CN102347482A - Static type semi-liquid-flow lithium sulfur battery - Google Patents
Static type semi-liquid-flow lithium sulfur battery Download PDFInfo
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- CN102347482A CN102347482A CN2011103217613A CN201110321761A CN102347482A CN 102347482 A CN102347482 A CN 102347482A CN 2011103217613 A CN2011103217613 A CN 2011103217613A CN 201110321761 A CN201110321761 A CN 201110321761A CN 102347482 A CN102347482 A CN 102347482A
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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 provides a static type semi-liquid-flow lithium sulfur battery. Monomer sulfur, inorganic sulfur or organic sulfur particles and electrolyte are mixed and then the mixture is added into an anode liquid storage box; cathode lithium powder is added into a cathode liquid storage box; and the anode liquid storage box, a diaphragm and the cathode liquid storage box of a battery are assembled to form the integrated static type semi-liquid-flow lithium sulfur battery with a high capacity.
Description
Technical field under the present invention: new forms of energy
Background technology
The energy, material and information technology are these world's three big pillars, and being widely used of oil makes the mankind enjoy fast, live easily, makes the U.S. become the country on the wheel; The waste gas that uses petroleum fuel to burn and produce is endangered environment, the human life of appealing to reduce pollution, low-carbon environment-friendly; Using electric automobile to replace traditional automobile, is the fine wishes of people, but the battery capacity that electric motor car now uses is not enough; Cost an arm and a leg, poor stability, the charging interval is long; The universal of electric automobile taken a step to difficult, and the technological most critical of electric motor car is the technology of battery, and the maturation of battery technology will make the electric motor car industry ripe.
Battery is made up of positive pole, negative pole, electrolyte, barrier film etc.
Lithium battery has become the portable energy source of modern society, if you have mobile phone, MP3, notebook computer, you have just had lithium battery so, more likely be that you have many lithium batteries.
But although lithium battery is fine, they still can not bear challenge, drive electric automobile of future generation, and problem is the positive electrode of lithium battery, and the positive electrode of lithium battery is a lithium, finite capacity.
Summary of the invention:
The chemist is permitted just knows that sulphur potentialization, the theoretical specific capacity of sulphur are 1672mAh/g many years ago, still; Sulphur also has many shortcomings, is that especially sulphur is not ideal conductor, in addition; Sulfide is easy to dissolving, and in many electrolyte, can be flushed away, meanwhile; In discharge process, sulphur is easy to expand and fragmentation.
Sulphur has the electrochemistry ability of polyelectron reduction reaction, and the relative atomic mass of sulphur is less, so elemental sulfur has the theoretical specific capacity up to 1672mA.h/g, and the theoretical energy content of battery density of lithium-sulfur cell can reach 2600Wh.Kg
-1Be far longer than employed commercialization secondary cell of present stage, sulphur aboundresources and cheap is in view of above reason; Lithium-sulfur cell has application advantage in following chemical power source development, therefore the research work around lithium-sulfur cell and critical material thereof is receiving extensive concern.
I combine present lithium-sulfur cell and flow battery, and some advantages of the direct fuel cell of methyl alcohol are designed silent oscillation half flow lithium-sulfur cell.Silent oscillation half flow lithium-sulfur cell be with lithium metal fine powder and electrolyte in metallic copper (aluminium) box as negative pole; As anodal secondary cell, its theoretical energy density is 2600wh.kg in metallic copper (aluminium) box for elemental sulfur or sulfenyl composite powder and electrolyte
-1, actual theoretical energy density can reach 300wh.kg at present
-1, in the coming years, might bring up to 600wh.kg
-1About, being considered to one of at present the most attractive secondary cell system, sulfenyl is anodal; Elemental sulfur electrode itself no matter, still in use, the oxygen-free of elemental sulfur electrode material own; Can not separate out by aerobic, (1) elemental sulfur, elemental sulfur mainly extensively is present in occurring in nature with free state; Belong to the resource of still underusing, under the normal temperature, elemental sulfur is mainly with S
8Form exist, when being applied to battery, suppose in the discharge process that the electron transfer number of each sulphur atom is 2, then S
8Theoretical specific capacity be 1672mAh.g
-1, theoretical discharge voltage is 2.287v, then theoretical energy density is 3823Wh.kg, is at present known except that oxygen, the positive electrode of the secondary cell that energy density is the highest.The positive electrode of silent oscillation half flow lithium-sulfur cell can use elemental sulfur, inorganic sulfur, or the organic sulfur material is used as positive pole; Because be half flow battery; So do not use collector plate, positive electrode is not coated on the pole plate, but in can or metal tube, form anodal; The cathode of lithium material is not coated on the pole plate, but in can or metal tube, forms negative pole.
Mix positive level particles of material and electrolyte in the anodal liquid storage box of packing into; In the negative pole liquid storage box of packing into after negative pole lithium and carbon particulate and the electrolyte mixing; Assemble anodal liquid storage box, barrier film, negative pole liquid storage box, just form complete jumbo silent oscillation half flow lithium-sulfur cell.
Description of drawings
Fig. 1 is the structural representation of box-like silent oscillation half flow lithium-sulfur cell.
Fig. 2 is column type silent oscillation half a flow lithium-sulfur cell structural representation.
Among Fig. 1: 1, positive pole; 2, anodal electrolysis mixed liquor; 3, barrier film; 4, negative pole electrolysis mixed liquor; 5, negative pole.
Among Fig. 2: 1, negative pole; 2, negative pole electrolysis mixed liquor; 3, positive pole; 4, barrier film.
Execution mode
The positive electrode preparation
Execution mode 1: elemental sulfur, acetylene black respectively at 60 ℃ and 120 ℃ of vacuumize 12h, are pressed m (elemental sulfur): m (acetylene black): m (polytetrafluoroethylene before use; The PTFE60% emulsion)=7: 2: 1 ratio prepares positive electrode, earlier elemental sulfur and acetylene black mixed grinding 2h, elemental sulfur and acetylene black mixed; Absolute ethyl alcohol is as solvent; Earlier being dissolved in the absolute ethyl alcohol dosage to PTFE pours into rapidly after mixing in the mixed-powder of sulphur and acetylene black, after stirring than adding the 20ml absolute ethyl alcohol for 1gPTFE; The mixture that obtains boils off absolute ethyl alcohol at 70 ℃ of vacuumize 12h, obtains the black block.
Execution mode 2: elemental sulfur-active carbon composite positive pole preparation
Elemental sulfur, active carbon (200 order), acetylene black are before use respectively at 60 ℃, 120 ℃ vacuumizes, elemental sulfur and active carbon; Press 8: 2 mixing and ball milling of mass ratio, ball milling speed is that per minute 350 changes ball milling 6h; Stop 0.5h, the 6h that regrinds grinds 24h so repeatedly; Sulphur is fully embedded in the hole of active carbon, make carbon-sulfur compound, press m (carbon-sulfur compound): m (acetylene black): m (PTFE; 60% emulsion)=8: 1: 1 ratio prepares positive electrode, earlier carbon-sulfur compound and acetylene black mixed grinding 2h, carbon-sulfur compound and acetylene black mixed; Absolute ethyl alcohol is dissolved in PTFE in the absolute ethyl alcohol as solvent, and dosage is than adding the 20ml absolute ethyl alcohol for 1gPTFE; Pour into rapidly in the mixed-powder of carbon-sulfur compound and acetylene black after mixing, after stirring, the mixture that obtains is at 70 ℃ of vacuumize 12h; Boil off absolute ethyl alcohol; Obtain the black block, grind to form fine powder and electrolyte mixing to the black block, form anodal mixed liquor.
Execution mode 3: elemental sulfur and material with carbon element are pressed 5: 1 mixing and ball milling of mass ratio, and ball milling speed is that per minute 350 changes, and the ball milling time is 6h; After making sulphur and material with carbon element fully mixing, put into the atmosphere box type furnace, continue to feed the about 30min of argon gas; To discharge the air of the inside, avoid under the high temperature sulphur oxidized.Then under the argon gas atmosphere that flows,, under this temperature, keep 5h about material with carbon element and elemental sulfur Hybrid Heating to 200 ℃; Then temperature is elevated to about 300 ℃; Under this temperature, keep 2h, obtain the black carbon sulfur compound, grind to form fine powder to the black carbon sulfur compound; Mix with electrolyte, form anodal mixed liquor.
Execution mode 4: press m (carbon-sulfur compound): m (acetylene black): m (PVDF)=8: 1: 1, preparation carbon-sulfur compound positive electrode, NMP is as solvent; Be dissolved in PVDF among the NMP earlier; (dosage adds 95gNMP than the PVDF for 5g), add carbon-sulfur compound and acetylene black again, magnetic agitation 2h.Obtain black mucus, add electrolyte again and form anodal mixed liquor.
Execution mode 5: the ferrous disulfide proportion of powder is 60%-99%, binding agent 0.5%-20%, and conductive additive 0.5%-20% mixes in the argon shield ball mill with above material, manufactures positive pole.
Electrolyte is commercial lithium-ion electrolyte, the LIPF of 1M
6/ Pc: EMC: DMC=(1: 1: 1) also can use other electrolyte of lithium ion battery.
The lithium ion battery Cellgard barrier film of barrier film commodity in useization.
Execution mode 6: negative pole; With carbonaceous mesophase spherules (MCMB) is main component; With quality is that 10% lithium powder of carbonaceous mesophase spherules (MCMB) quality mixes and forms composite material; Composite material and the conductive agent that accounts for composite negative pole quality 3% (KS modified graphite) and the binding agent PVDF Kynoar (being dissolved among the NMP of 10 times of quality) that accounts for composite negative pole quality 3% are mixed, and wherein the lithium powder is through surface passivation, and the solvent NMP in producing with its lithium ion battery is difficult for reaction; The particle diameter of lithium powder mixes above material at 10 μ m with the argon shield ball mill.
Mix positive electrode particulate and electrolyte in the anodal liquid storage box of packing into; In the negative pole liquid storage box of packing into after negative pole lithium and carbon particulate and the electrolyte mixing; Stamp a series of small pores at the contact-making surface of anodal liquid storage box and barrier film; Make the electrolyte of positive pole, negative pole produce the oxidation-reduction reaction at the barrier film place through these a series of pores, thereby produce electric current.
Claims (9)
1. the designing and preparation method of silent oscillation half a flow lithium-sulfur cell; It is characterized in that: described silent oscillation half flow lithium-sulfur cell is to be negative material with the particulate of lithium and the mixed liquor of electrolyte; Packing negative material in a small-sized aluminium (copper) box into, as the negative pole of battery, is positive electrode with the particulate of elemental sulfur, elemental sulfur compound, sulfur-based compound, inorganic sulfur, organic sulfur etc. and the mixed liquor of electrolyte; Pack positive electrode in a small-sized aluminium (copper) box into; As the positive pole of battery, assemble positive pole, barrier film, negative pole, form a complete jumbo silent oscillation lithium-sulfur cell.
2. the designing and preparation method of silent oscillation half flow lithium-sulfur cell as claimed in claim 1: it is characterized in that positive electrode can be an elemental sulfur.
3. the designing and preparation method of silent oscillation half flow lithium-sulfur cell as claimed in claim 1: it is characterized in that positive electrode can be an inorganic sulfur, comprising: MoS
2, SiS
2, LiS
2, MrS
2, FeS
2, V
2S
2, TiS
2, NiS, sulfuration europium, praseodymium sulfide, sulfuration erbium, lanthanum sulfide, gadolinium sulfide, sulfuration thulium, sulfuration holmium, sulfuration terbium, ferrous sulfide, ironic sulfide, copper sulfide, titanium disulfide, molybdenum trisulfide, vulcanized lead, cobalt disulfide.
4. the designing and preparation method of silent oscillation half flow lithium-sulfur cell as claimed in claim 1: it is characterized in that positive electrode can be an organic sulfur, comprising: to organic disulfide, gather organic disulfide, poly organic polysulfide thing, carbon sulphur polymer, comprise gather 2,2 '-two thioanilines (PDTDA), gather anthracene [1,9; 8-b, c, d, e] [4; 10,5-b, c, d; E] bis-[1,6,6a (6a-s) trithia] pentalene (PABTP), gather (2-phenyl-1; 3-dithia ring penta ring) (PPDT), gather [1,4-two is to (1,3-dithiolane base) benzene] (PDDTB)
Gather (ethene-1,1,2,2-four mercaptan)
Gather three sulfo-phosphorus nitrence [NPS
3] n
Gather 1,5-diamino-anthraquinone (PDAAQ).
5. the designing and preparation method of silent oscillation half flow lithium-sulfur cell as claimed in claim 1: it is characterized in that electrolytical range of choice: organic liquid, ionic liquid, organic liquid electrolyte can be selected for use and contain glycol dimethyl ether (DME); 1; 3-dioxolane (DOL), a kind of organic solvent of oxolane (THF), diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, ortho-xylene etc. or the mixture of several kinds of organic solvents.
Can also select commercial lithium-ion electrolyte 1M LipF for use
6/ PC: EMC: DMC (1: 1: 1) also can select LiTFSI, LIBFTI, LipF
6, LITF etc. comprises variable concentrations and ratio.
6. the designing and preparation method of silent oscillation half flow lithium-sulfur cell as claimed in claim 1: it is characterized in that barrier film, comprise the Nafion of Du Pont film, cellgard film, glass fibre membrane, Asahi Chemical Industry's film, east combustion film, germanic acid zinc lithium film, homemade amberplex.
7. the designing and preparation method of silent oscillation half flow lithium-sulfur cell as claimed in claim 1: it is characterized in that negative pole, comprise that the carbonaceous mesophase spherules (MCMB) and the lithium powder of different proportion confuse the negative electrode of the composite material making of formation.
8. the designing and preparation method of silent oscillation half flow lithium-sulfur cell as claimed in claim 1: it is characterized in that negative pole: comprise Si base material, Li
4Ti
5O
12, Sn sill and other novel negative materials.
9. the structural shape of silent oscillation half flow lithium-sulfur cell as claimed in claim 1: not only comprise box-like, square, also comprise cylindrical, aluminium plastic bag shape etc.
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| CN2011103217613A CN102347482A (en) | 2011-09-28 | 2011-09-28 | Static type semi-liquid-flow lithium sulfur battery |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102751490A (en) * | 2012-06-29 | 2012-10-24 | 上海交通大学 | Lithium ion battery anode material |
| CN103178284A (en) * | 2013-02-05 | 2013-06-26 | 上海交通大学 | Liquid flow lithium sulfur secondary battery |
| 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 |
| CN104852083A (en) * | 2015-05-14 | 2015-08-19 | 珠海泰坦储能科技有限公司 | Liquid form lithium sulphur battery energy storage system |
| CN105489912A (en) * | 2014-09-25 | 2016-04-13 | 北京好风光储能技术有限公司 | Lithium ion flow battery reactor |
| US20170200966A1 (en) * | 2013-02-04 | 2017-07-13 | Massachusetts Institute Of Technology | Metal sulfide electrodes and energy storage devices thereof |
| CN109360925A (en) * | 2012-04-13 | 2019-02-19 | 阿科玛股份有限公司 | Battery based on organic sulphur species |
| JP2020115459A (en) * | 2013-03-15 | 2020-07-30 | ２４エム・テクノロジーズ・インコーポレイテッド２４Ｍ Ｔｅｃｈｎｏｌｏｇｉｅｓ， Ｉｎｃ． | Asymmetric battery having semi-solid cathode and high energy density anode |
-
2011
- 2011-09-28 CN CN2011103217613A patent/CN102347482A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109360925A (en) * | 2012-04-13 | 2019-02-19 | 阿科玛股份有限公司 | Battery based on organic sulphur species |
| CN109360925B (en) * | 2012-04-13 | 2021-10-26 | 阿科玛股份有限公司 | Battery based on organosulfur species |
| CN102751490A (en) * | 2012-06-29 | 2012-10-24 | 上海交通大学 | Lithium ion battery anode material |
| US20170200966A1 (en) * | 2013-02-04 | 2017-07-13 | Massachusetts Institute Of Technology | Metal sulfide electrodes and energy storage devices thereof |
| CN103178284A (en) * | 2013-02-05 | 2013-06-26 | 上海交通大学 | Liquid flow lithium sulfur secondary battery |
| JP2020115459A (en) * | 2013-03-15 | 2020-07-30 | ２４エム・テクノロジーズ・インコーポレイテッド２４Ｍ Ｔｅｃｈｎｏｌｏｇｉｅｓ， Ｉｎｃ． | Asymmetric battery having semi-solid cathode and high energy density anode |
| US11394049B2 (en) | 2013-03-15 | 2022-07-19 | 24M Technologies, Inc. | Asymmetric battery having a semi-solid cathode and high energy density anode |
| 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 |
| WO2015043167A1 (en) * | 2013-09-24 | 2015-04-02 | 华为技术有限公司 | Lithium-ion battery and method for manufacturing lithium metal alloy |
| CN105489912A (en) * | 2014-09-25 | 2016-04-13 | 北京好风光储能技术有限公司 | Lithium ion flow battery reactor |
| CN105489912B (en) * | 2014-09-25 | 2017-11-28 | 北京好风光储能技术有限公司 | Lithium ion flow battery reactor |
| CN104852083A (en) * | 2015-05-14 | 2015-08-19 | 珠海泰坦储能科技有限公司 | Liquid form lithium sulphur battery energy storage system |
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Application publication date: 20120208 |