CN104979534A - Iodine-sulfur / carbon composite material and preparation method and application thereof - Google Patents

Iodine-sulfur / carbon composite material and preparation method and application thereof Download PDF

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Publication number
CN104979534A
CN104979534A CN201510291364.4A CN201510291364A CN104979534A CN 104979534 A CN104979534 A CN 104979534A CN 201510291364 A CN201510291364 A CN 201510291364A CN 104979534 A CN104979534 A CN 104979534A
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sulfur
lithium
iodine
composite material
elemental
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CN104979534B (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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention discloses an iodine-sulfur/carbon composite material and a preparation method and application thereof. The composite material consists of elemental sulfur, elemental iodine and electrically conductive carbon black in the mass ratio of 25-85:0.05-40:5-70. The preparation steps are as below: uniformly mixing elemental sulfur, elemental iodine and conductive carbon black, then heating to 120-158 DEG C, treating at constant temperature for 3-48 h, and cooling to obtain a lithium-sulfur battery cathode material. The above iodine-sulfur / carbon composite material can be used in lithium/sulfur rechargeable battery cathode material. According to the invention, elemental iodine is added to the sulfur electrode, so that after initial discharge, a solid electrolyte-lithium iodide is formed to improve lithium ion conductivity situation of the sulfur electrode and further improve the rate performance of lithium-sulfur battery. The invention has the advantages of simple preparation method, batch production, good electrochemical overall performance, excellent rate performance, good dispersion of active materials in the electrode and good cycling stability, etc.

Description

A kind of iodo-sulphur/carbon composite and preparation method thereof and application
Technical field
The invention belongs to field of chemical power source, relate to a kind of iodo-sulphur/carbon composite and preparation method thereof and application.
Background technology
Current business-like lithium ion cell positive is mainly with LiCoO 2, LiFePO 4, LiCo 1/3ni 1/3mn 1/3o 2be main, its specific capacity is near 140 mAh/g; Positive electrode is mainly graphite, and specific capacity is at about 372 mAh/g, and the lithium ion battery specific energy obtained often is difficult to surmount 200 Wh/kg.And lithium-sulfur cell take elemental sulfur as positive active material, specific capacity reaches 1675 mAh/g, negative pole take directly lithium metal as active material, therefore lithium-sulfur cell theoretical energy density reaches 2600 Wh/kg, and existing energy density reaches the report of 400 Wh/kg pilot sample batteries at present.Due to the specific energy that it is higher, therefore lithium-sulfur cell is a kind of stored energy system of future generation of great potential.But the current problem of lithium-sulfur cell is: one, and elemental sulfur and discharging product thereof are that electronic isolation and ion insulate; Its two, because elemental sulfur is different from discharging product lithium sulfide density, simultaneously discharge intermediate product be dissolved in electrolyte.Therefore in charge and discharge process, there will be dissolution and production and the volumetric expansion of active material, thus easily cause active material skewness and cause chemical property to decay in the electrodes.
For solving the conductivity problems of lithium-sulfur cell, researchers have carried out a large amount of experiments, devise numerous schemes: 1) use the organic conductive macromolecule such as polyaniline, polypyrrole material clad anode active material, thus improve the conductivity of electrode.2) porous carbon materials of Large ratio surface is used to improve the conductive aspects of sulfur electrode to strengthen the contact site of sulphur and carbon.But above scheme is all for the purpose of the electronic conductance improving sulfur electrode, and the same lithium ion insulation of sulfur electrode, after therefore improving the electronic conductivity of sulfur electrode, the lithium ion conduction situation improving sulfur electrode is also very important.In existing research, (the Wu Feixiang such as 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.) use carbon-lithium sulfide as lithium sulfur battery anode material, using lithium iodide as the additive application of electrolyte in lithium-sulfur cell, the oxidizing potential of initial charge process can be effectively reduced.
Summary of the invention
For the defect that elemental sulfur in current lithium-sulfur cell and discharging product lithium sulfide ion thereof insulate, the invention provides good iodo-sulphur/carbon composite of a kind of electrochemistry combination property and preparation method thereof and application, composite material prepared by the method has good conductivity, electrochemical stability, is beneficial to the high rate performance and cyclical stability that improve lithium-sulfur cell.
The object of the invention is to be achieved through the following technical solutions:
A kind of iodo-sulphur/carbon composite, be made up of elemental sulfur, iodine and conductive black, its mass ratio is 25 ~ 85:0.05 ~ 40:5 ~ 70, can be expressed as I 2-S/C, wherein: I 2represent I, S represents element sulphur, and C represents conductive black.
The preparation method of above-mentioned iodo-sulphur/carbon composite, concrete steps are as follows:
Elemental sulfur, iodine are mixed with conductive black, be then heated to 120 ~ 158 DEG C, constant temperature process 3 ~ 48 hours, obtains 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 one or more in Ketjen black, acetylene black, Super P, CMK-3, active carbon, carbon nano-tube, Graphene, carbon fiber.
Compared to prior art, tool of the present invention has the following advantages:
1, the present invention uses iodine to add sulfur electrode to, makes it after electric discharge first, generate solid electrolyte---lithium iodide, thus improve the lithium ion conduction situation of sulfur electrode and improve the high rate performance of lithium-sulfur cell.
2, the present invention have preparation method simple, can excellent, the active material advantage such as good dispersion, good cycling stability in the electrodes of mass production, electrochemistry good combination property, high rate performance.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained I 2-S/C composite material X-ray diffraction pattern;
Fig. 2 is the stable circulation linearity curve of embodiment 1 gained lithium-sulfur cell;
Fig. 3 is the stable circulation linearity curve of embodiment 2 gained lithium-sulfur cell;
Fig. 4 is the stable circulation linearity curve of embodiment 3 gained lithium-sulfur cell.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1:
(1) elemental sulfur of mass ratio 65:10:25, iodine are mixed with Ketjen black, above-mentioned material is heated to 155 DEG C and keeps 12 hours, obtain I 2-S/C composite material, its XRD diffraction pattern is as Fig. 1.
(2) I will obtained 2-S/C composite material and Super P; PVDF in mass ratio 8:1:1 is dispersed in nmp solvent; be coated on after forming uniform slurry on aluminium foil; dry at 50 DEG C and obtain positive pole; use metal lithium sheet under the protection of argon gas atmosphere, to be assembled into 2025 type button cells for negative pole, electrolyte is that the LiTFSI of l mol/L is dissolved in DOL:DME (v:v=1:1; DOL:1,3-dioxolanes; DME: glycol dimethyl ether).Electro-chemical test all at room temperature carries out.Charge-discharge test potential region is 1.7-2.6 V, and current density is 1 C, and the stable circulation linearity curve obtained as shown in Figure 2.
Embodiment 2:
(1) elemental sulfur of mass ratio 60:10:30, iodine are mixed with Super P, above-mentioned material is heated to 125 DEG C and keeps 24 hours, obtain I 2-S/C composite material.
(2) I will obtained 2-S/C composite material assembling button cell, the method for the assembled battery adopting same embodiment 1 same and charge-discharge test mode.Stable circulation linearity curve as shown in Figure 3.
Embodiment 3:
(1) elemental sulfur of mass ratio 60:5:35, iodine are mixed with CMK-3, above-mentioned material is heated to 130 DEG C and keeps 24 hours, obtain I 2-S/C composite material.
(2) I will obtained 2-S/C composite material assembling button cell, the method for the assembled battery adopting same embodiment 1 same and charge-discharge test mode.Stable circulation linearity curve as shown in Figure 4.
Embodiment 4:
As different from Example 1, the mass ratio of elemental sulfur, iodine and acetylene black is 35:15:50 to the present embodiment.
Embodiment 5:
As different from Example 1, the mass ratio of elemental sulfur, iodine and active carbon is 40:35:25 to the present embodiment.
Embodiment 6:
As different from Example 1, the mass ratio of elemental sulfur, iodine and conductive black is 70:20:10 to the present embodiment, and conductive black is the mixture of carbon nano-tube and Graphene, and the two mass ratio is 1:1.

Claims (4)

1. iodo-sulphur/carbon composite, is characterized in that described composite material is made up of elemental sulfur, iodine and conductive black, and its mass ratio is 25 ~ 85:0.05 ~ 40:5 ~ 70.
2. iodo-sulphur/carbon composite according to claim 1, is characterized in that described conductive black is one or more in Ketjen black, acetylene black, Super P, CMK-3, active carbon, carbon nano-tube, Graphene, carbon fiber.
3. a preparation method for iodo-sulphur/carbon composite according to claim 1, is characterized in that described method step is as follows:
Elemental sulfur, iodine are mixed with conductive black, be then heated to 120 ~ 158 DEG C, constant temperature process 3 ~ 48 hours, obtains lithium sulfur battery anode material after cooling.
4. iodo-sulphur/carbon composite according to 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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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN109509872A (en) * 2017-09-14 2019-03-22 中南大学 A kind of halide is as all solid lithium of electrode active material and catalyst sulphur/sodium-sulphur battery
CN112002895A (en) * 2020-08-20 2020-11-27 常州大学 Preparation method of organic sulfur positive electrode material of lithium-sulfur battery
CN112234185A (en) * 2020-10-28 2021-01-15 珠海冠宇电池股份有限公司 Positive pole piece and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3660163A (en) * 1970-06-01 1972-05-02 Catalyst Research Corp Solid state lithium-iodine primary battery

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3660163A (en) * 1970-06-01 1972-05-02 Catalyst Research Corp Solid state lithium-iodine primary battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
XIAO LIANG, ET AL.: "Highly dispersed sulfur in ordered mesoporous carbon sphere as a composite cathode for rechargeable polymer Li/S battery", 《JOURNAL OF POWER SOURCES》 *
Y.L.WANG, ET AL.: "Rechargeable lithium/iodine battery with superior high-rate capability by using iodine–carbon composite as cathode", 《ENERGY & ENVIRONMENTAL SCIENCE》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109509872A (en) * 2017-09-14 2019-03-22 中南大学 A kind of halide is as all solid lithium of electrode active material and catalyst sulphur/sodium-sulphur battery
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
CN112002895A (en) * 2020-08-20 2020-11-27 常州大学 Preparation method of organic sulfur positive electrode material of lithium-sulfur battery
CN112002895B (en) * 2020-08-20 2022-04-26 常州大学 Preparation method of organic sulfur positive electrode material of lithium-sulfur battery
CN112234185A (en) * 2020-10-28 2021-01-15 珠海冠宇电池股份有限公司 Positive pole piece and application thereof

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