CN102903974A - Lithium-sulfur secondary battery - Google Patents
Lithium-sulfur secondary battery Download PDFInfo
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- CN102903974A CN102903974A CN2012104030651A CN201210403065A CN102903974A CN 102903974 A CN102903974 A CN 102903974A CN 2012104030651 A CN2012104030651 A CN 2012104030651A CN 201210403065 A CN201210403065 A CN 201210403065A CN 102903974 A CN102903974 A CN 102903974A
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- lithium
- rechargeable battery
- sulfur
- positive electrode
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a lithium-sulfur secondary battery comprising a positive electrode current collector, a positive electrode material, a porous diaphragm and a lithium-containing negative electrode plate as well as electrolyte, which are compressed integrally in a battery shell from bottom to top. The lithium-sulfur secondary battery is characterized in that a cellulose membrane is compressed between the positive electrode material and the porous diaphragm, and is one of a nitrocellulose membrane, a cellulose acetate membrane and a regenerated cellulose membrane. According to the invention, because the cellulose membrane is compressed between the positive electrode material and the porous diaphragm, and prevents polysulfide from transferring to a metal lithium negative electrode plate along with electrolyte in the lithium-sulfur secondary battery, inhibits side reaction caused by a 'shuttle flying phenomenon', effectively improves the coulombic efficiency of the lithium-sulfur secondary battery, prolongs the service life of the battery, and also is simple to operate, low in cost, and easy for mass production.
Description
Technical field
The invention belongs to lithium-sulfur rechargeable battery system technical field, particularly relate to a kind of lithium-sulfur rechargeable battery.
Background technology
Lithium-sulfur rechargeable battery refers to adopt lithium metal as negative plate, and elemental sulfur, sulfenyl composite material or organic sulfur compound (being referred to as sulphurous materials) etc. are as anodal chargeable battery.Elemental sulfur can generate lithium sulfide (Li with the lithium reaction
2S), the theoretical capacity that this electrochemical reaction is calculated with elemental sulfur is up to 1672mAh/g, and elemental sulfur is cheap, safety non-toxic, be the novel anode active material that has development potentiality, have high-energy-density, long circulation life, high security, lithium-sulfur rechargeable battery has represented the developing direction of battery of future generation cheaply.But lithium-sulfur rechargeable battery is in charge and discharge process, because having a large amount of intermediate products in the sulfur electrode is dissolved in the electrolyte, they spread in electrolyte, can side reaction occur on the lithium metal surface, the coulombic efficiency that causes battery to circulate weekly low (referring to discharge capacity of the cell and ratio with charging capacity in the cyclic process), thus the application of lithium-sulfur rechargeable battery greatly hindered.
Find through retrieval, publication number is that CN 101587951A, name are called the patent of invention of " a kind of novel carbon-sulfur compound for lithium-sulfur cell ", by take the macropore carbon material of high pore volume, high conductivity, high-ratio surface as matrix, the form of sulphur with simple substance is filled in the nanometer and micrometer grade hole of matrix, the combination reaction of sulphur and carbon also can occur simultaneously, make the novel carbon-sulfur compound that sulphur exists with one or more chemical states in Carbon Materials, can improve specific energy, specific power and the cycle performance of lithium-sulfur rechargeable battery; Another publication number be CN 1838469A, the name be called " lithium-sulfur cell electrolyte and chargeable lithium-sulphur battery thereof " and patent of invention, this electrolyte is as solvent take one or more quaternary ammonium salts ionic liquid, to suppress the dissolubility of intermediate product polysulfide in electrolyte of electrode reaction, can improve capacity characteristic and the cycle life of Li-S battery; Also retrieve a publication number and be the patent of invention that CN 102130364A, name are called " a kind of lithium-sulfur rechargeable battery system with gel-type polymer electrolyte and preparation method ", formed by Polymer-supported support body, ionic liquid, organic solvent, mixing lithium salts and silicon dioxide granule; Its preparation method is that glyoxaline ion liquid, silicon dioxide and compound lithium salts are made coagulant liquid in being dissolved with the carbonates solution of high molecular polymer, then coating, dry, obtain the gel-type polymer electrolyte film, can prevent the dissolving of lithium-sulfur rechargeable battery system medium sulphide content in liquid electrolyte, ionic conductivity is high, and nonflammable, do not reveal.
The above-mentioned patent of invention that retrieves relevant lithium-sulfur rechargeable battery, solved separately the different problem of lithium-sulfur rechargeable battery, cause reduction of service life but the ubiquity coulombic efficiency is low, side reaction is high, and exist and make relative complex and the high problem of cost, so that lithium-sulfur rechargeable battery is difficult to form large-scale production.
Summary of the invention
The present invention provides a kind of lithium-sulfur rechargeable battery for solving the technical problem that exists in the known technology, so that the lithium-sulfur rechargeable battery enclosed pasture efficient of making is high, side reaction is low, long service life, making is simple, cost is low, is easy to large-scale production.
The technical scheme that the present invention takes is:
A kind of lithium-sulfur rechargeable battery comprises that battery container inside suppresses from bottom to top all-in-one-piece plus plate current-collecting body, positive electrode, porous septum and contain the cathode of lithium sheet, and electrolyte, is characterized in: also be suppressed with cellulose membrane between positive electrode and porous septum; Described cellulose membrane is a kind of of nitrocellulose filter, CAM and regenerated cellulose film.
The present invention can also adopt following technical scheme:
Described positive electrode is that sulphurous materials, binding agent, the conductive agent of mass ratio 60-80:2-20:4-40 mixes in organic solution, and forming solid content is the slurry of 15-40%; Described sulphurous materials is elemental sulfur S
8, many lithium sulfides Li
2S
n(1≤n≤8), carbon sulphur polymer (C
2S
x)
m(2.5≤x≤50, and m 〉=2) or the sulfenyl composite material is a kind of; Described binding agent is aqueous binders or PVDF binding agent; Conductive agent is SP conductive agent or multi-walled carbon nano-tubes conductive agent.
Described plus plate current-collecting body is stainless (steel) wire a kind of of the stainless steel band of aluminium net, nickel screen, nickel foam, stainless steel band, stainless (steel) wire, carbon coated of aluminium foil, the carbon coated of aluminium foil, aluminium net, carbon coated or carbon coated; Described porous septum is a kind of of polypropylene, polyethylene, Kynoar or polypropylene and poly duplicature; Described negative plate is a kind of of metal lithium sheet or lithium silicon alloy film, lithium-tin alloy sheet or lithium-aluminium alloy sheet; The solute of described electrolyte is lithium hexafluoro phosphate or lithium perchlorate or trifluoromethyl sulfonic acid lithium, and the solvent of electrolyte is one or more mixed solvent of ethylene carbonate methyl esters, propene carbonate, dimethyl carbonate, dioxolane, tetraethyleneglycol dimethyl ether or oxolane.
After being elemental sulfur with polyacrylonitrile 4-16:1 mixes in mass ratio, described sulfenyl composite material is heated to 250-400 ℃ and be incubated 1-16 hour and make under the nitrogen protection.
Described organic solution nmp solvent.
Described mixed solvent is the solvent that ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate are mixed into, or the solvent that is mixed into of butyl oxide link and tetraethyleneglycol dimethyl ether.
Advantage and good effect that the present invention has are:
The present invention is owing to being equipped with cellulose membrane between positive electrode and porous septum; Cellulose membrane has stoped polysulfide to move to the lithium anode sheet with electrolyte in lithium-sulfur rechargeable battery, suppressed the side reaction that " flying the shuttle phenomenon " causes, Effective Raise the enclosed pasture efficient of lithium-sulfur rechargeable battery, prolonged battery, and simple to operate, cost is low, is easy to large-scale production.
Description of drawings
Fig. 1 is present known lithium-sulfur rechargeable battery internal structure schematic diagram;
Fig. 2 is lithium-sulfur rechargeable battery internal structure schematic diagram of the present invention;
Fig. 3 is Fig. 1 and Fig. 2 cycle performance of battery comparison diagram;
Fig. 4 is weekly coulombic efficiency comparison diagram of Fig. 1 and Fig. 2 battery.
Among the figure, the 1-plus plate current-collecting body; The 2-positive electrode; The 3-cellulose membrane; The 4-porous septum; 5-contains the cathode of lithium sheet.
Embodiment
For further understanding summary of the invention of the present invention, Characteristic, hereby exemplify following examples, and cooperate accompanying drawing to be described in detail as follows:
A kind of lithium-sulfur rechargeable battery comprises that battery container inside suppresses from bottom to top all-in-one-piece plus plate current-collecting body, positive electrode, porous septum and contain the cathode of lithium sheet, and electrolyte.
Innovative point of the present invention is: also be suppressed with cellulose membrane between positive electrode and porous septum; Described cellulose membrane is a kind of of nitrocellulose filter, CAM and regenerated cellulose film; Described positive electrode is that sulphurous materials, binding agent, the conductive agent of mass ratio 60-80:2-20:4-40 mixes in organic solution, and forming solid content is the slurry of 15-40%; Described sulphurous materials is elemental sulfur S
8, many lithium sulfides Li
2S
n(1≤n≤8), carbon sulphur polymer (C
2S
x)
m(2.5≤x≤50, and m 〉=2) or the sulfenyl composite material is a kind of; Described binding agent is aqueous binders or PVDF binding agent; Conductive agent is SP conductive agent or multi-walled carbon nano-tubes conductive agent; Described plus plate current-collecting body is stainless (steel) wire a kind of of the stainless steel band of aluminium net, nickel screen, nickel foam, stainless steel band, stainless (steel) wire, carbon coated of aluminium foil, the carbon coated of aluminium foil, aluminium net, carbon coated or carbon coated; Described porous septum is a kind of of polypropylene, polyethylene, Kynoar or polypropylene and poly duplicature; Described negative plate is a kind of of metal lithium sheet or lithium silicon alloy film, lithium-tin alloy sheet or lithium-aluminium alloy sheet; The solute of described electrolyte is lithium hexafluoro phosphate or lithium perchlorate or trifluoromethyl sulfonic acid lithium, and the solvent of electrolyte is one or more mixed solvent of ethylene carbonate methyl esters, propene carbonate, dimethyl carbonate, dioxolane, tetraethyleneglycol dimethyl ether or oxolane; After being elemental sulfur with polyacrylonitrile 4-16:1 mixes in mass ratio, described sulfenyl composite material is heated to 250-400 ℃ and be incubated 1-16 hour and make under the nitrogen protection; Described organic solution nmp solvent; Described mixed solvent is the solvent that ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate are mixed into, or the solvent that is mixed into of butyl oxide link and tetraethyleneglycol dimethyl ether.
Embodiment 1
With elemental sulfur S
8, SP conductive agent, PVDF binding agent in mass ratio 60:30:10 in nmp solvent, mix, form solid content and be 30% slurry as positive electrode, be coated on the aluminium foil plus plate current-collecting body, in vacuum drying chamber, after dry 6 hours, be pressed into anode pole piece; Nitrocellulose filter is placed between the positive pole-face and Celgard2400 porous septum of anode pole piece, the porous septum another side is placed a slice as the lithium silicon alloy of negative plate, be pressed into one shown in Figure 2, place battery container, the injection solute is the electrolyte of lithium hexafluoro phosphate, ethylene carbonate methyl esters, makes CR2430 type lithium sulphur secondary button cell.After tested, the battery charging and discharging cut-ff voltage is 1.5-2.5V(vs.Li/Li
+), the charging and discharging specific capacity is calculated based on the elemental sulfur active material, does the charge and discharge cycles test with the 100mA/g current density, and specific discharge capacity is 984mAh/g for the first time, and specific capacity is 727.2mAh/g after 50 circulations.
Embodiment 2
With many lithium sulfides Li
2S
4, multi-walled carbon nano-tubes conductive agent, water-base cement in mass ratio 70:20:10 in water, mix, form solid content and be 35% slurry as positive electrode, all the other are identical with the preparation process of embodiment 1, as the lithium sulphur secondary button cell of preparation with cellulose membrane, test after making battery, do the charge and discharge cycles test with the 1C current density, specific discharge capacity is 805.0mAh/g for the first time, and specific capacity is 629.3mAh/g after 50 circulations.
Comparative example 1
It is shown in Figure 1 without cellulose membrane choosing internal structure, the battery that all the other are identical with embodiment 1 battery manufacturing process, and the battery for preparing with example 1 carries out charge-discharge performance relatively, as shown in Figure 3; Be further to show cellulose membrane to the iris action of polysulfide that " effect of shuttling back and forth " of establishment battery carried out weekly coulombic efficiency relatively with the battery of comparative example 1 and example 1 preparation, as shown in Figure 4.
Can find out from Fig. 3 and Fig. 4, introduce cellulose membrane in lithium-sulfur rechargeable battery, coulombic efficiency is apparently higher than traditional lithium-sulfur rechargeable battery weekly, establishment " effect of shuttling back and forth " of battery, thereby cycle performance is comparatively excellent.
Although the above is described the preferred embodiments of the present invention by reference to the accompanying drawings; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment only is schematic; be not restrictive; those of ordinary skill in the art is under enlightenment of the present invention; not breaking away from the scope situation that aim of the present invention and claim protect, can also make a lot of forms, these all belong within protection scope of the present invention.
Claims (6)
1. lithium-sulfur rechargeable battery, comprise that battery container inside suppresses from bottom to top all-in-one-piece plus plate current-collecting body, positive electrode, porous septum and contain the cathode of lithium sheet, and electrolyte, it is characterized in that: between positive electrode and porous septum, also be suppressed with cellulose membrane; Described cellulose membrane is a kind of of nitrocellulose filter, CAM and regenerated cellulose film.
2. a kind of lithium-sulfur rechargeable battery according to claim 1, it is characterized in that: described positive electrode is that sulphurous materials, binding agent, the conductive agent of mass ratio 60-80:2-20:4-40 mixes in organic solution, forming solid content is the slurry of 15-40%; Described sulphurous materials is elemental sulfur S
8, many lithium sulfides Li
2S
n(1≤n≤8), carbon sulphur polymer (C
2S
x)
m(2.5≤x≤50, and m 〉=2) or the sulfenyl composite material is a kind of; Described binding agent is aqueous binders or PVDF binding agent; Conductive agent is SP conductive agent or multi-walled carbon nano-tubes conductive agent.
3. a kind of lithium-sulfur rechargeable battery according to claim 1 and 2 is characterized in that: described plus plate current-collecting body is stainless (steel) wire a kind of of the stainless steel band of aluminium net, nickel screen, nickel foam, stainless steel band, stainless (steel) wire, carbon coated of aluminium foil, the carbon coated of aluminium foil, aluminium net, carbon coated or carbon coated; Described porous septum is a kind of of polypropylene, polyethylene, Kynoar or polypropylene and poly duplicature; Described negative plate is a kind of of metal lithium sheet or lithium silicon alloy film, lithium-tin alloy sheet or lithium-aluminium alloy sheet; The solute of described electrolyte is lithium hexafluoro phosphate or lithium perchlorate or trifluoromethyl sulfonic acid lithium, and the solvent of electrolyte is one or more mixed solvent of ethylene carbonate methyl esters, propene carbonate, dimethyl carbonate, dioxolane, tetraethyleneglycol dimethyl ether or oxolane.
4. a kind of lithium-sulfur rechargeable battery according to claim 2 is characterized in that: described sulfenyl composite material is that elemental sulfur is heated to 250-400 ℃ and be incubated 1-16 hour and make after 4-16:1 mixes in mass ratio with polyacrylonitrile under the nitrogen protection.
5. a kind of lithium-sulfur rechargeable battery according to claim 2 is characterized in that: described organic solution nmp solvent.
6. a kind of lithium-sulfur rechargeable battery according to claim 3, it is characterized in that: described mixed solvent is the solvent that ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate are mixed into, or the solvent that is mixed into of butyl oxide link and tetraethyleneglycol dimethyl ether.
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| CN201210403065.1A CN102903974B (en) | 2012-10-22 | 2012-10-22 | Lithium-sulfur secondary battery |
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| CN201210403065.1A CN102903974B (en) | 2012-10-22 | 2012-10-22 | Lithium-sulfur secondary battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104124413A (en) * | 2013-04-25 | 2014-10-29 | 上海萃智科技发展有限公司 | Lithium sulfur storage battery |
| CN104752661A (en) * | 2013-12-30 | 2015-07-01 | 现代自动车株式会社 | Separator Of Lithium Sulfur Secondary Battery |
| CN104952634A (en) * | 2015-06-05 | 2015-09-30 | 北京大学 | Ionic liquid-lithium salt gel polymer electrolyte and preparation and application thereof |
| CN105449175A (en) * | 2015-11-16 | 2016-03-30 | 国家纳米科学中心 | Carbon sulfur composite material for lithium-sulfur battery and preparation method and application for carbon sulfur composite material |
| CN105514325A (en) * | 2014-09-24 | 2016-04-20 | 中国科学院大连化学物理研究所 | Composite film for lithium-sulfur battery |
| US20210074992A1 (en) * | 2016-09-16 | 2021-03-11 | Pacesetter, Inc. | Battery Electrode And Methods Of Making |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185158A (en) * | 2011-04-14 | 2011-09-14 | 武汉理工大学 | Lithium sulfur battery provided with adsorption layer |
| CN102185127A (en) * | 2011-04-07 | 2011-09-14 | 武汉理工大学 | Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery |
-
2012
- 2012-10-22 CN CN201210403065.1A patent/CN102903974B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102185127A (en) * | 2011-04-07 | 2011-09-14 | 武汉理工大学 | Lithium sulphur battery anode piece added with absorbent and lithium sulphur battery |
| CN102185158A (en) * | 2011-04-14 | 2011-09-14 | 武汉理工大学 | Lithium sulfur battery provided with adsorption layer |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104124413A (en) * | 2013-04-25 | 2014-10-29 | 上海萃智科技发展有限公司 | Lithium sulfur storage battery |
| CN104752661A (en) * | 2013-12-30 | 2015-07-01 | 现代自动车株式会社 | Separator Of Lithium Sulfur Secondary Battery |
| CN104752661B (en) * | 2013-12-30 | 2020-02-21 | 现代自动车株式会社 | Separator for lithium-sulfur secondary battery |
| CN105514325A (en) * | 2014-09-24 | 2016-04-20 | 中国科学院大连化学物理研究所 | Composite film for lithium-sulfur battery |
| CN104952634A (en) * | 2015-06-05 | 2015-09-30 | 北京大学 | Ionic liquid-lithium salt gel polymer electrolyte and preparation and application thereof |
| CN104952634B (en) * | 2015-06-05 | 2019-07-19 | 北京大学 | A kind of ionic liquid-lithium salts gel polymer electrolyte and its preparation and application |
| CN105449175A (en) * | 2015-11-16 | 2016-03-30 | 国家纳米科学中心 | Carbon sulfur composite material for lithium-sulfur battery and preparation method and application for carbon sulfur composite material |
| US20210074992A1 (en) * | 2016-09-16 | 2021-03-11 | Pacesetter, Inc. | Battery Electrode And Methods Of Making |
| US11735706B2 (en) * | 2016-09-16 | 2023-08-22 | Pacesetter, Inc. | Methods of making battery electrodes with tubes, optimized solvent to powder weight ratios, and specified calendar roller diameters |
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| CN102903974B (en) | 2017-05-03 |
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