Wh/kg, 2800Wh/L) be considered to one of the most promising high-energy battery.
Lithium-sulfur cell is completely different from traditional lithium ion battery.The theoretical capacity of traditional lithium ion battery is limited to the deintercalation quantity of lithium ion, when discharging Lithium-ion embeding electrode material lattice in, deviate from again during charging, deintercalation quantity can not be too many, otherwise can cause these metal oxide materials structures that irreversible change occurs, finally cause battery to damage completely.And lithium-sulfur cell is by the fracture of sulphur sulfide linkage and is formed and come electric discharge and charging, so can realize more high power capacity charge and discharge.
But lithium-sulfur cell is usually using elemental sulfur or sulfenyl composite material as the positive pole of battery at present, there is following defect in use: (1) battery is in discharge process, many lithium sulfides that anode produces are soluble in electrolyte, cause the cycle life of battery not long; (2) the S amount of carrying of composite material is not high; (3) electrode volume expansion issues is still comparatively serious.
In view of this, special proposition the present invention.
Summary of the invention
The first object of the present invention is to provide a kind of lithium-sulphur cell positive electrode composite material, and this composite material, by poriferous titanium dioxide being wrapped in poly-naphthalene/sulphur composite material surface, makes battery many lithium sulfides that positive pole produces when discharging not be soluble in electrolyte.Secondly, the S that carries that lithium-sulphur cell positive electrode composite material provided by the invention substantially increases electrode material measures, and makes the content of sulphur in poly-naphthalene/sulphur composite material up to 65% ~ 80%.In addition, because poly-naphthalene and titanium dioxide have certain elasticity, both combine, and have dually slow down effect to the volumetric expansion of electrode.
The second object of the present invention is the preparation method providing a kind of described lithium-sulphur cell positive electrode composite material, the method first by chemical precipitation method prepare carry S amount up to 65% ~ 80% naphthalene/sulphur composite material, and then poriferous titanium dioxide is wrapped in the extexine of poly-naphthalene/sulphur composite material, final obtained stable, effective lithium-sulphur cell positive electrode composite material.
The third object of the present invention is to provide the positive pole be made up of lithium-sulphur cell positive electrode composite material provided by the present invention.
Present invention also offers a kind of lithium-sulfur cell, comprise the positive pole be made up of lithium-sulphur cell positive electrode composite material provided by the present invention.
In order to realize above-mentioned purpose of the present invention, spy by the following technical solutions:
A kind of lithium-sulphur cell positive electrode composite material, comprises poly-naphthalene/composite material and poriferous titanium dioxide; Described poriferous titanium dioxide is coated on described poly-naphthalene/sulphur composite layer.
Lithium-sulphur cell positive electrode composite material provided by the invention, at poly-naphthalene/coated porous titanium dioxide of sulphur composite layer.This layer of coated poriferous titanium dioxide forms barrier at poly-naphthalene/sulphur composite layer, make to gather/many lithium sulfides that naphthalene sulphur composite material in use generates are encased by poriferous titanium dioxide, are insoluble in electrolyte.Further, poriferous titanium dioxide has stronger adsorptivity, even if there are the many lithium sulfides of small part to be dissolved out, poriferous titanium dioxide also can adsorb many lithium sulfides, limits its loss by dissolution.
In the present invention, poly-naphthalene/sulphur composite material surface has wrapped up poriferous titanium dioxide, thus also can cover sulphur at the outer surface of poly-naphthalene, that can improve poly-naphthalene/sulphur composite material carries S amount, makes the content of sulphur in poly-naphthalene/sulphur composite material up to 65% ~ 80%.In addition, because poly-naphthalene and titanium dioxide have certain elasticity, both combine, and have dually slow down effect to the volumetric expansion of electrode.
A preparation method for lithium-sulphur cell positive electrode composite material provided by the present invention, comprises the steps:
(1) in hypo solution, add poly-naphthalene, stir after ultrasonic, and drip hydrochloric acid in the process stirred, again stir after hydrochloric acid dropwises, then mixed liquor is filtered successively, wash, dry, obtained poly-naphthalene/sulphur composite material;
(2) described poly-naphthalene/sulphur composite material is scattered in aqueous isopropanol, rear dropping ammoniacal liquor, ammoniacal liquor dropwises dropping two (acetylacetone based) metatitanic acid diisopropyl ester in backward mixed liquor and reacts, carry out successively after reaction terminates filtering, washing and drying, obtained described lithium-sulphur cell positive electrode composite material.In preparation method provided by the present invention, first prepare poly-naphthalene/sulphur composite material by chemical precipitation method.By this method, the content of the sulphur in the poly-naphthalene/sulphur composite material prepared reaches 65% ~ 80%, and what substantially increase poly-naphthalene/sulphur composite material carries S amount.
By the method provided in step (2), successfully poriferous titanium dioxide is wrapped in the extexine of poly-naphthalene/sulphur composite material, final obtained stable, effective lithium-sulphur cell positive electrode composite material.
In step (1), namely in the poly-naphthalene/sulphur composite material of preparation, sodium thiosulfate provides elemental sulfur.In order to the S that carries improving poly-naphthalene/sulphur composite material measures, be not that the consumption of sodium thiosulfate is the bigger the better.This is because poly-naphthalene is as the carrier carrying S, be the macromolecular material with fine and close layer structure, when the consumption of sodium thiosulfate is too large, affect the deposition effect of elemental sulfur in poly-naphthalene, the poly-naphthalene/sulphur composite structure of formation is not fine and close.Preferably, the present invention is when preparing poly-naphthalene/sulphur composite material, and the mass ratio of poly-naphthalene and hypo solution is 0.5:(150 ~ 180).
The concentration of hypo solution also affects the compactness of poly-naphthalene/sulphur composite material, preferably, in step (1), in described hypo solution, the mass fraction of sodium thiosulfate is 4.6% ~ 12.8%, the deposition rate of elemental sulfur can be controlled, the poly-naphthalene/sulphur composite material of obtained compact structure, improve and carry S amount.
In preparation method provided by the present invention, hydrochloric acid and sodium thiosulfate react and provide elemental sulfur, ensure when hydrochloric acid is excessive a little that sodium thiosulfate reacts completely as much as possible, preferably, the volume ratio of the solution of described hydrochloric acid and described sodium thiosulfate is (10 ~ 30): (150 ~ 200).The concentration of hydrochloric acid is preferably 10 ~ 12mol/L.
Ultrasonicly sodium thiosulfate can be penetrated sufficiently in the layer structure of poly-naphthalene, in order to ensure sodium thiosulfate fully to infiltrate in the layer structure of poly-naphthalene, preferably, in step (1), described ultrasonic frequency is 40 ~ 50KHz.
Hydrochloric acid and sodium thiosulfate react produces elemental sulfur, the drop rate of hydrochloric acid affects the deposition rate of elemental sulfur, in order to ensure the deposition effect of elemental sulfur in poly-naphthalene/sulphur composite material, preferably, in step (1), the dropping frequency of described hydrochloric acid is 2 ~ 3 drops/sec.
In chemical deposition process, stirring can make hydrochloric acid react with sodium thiosulfate fast, but should be affect sulphur in poly-naphthalene material surface distribution situation when the speed of stirring is too fast, preferably, in step (1), the speed of stirring is 300 ~ 400rpm.
Preferably, in step (1), the employing water of described washing and ethanol are with 1:(2 ~ 3) the formulated mixed liquor of volume ratio, this mixed liquor can not introduce impurity in material, also can remove impurity well.Meanwhile, the solid matter collected after filtering with this solution washing, also can not affect the structure of material.The impurity that water used in described cleaning solution contains is more few better, and most preferably, water used in described cleaning solution is any one in distilled water, deionized water or high purity water.
A kind of lithium-sulfur cell positive pole, comprises lithium-sulphur cell positive electrode composite material provided by the present invention.
A kind of lithium-sulfur cell, comprises the lithium-sulfur cell positive pole that lithium-sulphur cell positive electrode composite material provided by the present invention is prepared from.
Compared with prior art, beneficial effect of the present invention is:
(1) lithium-sulphur cell positive electrode composite material provided by the invention, at poly-naphthalene/coated porous titanium dioxide of sulphur composite layer.This layer of coated poriferous titanium dioxide forms barrier at poly-naphthalene/sulphur composite layer, make to gather/many lithium sulfides that naphthalene sulphur composite material in use generates are encased by poriferous titanium dioxide, are difficult to be dissolved in electrolyte.Further, poriferous titanium dioxide has stronger adsorptivity, even if there are the many lithium sulfides of small part to be dissolved out, poriferous titanium dioxide also can adsorb many lithium sulfides, limits its loss by dissolution.
(2) the lithium-sulphur cell positive electrode composite material provided in the present invention, poly-naphthalene/sulphur composite material surface has wrapped up poriferous titanium dioxide, to a certain extent, slow down many lithium sulfides that poly-naphthalene/sulfur electrode generates in electrochemical process and be dissolved in problem in electrolyte, thus also sulphur can be covered at the outer surface layer of poly-naphthalene, play the advantage that the surface area of poly-naphthalene is large, that greatly improves electrode material carries S amount, makes the content of sulphur in poly-naphthalene/sulphur composite material up to 65% ~ 80%.
(3) the lithium-sulphur cell positive electrode composite material provided in the present invention, because poly-naphthalene and titanium dioxide have certain elasticity, both combine, and have dually slow down effect to the volumetric expansion of electrode.
(4), in the preparation method of lithium-sulphur cell positive electrode composite material provided by the present invention, first poly-naphthalene/sulphur composite material is prepared by chemical precipitation method.By this method, the content of the sulphur in the poly-naphthalene/sulphur composite material prepared reaches 65% ~ 80%, and what substantially increase poly-naphthalene/sulphur composite material carries S amount.
(5) in the preparation method of lithium-sulphur cell positive electrode composite material provided by the present invention, the mass ratio of poly-naphthalene and sodium thiosulfate is 0.5:(7.22 ~ 22.03), make the poly-naphthalene/sulphur composite structure densification formed, thus ensure the sulfur content in poly-naphthalene/sulphur composite material.
(6) in the preparation method of lithium-sulphur cell positive electrode composite material provided by the present invention, in described hypo solution, the mass fraction of sodium thiosulfate is 4.6% ~ 12.8%, the deposition rate of elemental sulfur can be controlled, poly-naphthalene/sulphur the composite material of obtained compact structure, improves and carries S amount.
(7), in the preparation method of lithium-sulphur cell positive electrode composite material provided by the present invention, described ultrasonic frequency is 40 ~ 50KHz, ensures fully to be infiltrated into by sodium thiosulfate in the layer structure of poly-naphthalene.
(8) in the preparation method of lithium-sulphur cell positive electrode composite material provided by the present invention, the dropping frequency of hydrochloric acid is 2 ~ 3 drops/sec, controls the deposition rate of elemental sulfur, ensure that the deposition effect of elemental sulfur in poly-naphthalene/sulphur composite material.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below.
The stable circulation linearity curve of the lithium-sulfur cell that Fig. 1 provides for embodiment 1 and comparative example 2.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting the scope of the invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturer suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, be and can buy by commercially available the conventional products obtained.
Embodiment 1
S11: the poly-naphthalene of preparation
Dried for 4g 3,4,9,10-hexichol tetracarboxylic acid anhydride (PTCDA) is positioned in electric tube furnace, after vacuumizing applying argon gas through three times, mix up argon gas flow velocity (25mL/min), install device for absorbing tail gas (absorbing liquid is calcium hydroxide saturated aqueous solution), be then heat up with the speed of 5 DEG C/min under the condition of room temperature in initial temperature, be warming up to 530 DEG C, keep 8 hours at this temperature, then continue to heat up with the speed of 5 DEG C/min, be warming up to 1000 DEG C, and maintain 6 hours at such a temperature, then Temperature fall, obtains poly-naphthalene.
S12: the poly-naphthalene/sulphur composite material of preparation
7.22g sodium thiosulfate is dissolved in 150mL high purity water completely, then the poly-naphthalene that 0.5g is obtained is added in hypo solution, add magneton and stir; Stir after 1 hour, take out magneton, poly-naphthalene/sodium thiosulfate mixed liquor is put into Vltrasonic device ultrasonic 2 hours, ultrasonic frequency is 40KHz; After ultrasonic end, be reentered into magneton and stir; Now, drip hydrochloric acid while stirring, the concentration of hydrochloric acid is 10mol/L, and drop rate controls at 2 ~ 3 drops/sec, after all being added by 10mL hydrochloric acid, continue stirring 4 hours, then filter, wash the solid matter collected with high purity water, after washing terminates, by dry for the solid matter collected, obtain poly-naphthalene/sulphur composite material.
S13: the poly-naphthalene/sulphur composite material preparing poriferous titanium dioxide parcel
Take poly-naphthalene/sulphur composite material that 0.48g prepares, be placed in 40mL high purity water and 160mL isopropyl alcohol mixture, stir after 10 minutes, to this mixed solution and dripping 3mL ammoniacal liquor, the mass percentage of ammoniacal liquor is 25%; After ammoniacal liquor all drips, continue stirring 0.5 hour.
Stir after 0.5 hour, drip two (acetylacetone based) metatitanic acid diisopropyl ester solution that 1.6mL mass percentage is 75% in mixed reaction solution, point four droppings, drip 0.4mL at every turn, after each dropping terminates, need stir and drip for 0.5 hour again.
After whole dropping, react 4 hours at normal temperatures, then filter, successively with the object material after the solid matter collected after isopropyl alcohol and high purity water cleaning and filtering, dry cleaning, namely obtain the poly-naphthalene/sulphur composite material of the poriferous titanium dioxide parcel prepared by the present invention.
Embodiment 2
S21: the poly-naphthalene of preparation
Dried for 2g 3,4,9,10-hexichol tetracarboxylic acid anhydride (PTCDA) is positioned in electric tube furnace, after vacuumizing applying argon gas through three times, mix up argon gas flow velocity (25mL/min), install device for absorbing tail gas (absorbing liquid is calcium hydroxide saturated aqueous solution), be then heat up with the speed of 5 DEG C/min under the condition of room temperature in initial temperature, be warming up to 530 DEG C, keep 8 hours at this temperature, then continue to heat up with the speed of 5 DEG C/min, be warming up to 1100 DEG C, and maintain 6 hours at such a temperature, then Temperature fall, obtains poly-naphthalene.
S22: the poly-naphthalene/sulphur composite material of preparation
12g sodium thiosulfate is dissolved in 150mL distilled water completely, and the poly-naphthalene then prepared by 0.5g adds in hypo solution, adds magneton and stirs; Stir after 1 hour, take out magneton, poly-naphthalene/sodium thiosulfate mixed liquor is put into Vltrasonic device ultrasonic 3 hours, ultrasonic frequency is 50KHz; After ultrasonic end, be reentered into magneton and stir; Now, drip hydrochloric acid while stirring, the concentration of hydrochloric acid is 12mol/L, and drop rate controls at 2 ~ 3 drops/sec, after all being added by 13mL hydrochloric acid, continue stirring 4 hours, then filter, wash than the mixed liquor being 1:2 the solid matter collected with distilled water and ethanol contend, after washing terminates, by dry for the solid matter collected, obtain poly-naphthalene/sulphur composite material.
S23: the poly-naphthalene/sulphur composite material preparing poriferous titanium dioxide parcel
Take poly-naphthalene/sulphur composite material that 0.48g prepares, be placed in 40mL distilled water and 160mL isopropyl alcohol mixture, stir after 10 minutes, to this mixed solution and dripping 4mL ammoniacal liquor, the mass percentage of ammoniacal liquor is 25%; After ammoniacal liquor all drips, continue stirring 0.5 hour.
Stir after 0.5 hour, drip two (acetylacetone based) metatitanic acid diisopropyl ester solution that 1.6mL mass percentage is 75% in mixed reaction solution, point four droppings, drip 0.4mL at every turn, after each dropping terminates, need stir and drip for 0.5 hour again.
After whole dropping terminates, react 4 hours at normal temperatures, then filter, successively with the object material after the solid matter collected after isopropyl alcohol and high purity water cleaning and filtering, dry cleaning, namely obtain the poly-naphthalene/sulphur composite material of the poriferous titanium dioxide parcel prepared by the present invention.
Embodiment 3
S31: the poly-naphthalene of preparation
The same S11 of preparation method.
S32: the poly-naphthalene/sulphur composite material of preparation
In this step, the quality of sodium thiosulfate used is 18g, is dissolved in 180mL high purity water, and the quality of poly-naphthalene used is 0.5g, and the concentration of hydrochloric acid dripped is 12mol/L, and volume is 23mL, the same S12 of concrete preparation process, does not here describe in detail this.
S33: the poly-naphthalene/sulphur composite material preparing poriferous titanium dioxide parcel
The same S13 of preparation method.
Embodiment 4
S41: the poly-naphthalene of preparation
The same S21 of preparation method.
S42: the poly-naphthalene/sulphur composite material of preparation
In this step, the quality of sodium thiosulfate used is 22.03g, is dissolved in 180mL distilled water, and the quality of poly-naphthalene used is 0.5g, and the concentration of hydrochloric acid dripped is 10mol/L, and volume is 30mL, the same S22 of concrete preparation process, does not here describe in detail this.
S43: the poly-naphthalene/sulphur composite material preparing poriferous titanium dioxide parcel
The same S23 of preparation method.
Comparative example 1
In comparative example 1, the preparation method of poly-naphthalene is with embodiment 1.
Poly-naphthalene and the elemental sulfur of synthesis to be mixed in mass ratio at 1: 4, and fully grind well in mortar, then put into electric tube furnace and calcine, be first warming up to 150 DEG C, maintenance 5h, then continues to be warming up to 300 DEG C, and keeps 2h at this temperature, obtain poly-naphthalene/sulphur composite material.
Comparative example 2
In comparative example 2, the preparation method of poly-naphthalene is with embodiment 2.
Poly-naphthalene and the elemental sulfur of synthesis to be mixed in mass ratio at 1: 3, and fully grind well in mortar, then put into electric tube furnace and calcine, be first warming up to 150 DEG C, maintenance 5h, then continues to be warming up to 300 DEG C, and keeps 2h at this temperature, obtain poly-naphthalene/sulphur composite material.
Experimental example
Electrode material prepared by embodiment 1-4 and comparative example 1, comparative example 2 is all prepared into positive pole, is then assembled into battery.The assembling of positive plate preparation and battery is carried out all in accordance with the following methods.
The preparation of battery anode slice:
Be placed on respectively by the lithium-sulphur cell positive electrode composite material of preparation and mix thoroughly in mortar, then to mix at 7: 2: 1 in mass ratio with conductive agent carbon black, PVDF, grind, mix thoroughly, be coated on aluminium foil, vacuum drying at 65 DEG C, is then pressed into positive plate.
The assembling of battery:
In glove box, the above-mentioned positive plate made is combined into button cell together with negative pole, barrier film, electrolyte, shell, leaves standstill more than 24 hours, test; Wherein, negative pole is lithium; Electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li, 3-dioxolane solution, the concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/L, as the glycol dimethyl ether and 1 of solvent, the volume ratio of 3-dioxolanes is 2: 1, and diaphragm is lithium ion battery separator Celgrad2300 (ZheJiang NanYang Science Co., Ltd's production).
Performance test
Adopt Land test macro to carry out charge-discharge test to the lithium-sulfur cell that embodiment 1-2 and comparative example 1-2 provides, wherein, discharge and recharge interval is 1.0-3.0V, and charging and discharging currents density is 400mA/g.The specific discharge capacity of above-mentioned lithium-sulfur cell is as shown in table 1.
Table 1
In the performance test that the present invention carries out, charging and discharging currents density is 400mA/g.Theoretical routinely, current density increases, discharge capacity can reduce, even if but under so large current density, as can be seen from the result of table 1, the battery discharge specific capacity aspect that the poly-naphthalene/sulphur composite material wrapped up by poriferous titanium dioxide provided by the invention is prepared from still can reach good effect, and is significantly better than comparative example.
Although illustrate and describe the present invention with specific embodiment, however it will be appreciated that can to make when not deviating from the spirit and scope of the present invention many other change and amendment.Therefore, this means to comprise all such changes and modifications belonged in the scope of the invention in the following claims.
Claims (10)
1. a lithium-sulphur cell positive electrode composite material, is characterized in that, comprises poly-naphthalene/sulphur composite material and poriferous titanium dioxide; Described poriferous titanium dioxide is coated on described poly-naphthalene/sulphur composite material surface.
2. a preparation method for lithium-sulphur cell positive electrode composite material described in claim 1, is characterized in that, comprise the steps:
(1) in hypo solution, add poly-naphthalene, stir after ultrasonic, and drip hydrochloric acid in the process stirred, again stir after hydrochloric acid dropwises, then mixed liquor is filtered successively, wash, dry, obtained poly-naphthalene/sulphur composite material;
(2) be scattered in aqueous isopropanol by described poly-naphthalene/sulphur composite material, rear dropping ammoniacal liquor, ammoniacal liquor dropwises dropping two (acetylacetone based) metatitanic acid diisopropyl ester in backward mixed liquor and reacts; Carry out successively after reaction terminates filtering, washing and drying, obtained described lithium-sulphur cell positive electrode composite material.
3. preparation method according to claim 2, is characterized in that, in step (1), in described hypo solution, the mass percentage of sodium thiosulfate is 4.6% ~ 12.8%; The mass ratio of described poly-naphthalene and hypo solution is 0.5:(150 ~ 180).
4. preparation method according to claim 3, is characterized in that, in step (1), described hydrochloric acid is (10 ~ 30) with the ratio of the volume of hypo solution: (150 ~ 200); The concentration of described hydrochloric acid is 11 ~ 12mol/L.
5. preparation method according to claim 2, is characterized in that, in step (1), described ultrasonic frequency is 40 ~ 50KHz.
6. preparation method according to claim 2, is characterized in that, in step (1), the dropping frequency of described hydrochloric acid is 2 ~ 3 drops/sec.
7. preparation method according to claim 2, is characterized in that, in step (1), the speed of described stirring is 300 ~ 400rpm.
8. preparation method according to claim 2, is characterized in that, in step (1), described washing adopts water and ethanol with 1:(2 ~ 3) the formulated mixed liquor of volume ratio.
9. a lithium-sulfur cell positive pole, is characterized in that, comprises lithium-sulphur cell positive electrode composite material according to claim 1.
10. a lithium-sulfur cell, is characterized in that, comprises lithium-sulfur cell positive pole according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510292305.9A CN104835948B (en) | 2015-06-01 | 2015-06-01 | Lithium-sulphur cell positive electrode composite, preparation method and the positive pole being made from it, battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510292305.9A CN104835948B (en) | 2015-06-01 | 2015-06-01 | Lithium-sulphur cell positive electrode composite, preparation method and the positive pole being made from it, battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104835948A true CN104835948A (en) | 2015-08-12 |
| CN104835948B CN104835948B (en) | 2017-10-20 |
Family
ID=53813681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510292305.9A Active CN104835948B (en) | 2015-06-01 | 2015-06-01 | Lithium-sulphur cell positive electrode composite, preparation method and the positive pole being made from it, battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104835948B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470514A (en) * | 2015-12-29 | 2016-04-06 | 江西师范大学 | Composite material for lithium-sulfur battery positive electrode, preparation method, and positive electrode and battery prepared from composite material |
| CN105977461B (en) * | 2016-05-30 | 2018-10-12 | 华南师范大学 | A kind of preparation method of Li-S battery anode composite materials |
| CN109216668A (en) * | 2018-08-03 | 2019-01-15 | 河南师范大学 | A kind of spherical tio2 package lithium sulfide/sulphur composite material preparation method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1877887A (en) * | 2006-06-23 | 2006-12-13 | 清华大学 | Lithium-iron disulfide anode materials and method for preparing same |
| CN102623676A (en) * | 2012-03-29 | 2012-08-01 | 江西苏克尔新材料有限公司 | Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same |
| CN103579590A (en) * | 2013-05-09 | 2014-02-12 | 中国地质大学（武汉） | Preparation method for coating anode material of lithium battery |
| CN103840143A (en) * | 2014-03-19 | 2014-06-04 | 中南大学 | Preparation method of S/TiO2 composite material for anode of sodium-sulfur battery |
| CN204130629U (en) * | 2014-10-15 | 2015-01-28 | 南京中储新能源有限公司 | A kind of secondary aluminium cell graphene array anode composite |
| CN204243148U (en) * | 2014-10-10 | 2015-04-01 | 南京中储新能源有限公司 | A kind of secondary cell combination electrode and secondary aluminium cell |
-
2015
- 2015-06-01 CN CN201510292305.9A patent/CN104835948B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1877887A (en) * | 2006-06-23 | 2006-12-13 | 清华大学 | Lithium-iron disulfide anode materials and method for preparing same |
| CN102623676A (en) * | 2012-03-29 | 2012-08-01 | 江西苏克尔新材料有限公司 | Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same |
| CN103579590A (en) * | 2013-05-09 | 2014-02-12 | 中国地质大学（武汉） | Preparation method for coating anode material of lithium battery |
| CN103840143A (en) * | 2014-03-19 | 2014-06-04 | 中南大学 | Preparation method of S/TiO2 composite material for anode of sodium-sulfur battery |
| CN204243148U (en) * | 2014-10-10 | 2015-04-01 | 南京中储新能源有限公司 | A kind of secondary cell combination electrode and secondary aluminium cell |
| CN204130629U (en) * | 2014-10-15 | 2015-01-28 | 南京中储新能源有限公司 | A kind of secondary aluminium cell graphene array anode composite |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105470514A (en) * | 2015-12-29 | 2016-04-06 | 江西师范大学 | Composite material for lithium-sulfur battery positive electrode, preparation method, and positive electrode and battery prepared from composite material |
| CN105470514B (en) * | 2015-12-29 | 2018-04-03 | 江西师范大学 | Lithium-sulphur cell positive electrode composite, preparation method and the positive pole being made from it, battery |
| CN105977461B (en) * | 2016-05-30 | 2018-10-12 | 华南师范大学 | A kind of preparation method of Li-S battery anode composite materials |
| CN109216668A (en) * | 2018-08-03 | 2019-01-15 | 河南师范大学 | A kind of spherical tio2 package lithium sulfide/sulphur composite material preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104835948B (en) | 2017-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ban et al. | A high-performance and durable poly (ethylene oxide)-based composite solid electrolyte for all solid-state lithium battery | |
| CN103579590B (en) | A kind of preparation method of clad anode material of lithium battery | |
| CN103700820B (en) | A kind of lithium ion selenium battery with long service life | |
| CN107785603B (en) | Lithium-sulfur cell electrolyte and preparation method thereof and the battery for using the electrolyte | |
| CN102820454B (en) | Electrode composite material and preparation method thereof, positive pole, there is this anodal battery | |
| CN104151588B (en) | Diaphragm for lithium-sulfur batteries and preparation method of lithium-sulfur batteries | |
| CN102623676B (en) | Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same | |
| CN106099062A (en) | Silicon based composite material Si@C@TiO is covered in double-contracting2and preparation method thereof | |
| CN105226285B (en) | A kind of porous Si-C composite material and preparation method thereof | |
| CN102916195B (en) | Graphene-coated copper oxide composite cathode material and method for manufacturing same | |
| JP2002367678A (en) | Lithium-sulfur battery | |
| CN108306016A (en) | A method of cell positive material surface is modified using coupling agent | |
| CN106941161B (en) | A kind of preparation method of nitrogen-doped graphene/manganese dioxide/hollow sulphur composite material | |
| CN108172406B (en) | FeS is used as a catalyst2-xSexSodium ion capacitor with negative electrode material | |
| CN103219491A (en) | Copper sulfide anode and preparation method thereof | |
| CN106159267A (en) | A kind of preparation method of sulfur carbon composite | |
| CN104362316A (en) | Lithium-sulfur battery composite cathode material, and preparation method and application thereof | |
| CN105047861A (en) | Sulfur-carbon composite material and preparation method thereof | |
| CN104852040B (en) | A kind of preparation method of the nickel lithium manganate cathode material of high multiplying power lithium ion battery | |
| CN109950487A (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN104638246A (en) | Graphene-based flexible lithium-sulfur battery positive electrode material, preparation method of positive electrode material and preparation method of positive electrode | |
| CN108321438A (en) | Full graphite lithium-sulfur cell and preparation method thereof | |
| CN110416533A (en) | A kind of ion battery composite material and preparation method and ion battery | |
| CN107732203A (en) | A kind of preparation method of nano ceric oxide/graphene/sulphur composite | |
| CN103606656B (en) | A kind of preparation method of the lead oxide/graphene nanocomposite material for plumbous charcoal superbattery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |