CN104979534B - A kind of iodine sulphur/carbon composite and preparation method and application - Google Patents

A kind of iodine sulphur/carbon composite and preparation method and application Download PDF

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Publication number
CN104979534B
CN104979534B CN201510291364.4A CN201510291364A CN104979534B CN 104979534 B CN104979534 B CN 104979534B CN 201510291364 A CN201510291364 A CN 201510291364A CN 104979534 B CN104979534 B CN 104979534B
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sulfur
lithium
iodine
carbon composite
sulphur
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CN104979534A (en
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左朋建
张瀚
花俊夫
尹鸽平
高云智
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Harbin Institute of Technology
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Harbin Institute of Technology
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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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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 discloses a kind of iodine sulphur/carbon composite and preparation method and application, the composite is made up of elemental sulfur, iodine and conductive black, and its mass ratio is 25 ~ 85：0.05~40：5 ~ 70, preparation process is as follows：Elemental sulfur, iodine are well mixed with conductive black, are then heated to 120 ~ 158 DEG C, constant temperature is handled 3 ~ 48 hours, and lithium sulfur battery anode material is obtained after cooling.Above-mentioned iodine sulphur/carbon composite can be used for the positive electrode of lithium-sulfur rechargeable battery.The present invention is added to sulfur electrode using iodine, make its generation solid electrolyte --- lithium iodide after electric discharge first, improve the high rate performance of lithium-sulfur cell so as to improve the lithium ion conduction situation of sulfur electrode, have the advantages that preparation method it is simple, can mass production, electrochemistry good combination property, high rate performance be excellent, active material good dispersion, good cycling stability in the electrodes.

Description

A kind of iodo- sulphur/carbon composite and preparation method and application
Technical field
The invention belongs to field of chemical power source, is related to a kind of iodo- sulphur/carbon composite and preparation method and application.
Background technology
Current commercialized lithium ion cell positive is mainly with LiCoO2、LiFePO4、LiCo1/3Ni1/3Mn1/3O2Based on, its Specific capacity is near 140 mAh/g；Positive electrode is mainly graphite, and specific capacity is in 372 mAh/g or so, resulting lithium ion Battery specific energy is often difficult to surmount 200 Wh/kg.And lithium-sulfur cell, using elemental sulfur as positive active material, specific capacity reaches 1675 mAh/g, negative pole is directly using lithium metal as active material, therefore lithium-sulfur cell theoretical energy density reaches 2600 Wh/kg, and Has the report that energy density reaches 400 Wh/kg pilot sample batteries at present.Due to its higher ratio energy, therefore lithium sulphur is electric Pond is a kind of energy stores system of future generation of great potential.But lithium-sulfur cell it is current the problem of be：First, elemental sulfur and Its discharging product is that electronic isolation insulate with ion；Second, because elemental sulfur is different from discharging product lithium sulfide density, put simultaneously Electric intermediate product is dissolved in electrolyte.Therefore in charge and discharge process, it may appear that the dissolving of active material and precipitation and volumetric expansion, So as to easily cause active material in the electrodes skewness and cause chemical property to decay.
To solve the conductivity problems of lithium-sulfur cell, researchers have carried out substantial amounts of experiment, have devised numerous schemes： 1）Using the organic conductive macromolecule material clad anode active material such as polyaniline, polypyrrole, so as to improve the electric conductivity of electrode. 2）Improve the conductive aspects of sulfur electrode using the porous carbon materials of Large ratio surface to strengthen contact site of the sulphur with carbon.But with Upper scheme is and the sulfur electrode same lithium ion insulation for the purpose of the electronic conductance for improving sulfur electrode, therefore improves sulfur electrode Electronic conductivity after, the lithium ion conduction situation for improving sulfur electrode is also particularly significant.In existing research, Wu Feixiang Deng（Wu Feixiang, Lee Jung Tae, Nitta Naoki, et al. Lithium Iodide as a Promising Electrolyte Additive for Lithium–Sulfur Batteries: Mechanisms of Performance Enhancement[J]. Advanced Materials, 2015, 27(1): 101-108.）Lithium is used as using carbon-lithium sulfide Sulphur cell positive electrode material, using lithium iodide as the additive application of electrolyte in lithium-sulfur cell, can effectively reduce first The oxidizing potential of charging process.
The content of the invention
The defects of for elemental sulfur in current lithium-sulfur cell and its discharging product vulcanization lithium ion insulation, the invention provides Good iodo- sulphur/carbon composite of a kind of electrochemistry combination property and preparation method and application, composite wood prepared by this method Material is with preferable electric conductivity, electrochemical stability, beneficial to the high rate performance and cyclical stability for improving lithium-sulfur cell.
The purpose of the present invention is achieved through the following technical solutions：
A kind of iodo- sulphur/carbon composite, is made up of elemental sulfur, iodine and conductive black, and its mass ratio is 25 ~ 85： 0.05~40：5 ~ 70, I can be expressed as2- S/C, wherein：I2I is represented, S represents element sulphur, and C represents conductive black.
The preparation method of above-mentioned iodo- sulphur/carbon composite, is comprised the following steps that：
Elemental sulfur, iodine are well mixed with conductive black, are then heated to 120 ~ 158 DEG C, constant temperature processing 3 ~ 48 is small When, obtain lithium sulfur battery anode material after cooling.
Above-mentioned iodo- sulphur/carbon composite can be used for the positive electrode of lithium-sulfur rechargeable battery.
In the present invention, conductive black can be Ketjen black, acetylene black, Super P, CMK-3, activated carbon, CNT, stone One or more in black alkene, carbon fiber.
Compared to prior art, the invention has the advantages that：
1st, the present invention is added to sulfur electrode using iodine, makes its generation solid electrolyte --- iodine after electric discharge first Change lithium, improve the high rate performance of lithium-sulfur cell so as to improve the lithium ion conduction situation of sulfur electrode.
2nd, the present invention have preparation method it is simple, can mass production, electrochemistry good combination property, high rate performance it is excellent, Active material in the electrodes good dispersion, good cycling stability the advantages that.
Brief description of the drawings
Fig. 1 is the gained I of embodiment 12- S/C composite X-ray diffraction patterns；
Fig. 2 is the stable circulation linearity curve of the gained lithium-sulfur cell of embodiment 1；
Fig. 3 is the stable circulation linearity curve of the gained lithium-sulfur cell of embodiment 2；
Fig. 4 is the stable circulation linearity curve of the gained lithium-sulfur cell of embodiment 3.
Embodiment
Technical scheme is further described below in conjunction with the accompanying drawings, but is not limited thereto, it is every to this Inventive technique scheme is modified or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, all should cover In protection scope of the present invention.
Embodiment 1：
（1）By mass ratio 65:10:25 elemental sulfur, iodine are well mixed with Ketjen black, and above-mentioned material is heated to 155 DEG C are kept for 12 hours, obtain I2- S/C composites, its XRD diffraction pattern such as Fig. 1.
（2）The I that will be obtained2- S/C composites and Super P, PVDF in mass ratio 8:1:1 is dispersed in nmp solvent, Formed after uniform slurry coated on aluminium foil, at 50 DEG C drying obtain positive pole, the use of metal lithium sheet is negative pole in argon 2025 type button cells are assembled under the protection of gas atmosphere, electrolyte is that l mol/L LiTFSI is dissolved in DOL：DME (v:v= 1:1;DOL:1,3-dioxolanes; DME:Glycol dimethyl ether).Electro-chemical test is carried out at room temperature.Charge-discharge test Potential region is 1.7-2.6 V, and current density is 1 C, and obtained stable circulation linearity curve is as shown in Figure 2.
Embodiment 2：
（1）By mass ratio 60:10:30 elemental sulfur, iodine are well mixed with Super P, and above-mentioned material is heated to 125 DEG C are kept for 24 hours, obtain I2- S/C composites.
（2）The I that will be obtained2- S/C composites assemble button cell, using the side of the same assembled battery of same embodiment 1 Method and charge-discharge test mode.Stable circulation linearity curve is as shown in Figure 3.
Embodiment 3：
（1）By mass ratio 60:5:35 elemental sulfur, iodine are well mixed with CMK-3, and above-mentioned material is heated into 130 DEG C keep 24 hours, obtain I2- S/C composites.
（2）The I that will be obtained2- S/C composites assemble button cell, using the side of the same assembled battery of same embodiment 1 Method and charge-discharge test mode.Stable circulation linearity curve is as shown in Figure 4.
Embodiment 4：
As different from Example 1, the mass ratio of elemental sulfur, iodine and acetylene black is 35 to the present embodiment：15：50.
Embodiment 5：
As different from Example 1, the mass ratio of elemental sulfur, iodine and activated carbon is 40 to the present embodiment：35：25.
Embodiment 6：
As different from Example 1, the mass ratio of elemental sulfur, iodine and conductive black is 70 to the present embodiment:20:10, Conductive black is the mixture of CNT and graphene, and the two mass ratio is 1:1.

Claims (3)

1. a kind of iodo- sulphur/carbon composite, it is characterised in that the composite is by elemental sulfur, iodine and conductive black group Into its mass ratio is 25 ~ 85：0.05~40：5 ~ 70, specific preparation method is as follows：Elemental sulfur, iodine and conductive black are mixed Close uniformly, be then heated to 120 ~ 158 DEG C, constant temperature is handled 3 ~ 48 hours, and iodo- sulphur/carbon composite is obtained after cooling.
2. iodo- sulphur/carbon composite according to claim 1, it is characterised in that the conductive black is Ketjen black, acetylene One or more in black, Super P.
3. iodo- sulphur/carbon composite described in a kind of claim 1 is applied in lithium-sulfur rechargeable battery anode material.
CN201510291364.4A 2015-06-01 2015-06-01 A kind of iodine sulphur/carbon composite and preparation method and application Active CN104979534B (en)

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CN109509872B (en) * 2017-09-14 2021-01-01 中南大学 All-solid-state lithium sulfur/sodium sulfur battery with halide serving as electrode active substance and catalyst
CN107834074A (en) * 2017-11-02 2018-03-23 四川华昆能源有限责任公司 A kind of preparation method of lithium-sulfur cell solid state cathode additive and the sulphur negative electrode containing the additive
CN112002895B (en) * 2020-08-20 2022-04-26 常州大学 Preparation method of organic sulfur positive electrode material of lithium-sulfur battery
CN112234185B (en) * 2020-10-28 2022-08-30 珠海冠宇电池股份有限公司 Positive pole piece and application thereof

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