CN102623676B - Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same - Google Patents
Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same Download PDFInfo
- Publication number
- CN102623676B CN102623676B CN201210088258.2A CN201210088258A CN102623676B CN 102623676 B CN102623676 B CN 102623676B CN 201210088258 A CN201210088258 A CN 201210088258A CN 102623676 B CN102623676 B CN 102623676B
- Authority
- CN
- China
- Prior art keywords
- lithium
- naphthalene
- poly
- composite material
- positive pole
- 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.)
- Active
Links
Classifications
-
- 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 a composite material for a positive pole of a lithium-sulfur battery, and a positive pole and a battery both made of the material. The composite material is the mixture of polynaphthylene or polynaphthylene derivative with the mass percentage of 20-34 percent, and sulfur. The preparation method for the composite material comprises the steps that firstly, the polynaphthylene or the polynaphthylene derivative is uniformly mixed with the sulfur; secondly, the mixture is placed in an electric tube furnace at the temperature of 150 DEG C for 5-8 hours, and then at the temperature of 300 DEG C for 2-3 hours; and lastly, the material is reduced to room temperature through natural cooling, so as to obtain the composite material. The invention also provides the positive pole for the lithium-sulfur battery and the battery which are made of the composite material. The lithium-sulfur battery provide by the invention has high discharge specific capacity, meanwhile, the utilization ratio of active substance is effectively improved, the cycling stability of the battery is also improved to a certain extent, and the cost of the battery is reduced.
Description
Technical field
The Anode and battery that the present invention relates to a kind of anode composite material of lithium sulfur battery and be made up of it, belongs to technical field of energy material.
Background technology
From the development of current battery, the production technology of lithium ion battery (comprising lithium-sulfur cell) reaches its maturity, and is progressively applied to the various aspects of the modern life.In recent years, the negative material of lithium ion battery oneself obtain important breakthrough, but the positive electrode slower development of lithium ion, be no matter the ternary material of layer assembling structure, the LiFePO of polyanionic
4, or the LiMn of spinel structure
2o
4, theoretical specific capacity is all less than 200mAhg
-1.Therefore, the exploitation of new high-energy-density, long circulation life, low cost and eco-friendly novel anode material is particularly important.And take lithium metal as the secondary cell of composite material as positive pole of negative pole, elemental sulfur or sulphur, its theoretical energy density is 2600Whkg
-1, be considered to one of secondary cell system of current most research attraction.
Yao Zhendong etc. (Yao Zhendong, Wei Wei, Wang Jiulin etc. lithium-sulfur rechargeable battery anode progress. Acta PhySico-Chimica Sinica, 2011,27 (5): 1005-1016.) point out that current lithium-sulfur rechargeable battery also exists several key issue: (1) elemental sulfur is at room temperature insulator; (2) elemental sulfur can be reduced into the polysulfide of Yi Rong in discharge process, causes active material to run off, and after polysulfide is dissolved in electrolyte, can worsen the ionic conductivity of electrolyte; (3) be dissolved in the direct contacting metal cathode of lithium of polysulfide of electrolyte, self discharge reaction occurs; (4) in charge and discharge process can there is corresponding pucker & bloat in sulfur electrode, destroys the physical structure of electrode to a certain extent.
Wu Feng etc. (Wu Feng, Wu Shengxian, Chen outstanding personality etc. multi-walled carbon nano-tubes is to the modification of elemental sulfur positive electrode chemical property. new carbon, 2010,6 (25): 421-425.) record: for the problem existing for sulfur electrode, researcher forms sulphur composite material by adding conducting polymer such as polyaniline, polypyrrole or carbon class adsorbent in elemental sulfur, examples of such additives effectively can stop the dissolving of polysulfide while improving sulfur electrode electric conductivity, improves the chemical property of battery to a certain extent.
Lithium-sulfur cell generally by the composite material of sulphur or sulphur as positive pole, form with corresponding negative pole, electrolyte, diaphragm and shell.Conventional positive pole, by the composite material of sulphur or sulphur, conductive agent, adhesive and related solvents mix and blend form slurry, is coated on collector, dries, roll compacting becomes positive plate.Carbon nano-tube has unique mechanics, characteristic electron and chemical characteristic, can be widely used in the chemical property improving electrode material.
(the Juchen Guo such as Juchen Guo, Yunhua Xu, and Chunsheng Wang, Sulfur-ImpregatedDisordered Carbon Nanotubes Cathode for Lithium Sulfur Batteries.Nano Lett., 2011,11:4288-4294.) report a kind of composite material of carbon nano-tube/sulphur, its initial discharge specific capacity can reach 1000mAhg
-1above.Although carbon nano-tube/sulphur composite material, compared with other composite material, exists obvious advantage, it also has some to need badly to improve part, such as: the total content of sulphur is little, and the utilance of sulphur is not high, and cyclical stability has much room for improvement.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of lithium-sulphur cell positive electrode composite material, by through poly-naphthalene and sulphur mixing, utilize a kind of composite material that can be used in lithium-sulphur cell positive electrode that poly-naphthalene obtains the package action of sulphur and good conductivity.
The present invention also aims to the preparation method that above-mentioned lithium-sulphur cell positive electrode composite material is provided.
The present invention also aims to provide a kind of lithium-sulfur cell positive pole, it utilizes above-mentioned composite material to make.
The present invention also aims to provide a kind of lithium-sulfur cell, its just very above-mentioned lithium-sulfur cell positive pole.
For achieving the above object, the present invention provide firstly a kind of lithium-sulphur cell positive electrode composite material, and it is made up of poly-naphthalene or derivatives thereof and sulphur, and wherein, the poly-mass percent of naphthalene or derivatives thereof in this lithium-sulphur cell positive electrode composite material is 20-34%.
In above-mentioned anode composite material of lithium sulfur battery, preferably, adopt the structure of poly-naphthalene to be shown below:
Wherein, n is >=100;
The poly-naphthalene derivatives adopted obtains by modifying poly-naphthalene, even if poly-naphthalene connection-NO
2,-NH
2or-SO
3obtain Deng functional group.
Present invention also offers the preparation method of above-mentioned lithium-sulphur cell positive electrode composite material, it comprises the following steps: will gather naphthalene or poly-naphthalene derivatives and sulphur and mix (wherein, the quality of poly-naphthalene or poly-naphthalene derivatives may be controlled to the 20-34% of the gross mass accounting for poly-naphthalene or poly-naphthalene derivatives and sulphur), put into electric tube furnace, be warming up to 150 DEG C and keep 5h-8h, and then be warming up to 300 DEG C of maintenance 2h-3h, finally naturally cool to room temperature and obtain this lithium-sulphur cell positive electrode composite material.
In the preparation method of above-mentioned lithium-sulphur cell positive electrode composite material, poly-naphthalene can be prepared by following steps: by 3,4,9,10-perylene tetracarboxylic acid dianhydride is placed in electric tube furnace, after vacuumizing applying argon gas through three times (wherein, vacuum degree when vacuumizing will reach more than-0.1MPa, during applying argon gas, the pressure in electric tube furnace be made to reach 0-0.03MPa), argon gas stream speed is adjusted to 20-30mL/min, be warming up to 530 DEG C and keep 6-10 hour, and then be warming up to 600 DEG C-3500 DEG C maintenances 5-10 hour, then Temperature fall, obtain poly-naphthalene.
In the preparation method of above-mentioned lithium-sulphur cell positive electrode composite material, poly-naphthalene derivatives can be prepared by following steps:
Concentration is that the sulfuric acid of 98wt% is as solvent, be 20-30mL/g as the sulfuric acid of solvent and the ratio of poly-naphthalene, stir, and in reactor, drip by constant pressure funnel concentration is 65-68% nitric acid and concentration is the sulfuric acid of 98%, the mol ratio of poly-naphthalene and nitric acid is 1:4-8, and this nitric acid is with HNO
3meter, the sulfuric acid of dropping and the volume ratio of nitric acid are 1-2:1, and in the process dripping nitric acid and sulfuric acid, temperature controls at 75-82 DEG C, drips and finishes, then stir 1.5 hours, obtain reactant liquor;
Then reactant liquor is poured in frozen water, after fully stirring, add appropriate alkali (such as NaOH) and be neutralized to pH value and reach 7, be down to room temperature, filter, the solid obtained after filtration high-purity washing 3 times, dry, obtain poly-naphthalene derivatives.
According to specific embodiment of the invention scheme, preferably, above-mentioned poly-naphthalene derivatives can be prepared by following concrete steps:
2g is gathered naphthalene and is placed in 250mL there-necked flask, add the sulfuric acid that 40mL-80mL concentration is 98wt%, be heated to 80 DEG C, then drip the mixed acid that nitric acid that 24mL-48mL concentration is 65-68wt% and 28mL-56mL concentration are the sulfuric acid composition of 98wt%, in the process dripping mixed acid, temperature remains on 80 DEG C, after being added dropwise to complete, continue to react 1.5 hours at this temperature, then naturally cool to room temperature, obtain reactant liquor;
Then reactant liquor is poured in 300mL frozen water, after fully stirring, add appropriate alkali and be neutralized to pH value and reach 7, temperature is adjusted to room temperature, filters, the solid obtained after filtration high-purity washing 3 times, dry, obtain poly-naphthalene derivatives, be i.e. the itrated compound of poly-naphthalene.
Present invention also offers a kind of lithium-sulfur cell positive pole, it is prepared by lithium-sulphur cell positive electrode composite material provided by the present invention.
According to specific embodiment of the invention scheme, this lithium-sulfur cell positive pole can be prepared by following steps:
Described lithium-sulphur cell positive electrode composite material, conductive agent and adhesive are mixed according to the mass ratio of 7:2:1, be coated on collector, vacuum drying at 60-70 DEG C, then roll compacting obtains this lithium-sulfur cell positive pole.
According to specific embodiment of the invention scheme, in above-mentioned lithium-sulfur cell positive pole, the conductive agent adopted can be the arbitrary conductive agent of lithium-sulfur cell energy, the adhesive adopted can be the arbitrary adhesive of lithium-sulfur cell energy, preferably, above-mentioned conductive agent comprises the combination of one or more in carbon black, acetylene black and graphite powder etc., and above-mentioned adhesive comprises the combination of one or more in Kynoar (PVDF), cyclodextrin and gel etc.
In above-mentioned lithium-sulfur cell, the collector adopted can be arbitrary conductive metal foil, and preferably, above-mentioned conductive metal foil is aluminium foil.
Present invention also offers a kind of lithium-sulfur cell, it comprises positive pole, negative pole, electrolyte, barrier film and shell, wherein, and above-mentioned lithium-sulfur cell positive pole just very provided by the present invention.
In lithium-sulfur cell provided by the invention, its negative pole, electrolyte, barrier film and shell can be in lithium-sulfur cell commonly use.According to specific embodiment of the invention scheme, preferably, above-mentioned negative pole is lithium, above-mentioned electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li (LiTFSI), 3-dioxolane solution, wherein, the concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/L, be 2:1 as the glycol dimethyl ether (DME) of solvent and the volume ratio of DOX (DOL).The lithium ion battery diaphragm (the lithium ion battery diaphragm Celgrad2300 that such as ZheJiang NanYang Science Co., Ltd produces) that the diaphragm adopted in above-mentioned lithium-sulfur cell can be commonly used for this area; Better performance can be had by the lithium-sulfur cell adopting these assemblies and positive pole provided by the present invention to form.
Lithium-sulphur cell positive electrode composite material provided by the present invention adopts poly-naphthalene and its derivative to carry out alternative carbon nano-tube, poly-naphthalene not only has good conductivity, also has good layer structure, particularly outstanding is that poly-naphthalene and its derivative itself also has capacity, carbon nano-tube is replaced with poly-naphthalene and its derivative, poly-naphthalene and its derivative can have certain package action to sulphur as carbon nano-tube, there is good conductivity, but also (sulphur is as positive active material to have the incomparable cooperative effect of carbon nano-tube, there is higher discharge capacity, and as the poly-naphthalene of load material, not only there is good conductivity and the covering property to sulphur, itself also has discharge capacity, from this angle, the anode composite material that they form just comprises the discharge capacity sum of two aspects, there is synergy.And be there is no discharge capacity as the material itself of carbon nano-tube, these loads of Graphene).The specific discharge capacity of lithium-sulfur cell provided by the present invention is high, significantly improves the utilance of active material, and improves the cyclical stability of battery to a certain extent, decreases the cost of battery.
Accompanying drawing explanation
The discharge curve first of the lithium-sulfur cell that Fig. 1 is embodiment 1, comparative example 1 and comparative example 2 provide;
The stable circulation linearity curve of the lithium-sulfur cell that Fig. 2 is embodiment 1, comparative example 1 and comparative example 2 provide;
The electrochemical impedance curve of the lithium-sulfur cell that Fig. 3 provides for embodiment 1 and comparative example 1;
The electrochemical impedance curve of the lithium-sulfur cell that Fig. 4 provides for comparative example 2;
Fig. 5 is the structural representation of lithium-sulfur cell;
Fig. 6 is the infrared spectrum of the poly-naphthalene that embodiment 1 is synthesized;
Fig. 7 is the infrared spectrum of the poly-naphthalene that embodiment 4 is synthesized.
Main Reference label declaration:
Shell 5 on lower casing 1 positive pole 2 barrier film 3 negative pole 4
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide a kind of lithium-sulfur cell, it is prepared by following steps:
1, the synthesis of poly-naphthalene:
4g oneself dried 3, 4, 9, 10-perylene tetracarboxylic acid dianhydride (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), then be 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, obtain poly-naphthalene, its infrared spectrum as shown in Figure 6.
2, the preparation of battery anode slice:
Poly-naphthalene and the sulphur of synthesis in mass ratio 1:3 mix, 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 keep 2h at this temperature);
Calcined product is mixed thoroughly in mortar, then with conductive agent carbon black, PVDF in mass ratio 7:2:1 mix, grind, mix thoroughly, be coated on aluminium foil, vacuum drying at 60-70 DEG C, is then pressed into positive plate.
3, the assembling of battery:
In glove box, the above-mentioned positive pole 2 made is combined into button cell (as shown in Figure 5 with negative pole 4, barrier film 3, electrolyte, shell together with (shell is made up of with lower casing 1 two parts upper shell 5), electrolyte is filled in button cell inside, do not show in figure), leave 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 Celgrad2300.
Embodiment 2
Present embodiments provide a kind of lithium-sulfur cell, it is prepared by following steps:
1, the synthesis of poly-naphthalene is with embodiment 1.
2, the preparation of battery anode slice:
Poly-naphthalene and the sulphur of synthesis in mass ratio 1:4 mix, fully grind well in mortar, then put into electric tube furnace and calcine (be first warming up to 150 DEG C, maintenance 5h-8h, then continues to be warming up to 300 DEG C, and keep 2-3h at this temperature);
Calcined product is mixed thoroughly in mortar, then with conductive agent carbon black, PVDF in mass ratio 7:2:1 mix, grind, mix thoroughly, be coated on aluminium foil, at 60-70 DEG C dry, be then pressed into positive plate.
3, the assembling of battery:
In glove box, the above-mentioned positive pole made is combined into button cell together with negative pole, barrier film, electrolyte, shell, leaves standstill 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 Celgrad2300.
Embodiment 3
Present embodiments provide a kind of lithium-sulfur cell, it is prepared by following steps:
1, the synthesis of the itrated compound of poly-naphthalene:
The poly-naphthalene that 2g embodiment 1 is synthesized is placed in 250mL there-necked flask, add 50mL sulfuric acid (concentration is 98wt%) again, stir, be heated to 80 DEG C, and in there-necked flask, drip by constant pressure funnel the mixed acid that concentration is 65-68wt% nitric acid (24mL) and concentration are the sulfuric acid (28mL) of 98wt%, in the process dripping mixed acid, remain that internal temperature is at 80 DEG C, drip and finish, continue to react 1.5 hours at this temperature, then room temperature is naturally cooled to, then this reactant liquor is poured in 300mL frozen water, after abundant stirring, add appropriate alkali neutralization, till causing pH=7, filter, then the solid high-purity washing 3 times obtained after filtration, dry, finally obtain 2.68g product, the i.e. itrated compound of poly-naphthalene.
2, the preparation of battery anode slice:
Poly-naphthalene itrated compound and the sulphur of synthesis in mass ratio 1:3 mix, fully grind well in mortar, then put into electric tube furnace and calcine (be first warming up to 150 DEG C, maintenance 5h-8h, then continues to be warming up to 300 DEG C, and keep 2-3h at this temperature);
Calcined product is mixed thoroughly in mortar, then with conductive agent carbon black, PVDF in mass ratio 7:2:1 mix, grind, mix thoroughly, be coated on aluminium foil, at 60-70 DEG C dry, be then pressed into positive plate.
3, 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 that lithium ion battery separator Celgrad2300(ZheJiang NanYang Science Co., Ltd produces).
Embodiment 4
Present embodiments provide a kind of lithium-sulfur cell, it is prepared by following steps:
1, the synthesis of poly-naphthalene:
2g oneself dried 3, 4, 9, 10-perylene tetracarboxylic acid dianhydride (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), then be 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, obtain poly-naphthalene, its infrared spectrum as shown in Figure 7.
2, the preparation of battery anode slice:
Poly-naphthalene and the sulphur of synthesis in mass ratio 1:3 mix, 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 keep 2h at this temperature);
Calcined product is mixed thoroughly in mortar, then with conductive agent carbon black, PVDF in mass ratio 7:2:1 mix, grind, mix thoroughly, be coated on aluminium foil, vacuum drying at 65 DEG C, is then pressed into positive plate.
3, the assembling of battery:
In glove box, the above-mentioned positive pole 2 made is combined into button cell (as shown in Figure 5 with negative pole 4, barrier film 3, electrolyte, shell together with (shell is made up of with lower casing 1 two parts upper shell 5), electrolyte is filled in button cell inside, do not show in figure), leave 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 Celgrad2300.
Comparative example 1
This comparative example provides a kind of lithium-sulfur cell, and it is prepared by following steps:
1, the preparation of battery anode slice:
By carbon nano-tube and sulphur in mass ratio 1:3 mix, fully grind well in mortar, then put into electric tube furnace calcining (be first warming up to 150 DEG C, keep 5h-8h, then continue to be warming up to 300 DEG C, and keep 2-3h at this temperature);
Calcined product is mixed thoroughly in mortar, then with conductive agent carbon black, PVDF in mass ratio 7:2:1 mix, grind, mix thoroughly, be coated on aluminium foil, at 60-70 DEG C dry, be then pressed into positive plate.
2, 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 24 hours, test; Wherein, negative pole is lithium; Electrolyte is glycol dimethyl ether and the DOX solution of bis trifluoromethyl sulfonic acid imide li, and the concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/L, is 2:1 as the glycol dimethyl ether of solvent and the volume ratio of DOX; Diaphragm is lithium ion battery separator Celgrad2300.
Comparative example 2
This comparative example provides a kind of lithium-sulfur cell, and it is prepared by following steps:
1, the preparation of battery anode slice:
By carbon black and sulphur in mass ratio 1:3 mix, fully grind well in mortar, then put into electric tube furnace calcining (be first warming up to 150 DEG C, keep 5h-8h, then continue to be warming up to 300 DEG C, and keep 2-3h at this temperature);
Calcined product is mixed thoroughly in mortar, then with conductive agent carbon black, PVDF in mass ratio 7:2:1 mix, grind, mix thoroughly, be coated on aluminium foil, at 60-70 DEG C dry, be then pressed into positive plate.
2, 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 24 hours, test; Wherein, negative pole is lithium; Electrolyte is glycol dimethyl ether and the DOX solution of bis trifluoromethyl sulfonic acid imide li, and the concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/L, is 2:1 as the glycol dimethyl ether of solvent and the volume ratio of DOX; Diaphragm is Celgrad2300.
Performance test:
Land test macro is adopted to carry out charge-discharge test to the lithium-sulfur cell that embodiment 1-4 and comparative example 1-2 provides, wherein, discharge and recharge interval is 1.0-3.0V, charging and discharging currents density is 100mAh/g, the specific discharge capacity of above-mentioned lithium-sulfur cell is as shown in table 1, and discharge curve and cyclical stability test result are respectively as depicted in figs. 1 and 2 first.
Adopt CHI660d electrochemical workstation to carry out ac impedance measurement to the lithium-sulfur cell that embodiment 1-4 and comparative example 1-2 provides, wherein, AC impedance frequency range is 10
-2-10
5hz, amplitude is 5mv, shown in electrochemical impedance test result Fig. 3 and Fig. 4.
In Fig. 1,3 and 4, A represents the lithium-sulfur cell that embodiment 1 provides, and B represents the lithium-sulfur cell that comparative example 1 provides, and C represents the lithium-sulfur cell that comparative example 2 provides.In fig. 2, curve 1 represents the lithium-sulfur cell that embodiment 1 provides, and curve 2 represents the lithium-sulfur cell that comparative example 1 provides, and curve 3 represents the lithium-sulfur cell that comparative example 2 provides.
The specific discharge capacity of the lithium-sulfur cell that table 1 embodiment 1-4 and comparative example 1-2 provides
As can be seen from the content of table 1 and Fig. 1-4, the employing that embodiment 1-4 provides gathers naphthalene/sulphur composite material lithium-sulfur cell in discharge capacity, cyclical stability, the internal resistance of cell, is obviously better than the lithium-sulfur cell that comparative example 1-2 provides.
Claims (11)
1. a lithium-sulphur cell positive electrode composite material, it is made up of poly-naphthalene or derivatives thereof and sulphur, and wherein, the mass percent of described poly-naphthalene or derivatives thereof in this lithium-sulphur cell positive electrode composite material is 20-34%;
Wherein, the structure of described poly-naphthalene is shown below:
Wherein, n >=100;
Described poly-naphthalene derivatives makes poly-naphthalene connection-NO
2,-NH
2or-SO
3obtain.
2. the preparation method of lithium-sulphur cell positive electrode composite material according to claim 1, it comprises the following steps:
Naphthalene or poly-naphthalene derivatives and sulphur will be gathered mix, put into electric tube furnace, and be warming up to 150 DEG C and keep 5h-8h, and then be warming up to 300 DEG C of maintenance 2h-3h, and finally naturally cool to room temperature and obtain described lithium-sulphur cell positive electrode composite material.
3. preparation method according to claim 2, wherein, described poly-naphthalene is prepared by following steps:
3,4,9,10-perylene tetracarboxylic acid dianhydride is placed in electric tube furnace, after vacuumizing applying argon gas through three times, argon gas stream speed is adjusted to 20-30mL/min, is warming up to 530 DEG C and keeps 6-10 hour, and then being warming up to 600 DEG C-3500 DEG C maintenance 5-10 hour, Temperature fall, obtains described poly-naphthalene.
4. the preparation method according to Claims 2 or 3, wherein, described poly-naphthalene derivatives is prepared by following steps:
Poly-naphthalene is placed in reactor, adding concentration is that the sulfuric acid of 98wt% is as solvent, be 20-30mL/g as the sulfuric acid of solvent and the ratio of poly-naphthalene, stir, and in reactor, drip by constant pressure funnel concentration is 65-68% nitric acid and concentration is the sulfuric acid of 98%, the mol ratio of described poly-naphthalene and described nitric acid is 1:4-8, and described nitric acid is with HNO
3meter, the sulfuric acid of dropping and the volume ratio of nitric acid are 1-2:1, and in the process dripping nitric acid and sulfuric acid, temperature controls at 75-82 DEG C, drips and finishes, then stir 1.5 hours, obtain reactant liquor;
Then reactant liquor is poured in frozen water, after fully stirring, add appropriate alkali and be neutralized to pH value and reach 7, temperature is adjusted to room temperature, filters, the solid obtained after filtration high-purity washing 3 times, dry, obtain described poly-naphthalene derivatives.
5. preparation method according to claim 4, wherein, described poly-naphthalene derivatives is prepared by following steps:
2g is gathered naphthalene and is placed in 250mL there-necked flask, add the sulfuric acid that 40mL-80mL concentration is 98wt%, be heated to 80 DEG C, then drip the mixed acid that nitric acid that 24mL-48mL concentration is 65-68wt% and 28mL-56mL concentration are the sulfuric acid composition of 98wt%, in the process dripping mixed acid, temperature remains on 80 DEG C, after being added dropwise to complete, continue to react 1.5 hours at this temperature, then naturally cool to room temperature, obtain reactant liquor;
Then reactant liquor is poured in 300mL frozen water, after fully stirring, add appropriate alkali and be neutralized to pH value and reach 7, temperature is adjusted to room temperature, filters, the solid obtained after filtration high-purity washing 3 times, dry, obtain described poly-naphthalene derivatives.
6. a lithium-sulfur cell positive pole, it is prepared by lithium-sulphur cell positive electrode composite material according to claim 1.
7. lithium-sulfur cell positive pole according to claim 6, wherein, this lithium-sulfur cell positive pole is prepared by following steps:
Described lithium-sulphur cell positive electrode composite material, conductive agent and adhesive are mixed according to the mass ratio of 7:2:1, be coated on collector, vacuum drying at 60-70 DEG C, then roll compacting obtains this lithium-sulfur cell positive pole.
8. lithium-sulfur cell positive pole according to claim 7, wherein, described conductive agent comprises the combination of one or more in carbon black, acetylene black and graphite powder;
Described adhesive comprises the combination of one or more in Kynoar, cyclodextrin and gel;
Described collector is conductive metal foil.
9. lithium-sulfur cell positive pole according to claim 8, wherein, described conductive metal foil is aluminium foil.
10. a lithium-sulfur cell, it comprises positive pole, negative pole, electrolyte, barrier film and shell, wherein, the lithium-sulfur cell positive pole described in described any one of just very claim 6-9.
11. lithium-sulfur cells according to claim 10, wherein, described negative pole is lithium, described electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li, 3-dioxolane solution, wherein, the concentration of described bis trifluoromethyl sulfonic acid imide li is 1mol/L, be 2:1 as the glycol dimethyl ether of solvent and the volume ratio of DOX.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210088258.2A CN102623676B (en) | 2012-03-29 | 2012-03-29 | Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210088258.2A CN102623676B (en) | 2012-03-29 | 2012-03-29 | Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102623676A CN102623676A (en) | 2012-08-01 |
| CN102623676B true CN102623676B (en) | 2015-03-04 |
Family
ID=46563456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210088258.2A Active CN102623676B (en) | 2012-03-29 | 2012-03-29 | Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102623676B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466232A (en) * | 2013-09-24 | 2015-03-25 | 华为技术有限公司 | Lithium-ion battery and preparation method of lithium metal alloy |
| CN104078681B (en) * | 2014-05-23 | 2015-07-22 | 南京中储新能源有限公司 | Sulfhydryl polymer positive electrode and secondary aluminium battery using same |
| CN104103835B (en) * | 2014-07-10 | 2017-01-11 | 华中科技大学 | Cathode material for sodium ion battery, and preparation method of cathode material |
| CN106159272A (en) * | 2015-04-27 | 2016-11-23 | 中国人民解放军63971部队 | A kind of nitrogenous binding agent for lithium-sulfur cell and preparation method thereof |
| CN104835948B (en) * | 2015-06-01 | 2017-10-20 | 江西师范大学 | Lithium-sulphur cell positive electrode composite, preparation method and the positive pole being made from it, battery |
| CN105390663A (en) * | 2015-10-16 | 2016-03-09 | 广东烛光新能源科技有限公司 | Sulfur-containing electrode, lithium-sulfur battery containing sulfur-containing electrode and manufacturing method for lithium-sulfur battery |
| 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 |
| CN105529490B (en) * | 2016-02-05 | 2017-04-26 | 驰特（佛山）新能源科技有限公司 | Preparation method for lithium-sulfur battery |
| CN105778111A (en) * | 2016-03-08 | 2016-07-20 | 苏州珍展科技材料有限公司 | Preparation method and application of novel laminar composite |
| CN110618175A (en) * | 2019-10-09 | 2019-12-27 | 哈尔滨工业大学 | Electrochemical detection device and method for soluble polysulfide in metal/sulfur battery |
| CN116376279A (en) * | 2023-03-01 | 2023-07-04 | 武汉大学 | Sulfur-phenylenediamine polymer composite material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740758A (en) * | 2010-01-04 | 2010-06-16 | 北京航空航天大学 | Preparation method of vulcanized conducting polymer composite anode for lithium ion battery |
| CN102263257A (en) * | 2011-06-28 | 2011-11-30 | 中国科学院金属研究所 | High energy flexible electrode material and preparation method thereof and application thereof in storage battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002110237A (en) * | 2000-08-17 | 2002-04-12 | Samsung Sdi Co Ltd | Positive electrode active material composition for lithium-sulfur battery, its manufacturing method and lithium-sulfur battery |
-
2012
- 2012-03-29 CN CN201210088258.2A patent/CN102623676B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101740758A (en) * | 2010-01-04 | 2010-06-16 | 北京航空航天大学 | Preparation method of vulcanized conducting polymer composite anode for lithium ion battery |
| CN102263257A (en) * | 2011-06-28 | 2011-11-30 | 中国科学院金属研究所 | High energy flexible electrode material and preparation method thereof and application thereof in storage battery |
Non-Patent Citations (1)
| Title |
|---|
| 聚萘的合成及其光电器件;黄美荣 等;《化学进展》;20100131;第22卷(第1期);第113页-第118页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102623676A (en) | 2012-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102623676B (en) | Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same | |
| CN103199258B (en) | Anode material for lithium-ion batteries, anode preparation method and lithium ion battery | |
| CN101867038B (en) | Method for preparing anode composite material for lithium sulfur secondary batteries | |
| CN103219491B (en) | Copper sulfide anode and preparation method thereof | |
| CN102867940B (en) | Process for preparing lithium sulfur battery modified anode | |
| CN103515614B (en) | A kind of additives for battery, positive electrode containing this additive and preparation method thereof | |
| CN103236530B (en) | Si-C composite material and preparation method thereof, lithium ion battery containing this material | |
| CN111276678B (en) | Single-layer graphene coated FeS2Preparation method and application of carbon nanotube material | |
| CN103579590A (en) | Preparation method for coating anode material of lithium battery | |
| WO2012146046A1 (en) | Polyimide capacitance battery and manufacturing method thereof | |
| CN104362294B (en) | A kind of porous sulphur positive pole for lithium-sulfur cell, its preparation method and lithium-sulfur cell | |
| CN104617283B (en) | The preparation method of a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode and the preparation method of positive pole | |
| CN106920936B (en) | High-performance organic lithium ion battery positive electrode material and preparation method thereof | |
| CN105280949A (en) | Lithium sulfur battery using manganese dioxide/graphene as cathode barrier layer | |
| CN108630889A (en) | A kind of lithium-sulfur cell and its anode and preparation method using nitride/graphene as interlayer | |
| CN103515595A (en) | Sulfur/polypyrrole-graphene composite material, preparation method thereof, battery positive electrode and lithium-sulfur battery | |
| CN103682413A (en) | High-rate long-cycle-life lithium iron phosphate battery and preparation method thereof | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN106159221A (en) | A kind of nano-sized carbon sulfur composite for lithium-sulfur cell | |
| CN105914394A (en) | Composite cathode material of low-temperature lithium ion battery, cathode plate of low-temperature lithium ion battery, preparation method thereof, and lithium ion battery | |
| CN108321438A (en) | Full graphite lithium-sulfur cell and preparation method thereof | |
| CN107681130A (en) | A kind of preparation method of the lithium sulfur battery anode material of solid electrolyte | |
| CN114583093A (en) | Preparation method and application of high-energy-density hard carbon composite negative electrode material | |
| CN103236533A (en) | Potassium vanadate nanobelt material for lithium ion battery and preparation method thereof | |
| CN114613974A (en) | Long-life quick-charging type lithium ion battery cathode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |