CN102201567A - Preparation method for anode of lithium-sulfur battery - Google Patents
Preparation method for anode of lithium-sulfur battery Download PDFInfo
- Publication number
- CN102201567A CN102201567A CN2011100956505A CN201110095650A CN102201567A CN 102201567 A CN102201567 A CN 102201567A CN 2011100956505 A CN2011100956505 A CN 2011100956505A CN 201110095650 A CN201110095650 A CN 201110095650A CN 102201567 A CN102201567 A CN 102201567A
- Authority
- CN
- China
- Prior art keywords
- preparation
- wafer
- fiber film
- lithium
- sulphur
- 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.)
- Pending
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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method for an anode of a lithium-sulfur battery, which comprises the following steps of: (1) the pretreatment of a metal foil: cutting the metal foil, wiping a surface of a wafer by using an acetone-contained cotton ball, putting the wafer in distilled water for cleaning in ultrasound, and taking out and airing the wafer; (2) the preparation of a carbon fiber film: putting the wafer in a cavity of a chemical vapor deposition device, and preparing the carbon fiber film on the surface of the wafer through a method of decomposing or thermally decomposing a reaction gas by a plasma, wherein the wafer serves as a catalyst; and (3) the sulfurizing of the carbon fiber film: uniformly spreading sulfur powder on the surface of the carbon fiber film, putting a metal wafer in a tubular furnace to preserve the heat of the metal wafer in the atmosphere of argon, and cooling the wafer to the room temperature to prepare the anode of the lithium-sulfur battery. Compared with the prior art, the preparation method has the advantage of being capable of greatly improving anode conductivity and polysulfide adsorbability, and therefore, large specific discharge capacity and high circular anode discharge stability are obtained; in addition, the anode is in no need of drying, so that the preparation method has the advantage of saving time.
Description
Technical field
The present invention relates to a kind of preparation method of lithium-sulphur cell positive electrode, belong to field of electrochemical batteries.
Background technology
Lithium-sulfur cell is a kind of secondary cell that utilizes lithium and sulphur generation chemical reaction, its negative pole adopts metal lithium sheet, sulphurous materials just very, and negative pole produces lithium ion during discharge, sulphur in the positive pole and lithium ion reaction generate sulfide, reverse the carrying out of both positive and negative polarity reaction during charging.The Theoretical Mass specific capacity of elemental sulfur is 1675mAh/g, and this will be higher than the theoretical specific discharge capacity (LiCoO of the metal oxide of common lithium ion cell positive employing
2, LiNiO
2And LiMn
2O
4Theoretical specific discharge capacity be respectively 274mAh/g, 274mAh/g and 148mAh/g), in addition, elemental sulfur is cheap, and is environmentally friendly, this makes lithium-sulfur cell in the field of batteries of small-sized electronic product broad prospect of application be arranged.
Because elemental sulfur is that (conductivity is 5 * 10 25 ℃ the time for electronics and ion insulator
-30Scm
-1), anodal common preparation method is that blade coating made positive pole after sulphur, acetylene black (conductive agent) and binding agent (as Kynoar PVDF) evenly were mixed and made into slurry after the drying on metal forming (collector).Because positive pole is to rely on the intergranular contact conduction of acetylene black, the Li that anodal reaction generates
2S
2And Li
2Insulants such as S can cause the conduction approach to destroy, and cause anodal conductivity to descend; Simultaneously, the binding agent that contains in the positive pole is mainly high molecular polymer, their poorly conductive, and this has reduced anodal conductivity again, causes the utilance of sulphur and positive discharge specific capacity not high.In addition, the polysulfide that anodal reaction generates during discharge can irreversibly be dissolved in electrolyte and lose, and this causes anodal circulation discharge stability not high.
The researcher attempts several different methods and promotes anodal conductivity and strengthen anodal adsorptivity to polysulfide, people's [electrochemistry such as king's Chong, 2010,16 (2): 168-171] attempt adding the porous carbon gel and improve cathode performance, after they make the carbon gel, after the heating of itself and sulphur mixed, mix with conductive agent and adhesive again, after mixture is coated on the aluminium foil, promptly make positive pole after the drying.The adding of porous carbon gel has strengthened anodal adsorptivity to polysulfide, promoted anodal circulation discharge stability, but, the carbon gel does not have satisfactory electrical conductivity owing to have loose structure, make it not high, and the adhesive of poorly conductive can reduce anodal conductivity in the positive pole to the lifting degree of cathode performance.People such as Wu Feng [novel charcoal material, 2010,25 (6): 421-425] attempt in positive pole, adding multiple-wall carbon nanotube with satisfactory electrical conductivity, after they mix the heating of CNT (carbon nano-tube) and sulphur, mix with acetylene black and Kynoar PVDF again, after mixture is coated on the aluminium foil, make positive pole behind 60 ℃ of vacuumize 24h.CNT (carbon nano-tube) forms conductive network in positive pole, promoted anodal conductivity, and its surface hinders it by the suction-operated to polysulfide and be dissolved in electrolyte, has promoted anodal circulation discharge stability.But CNT (carbon nano-tube) is reunited easily owing to its bigger serface, causes it to be difficult to be dispersed in the positive pole, and this is unfavorable for making up the favorable conductive structure; And contain the Kynoar PVDF of poorly conductive in the positive pole, it can reduce anodal conductivity.Therefore, make up the use that evenly distributes and conduct electricity good structure and avoid binding agent and can big degree improve cathode performance.
Summary of the invention
Problem to be solved by this invention is the preparation method of a kind of lithium-sulphur cell positive electrode of proposing at above-mentioned prior art, it prepares earlier carbon-fiber film on metal collector, after sulphur is infiltrated in the carbon-fiber film by heating, promptly make positive pole with sulphur/carbon fiber composite membrane, need not add binding agent in the electrode production process, and must be not dry.
The present invention for the solution that problem adopts of the above-mentioned proposition of solution is: a kind of preparation method of lithium-sulphur cell positive electrode is characterized in that including following steps:
1) preliminary treatment of metal forming:
Metal forming is cut into the metal disk that diameter is 11-13mm, earlier with inhaling surperficial 3-4 minute of the cotton balls wiping metal disk that acetone is arranged, after metal disk was put into the distilled water ultrasonic cleaning 2-3 minute, taking-up is dried;
2) preparation of carbon-fiber film:
Metal disk after step 1) handled is put into the cavity of chemical vapor deposition unit, by the method for plasma decomposes reacting gas or pyrolysis gas, is catalyst with the metal disk, at its surface preparation carbon-fiber film;
3) carbon-fiber film sulfurizing:
With step 2) preparation the carbon-fiber film surface evenly sprinkle the sulphur powder, sulphur opaque amount on each metal disk is 0.8-1.2g, then metal disk is put into tube furnace, 170-230 ℃ of following insulation 3-5h in being full of the atmosphere of argon gas makes lithium-sulphur cell positive electrode after being cooled to room temperature.
Press such scheme, described metal forming is iron foil or nickel foil.
Press such scheme, described chemical vapor deposition unit is microwave chemical vapor phase growing apparatus or hot-wire chemical gas-phase deposition device.
Press such scheme, step 2) described reacting gas is H
2And CH
4Mist; H
2And CH
3CH
2The mist of OH steam; H
2And CH
3COCH
3Any one group of mist in the mist of steam.
The present invention prepares carbon-fiber film on the metal forming collector, sulphur is infiltrated in the back in carbon-fiber film, make sulphur/carbon fiber composite membrane.Having high conductivity and equally distributed carbon fiber provides the good conductive passage for sulphur, and does not contain the binding agent of poorly conductive in the positive pole, thereby big degree promotes the utilance and the positive discharge specific capacity of sulphur.In addition, the big surface of carbon fiber suppresses polysulfide by suction-operated and is dissolved in the electrolyte, improves anodal circulation discharge stability.
The present invention compared with prior art has the following advantages: the present invention's degree greatly promotes anodal conductivity and to the adsorptivity of polysulfide, thereby obtains big specific discharge capacity and high positive pole circulation discharge stability.In addition, need not be dry in the anodal preparation, have the timesaving advantage.
Description of drawings
Fig. 1 is the SEM figure of carbon-fiber film of the lithium-sulphur cell positive electrode of embodiment 4 preparation.
Embodiment
The invention will be further described below in conjunction with embodiment, but can not be as limitation of the invention.
Embodiment 1:
Nickel foil is cut into the disk that diameter is 12mm, the cotton balls wiping disk surfaces 3 minutes of acetone is arranged with suction earlier, after disk was put into the distilled water ultrasonic cleaning 3 minutes, taking-up is dried.
Nickel disk after will drying is put into the cavity of microwave chemical vapor phase growing apparatus, and reacting gas is H
2And CH
4, produce plasma decomposes H by microwave-excitation
2And CH
4, microwave power is 400W, H
2And CH
4Volume flow be respectively 40sccm (mark condition under ml/min) and 30sccm, reaction pressure is 2KPa, is catalyst with the nickel disk, at its surface preparation carbon-fiber film, preparation time is 40 minutes.
The carbon-fiber film surface of preparation is evenly sprinkled the sulphur powder, and sulphur opaque amount is 0.8g on each membrane disk, after disk is put into tube furnace, 180 ℃ of following insulation 4h in being full of the atmosphere of argon gas make lithium-sulphur cell positive electrode after being cooled to room temperature.
Embodiment 2:
Iron foil is cut into the disk that diameter is 13mm, the cotton balls wiping disk surfaces 4 minutes of acetone is arranged with suction earlier, after disk was put into the distilled water ultrasonic cleaning 3 minutes, taking-up is dried.
Iron disk after will drying is put into the cavity of microwave chemical vapor phase growing apparatus, and reacting gas is H
2And CH
3CH
2The OH steam is (by H
2Carry), produce plasma decomposes H by microwave-excitation
2And CH
3CH
2OH steam, microwave power are 400W, H
2(H
2+ CH
3CH
2OH) volume flow is respectively 30sccm and 80sccm, and reaction pressure is 2.5KPa, is catalyst with the iron disk, and at its surface preparation carbon-fiber film, preparation time is 35 minutes.
The carbon-fiber film surface of preparation is evenly sprinkled the sulphur powder, and sulphur opaque amount is 1g on each membrane disk, after disk is put into tube furnace, 200 ℃ of following insulation 3h in being full of the atmosphere of argon gas make lithium-sulphur cell positive electrode after being cooled to room temperature.
Embodiment 3:
Nickel foil is cut into the disk that diameter is 11mm, the cotton balls wiping disk surfaces 3 minutes of acetone is arranged with suction earlier, after disk was put into the distilled water ultrasonic cleaning 3 minutes, taking-up is dried.
Nickel disk after will drying is put into the cavity of hot-wire chemical gas-phase deposition device, and reacting gas is H
2And CH
4, by, heated filament heat production decomposing H
2And CH
4, heater power is 500W, H
2And CH
4Volume flow be respectively 60sccm and 50sccm, reaction pressure is 2KPa, with, the nickel disk is a catalyst, at its surface preparation carbon-fiber film, preparation time is 40 minutes.
The carbon-fiber film surface of preparation is evenly sprinkled the sulphur powder, and sulphur opaque amount is 1g on each membrane disk, after disk is put into tube furnace, 190 ℃ of following insulation 4h in being full of the atmosphere of argon gas make lithium-sulphur cell positive electrode after being cooled to room temperature.
Embodiment 4:
Iron foil is cut into the disk that diameter is 12mm, the cotton balls wiping disk surfaces 4 minutes of acetone is arranged with suction earlier, after disk was put into the distilled water ultrasonic cleaning 3 minutes, taking-up is dried.
Iron disk after will drying is put into the cavity of hot-wire chemical gas-phase deposition device, and reacting gas is H
2And CH
3COCH
3Steam is (by H
2Carry), by heated filament heat production decomposing H
2And CH
3COCH
3, heater power is 500W, H
2(H
2+ CH
3COCH
3) volume flow be respectively 30sccm and 70sccm, reaction pressure is 2KPa, is catalyst with the iron disk, at its surface preparation carbon-fiber film, preparation time is 40 minutes.
The carbon-fiber film surface of preparation is evenly sprinkled the sulphur powder, and sulphur opaque amount is 1.2g on each membrane disk, after disk is put into tube furnace, 210 ℃ of following insulation 3h in being full of the atmosphere of argon gas make lithium-sulphur cell positive electrode after being cooled to room temperature.
Fig. 1 is the SEM figure of carbon-fiber film of the lithium-sulphur cell positive electrode of embodiment 4 preparation, as can be seen from Figure 1, according to carbon fiber in the carbon-fiber film of such scheme preparation mainly along vertical metal paper tinsel surface direction, equally distributed carbon fiber provides the passage of the good conductive from sulphur to the metal collector, and big degree promotes the conductivity of sulphur.In addition, the big surface energy absorption polysulfide of carbon fiber suppresses it and is dissolved in the electrolyte.
In order to verify performance by the positive pole of such scheme preparation, with the just very lithium-sulphur cell positive electrode of embodiment 4 preparations, be negative pole with the metal lithium sheet, electrolyte adopts 1mol/L LiClO
4/ (DOL+DME) (1,3-dioxolanes+dimethoxy-ethane, both volume ratios are 1: 1), barrier film is Celgard 2320 type films, assembled battery in being full of the vacuum glove box of argon gas.After battery is carried out charge-discharge test on the electric battery test system of indigo plant, when current density is 0.4mA/cm
2The time, the first specific discharge capacity of sulphur/carbon fiber composite membrane positive pole is 973mAh/g, specific discharge capacity behind 50 cycle charge-discharges is 639mAh/g, and adopt sulphur, acetylene black and binding agent to mix the back blade coating on iron foil, the first specific discharge capacity of the positive pole of dry back preparation is 681mAh/g, the specific discharge capacity that circulates after 50 times is 247mAh/g, and this sulphur/carbon fiber composite membrane that shows preparation is just having high specific discharge capacity and good cyclical stability.
Claims (4)
1. the preparation method of a lithium-sulphur cell positive electrode is characterized in that including following steps:
1) preliminary treatment of metal forming:
Metal forming is cut into the metal disk that diameter is 11-13mm, earlier with inhaling surperficial 3-4 minute of the cotton balls wiping metal disk that acetone is arranged, after metal disk was put into the distilled water ultrasonic cleaning 2-3 minute, taking-up is dried;
2) preparation of carbon-fiber film:
Metal disk after step 1) handled is put into the cavity of chemical vapor deposition unit, by the method for plasma decomposes reacting gas or pyrolysis gas, is catalyst with the metal disk, at its surface preparation carbon-fiber film;
3) carbon-fiber film sulfurizing:
With step 2) preparation the carbon-fiber film surface evenly sprinkle the sulphur powder, sulphur opaque amount on each metal disk is 0.8-1.2g, then metal disk is put into tube furnace, 170-230 ℃ of following insulation 3-5h in being full of the atmosphere of argon gas makes lithium-sulphur cell positive electrode after being cooled to room temperature.
2. by the preparation method of the described lithium-sulphur cell positive electrode of claim 1, it is characterized in that described metal forming is iron foil or nickel foil.
3. by the preparation method of claim 1 or 2 described lithium-sulphur cell positive electrodes, it is characterized in that described chemical vapor deposition unit is microwave chemical vapor phase growing apparatus or hot-wire chemical gas-phase deposition device.
4. by the preparation method of claim 1 or 2 described lithium-sulphur cell positive electrodes, it is characterized in that step 2) described reacting gas is H
2And CH
4Mist, H
2And CH
3CH
2The mist of OH steam, H
2And CH
3COCH
3Any one group of mist in the mist of steam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100956505A CN102201567A (en) | 2011-04-18 | 2011-04-18 | Preparation method for anode of lithium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100956505A CN102201567A (en) | 2011-04-18 | 2011-04-18 | Preparation method for anode of lithium-sulfur battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102201567A true CN102201567A (en) | 2011-09-28 |
Family
ID=44662072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100956505A Pending CN102201567A (en) | 2011-04-18 | 2011-04-18 | Preparation method for anode of lithium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102201567A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107749468A (en) * | 2017-09-26 | 2018-03-02 | 哈尔滨工业大学 | A kind of preparation method and application of carbon nano-fiber with multilevel hierarchy, metal phase molybdenum disulfide and sulphur composite |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100551005B1 (en) * | 2003-10-21 | 2006-02-13 | 삼성에스디아이 주식회사 | Positive electrode for lithium-sulfur battery and lithium-sulfur battery comprising same |
| CN101378120A (en) * | 2008-10-13 | 2009-03-04 | 武汉工程大学 | Method for preparing lithium battery anode |
| CN101562244A (en) * | 2009-06-02 | 2009-10-21 | 北京理工大学 | Method for preparing elemental sulfur composite material used by lithium secondary battery |
-
2011
- 2011-04-18 CN CN2011100956505A patent/CN102201567A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100551005B1 (en) * | 2003-10-21 | 2006-02-13 | 삼성에스디아이 주식회사 | Positive electrode for lithium-sulfur battery and lithium-sulfur battery comprising same |
| CN101378120A (en) * | 2008-10-13 | 2009-03-04 | 武汉工程大学 | Method for preparing lithium battery anode |
| CN101562244A (en) * | 2009-06-02 | 2009-10-21 | 北京理工大学 | Method for preparing elemental sulfur composite material used by lithium secondary battery |
Non-Patent Citations (1)
| Title |
|---|
| 李丹丹等: "锂二次电池正极含硫复合材料的研究", 《电池工业》, vol. 12, no. 5, 31 October 2007 (2007-10-31) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107749468A (en) * | 2017-09-26 | 2018-03-02 | 哈尔滨工业大学 | A kind of preparation method and application of carbon nano-fiber with multilevel hierarchy, metal phase molybdenum disulfide and sulphur composite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103236560B (en) | A kind of sulfur/carbon composite anode material of lithium-sulfur cell and its preparation method and application | |
| CN102867940B (en) | Process for preparing lithium sulfur battery modified anode | |
| CN102810673B (en) | Method for preparing carbon-coated MnO coaxial nanowire cathode material for lithium ion batteries | |
| CN108649190A (en) | Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite and its preparation method and application | |
| CN103390752B (en) | Graphene-based matrix material, its preparation method and the application in lithium-sulfur cell thereof | |
| CN104393233B (en) | Graphene array-based carbon-sulfur composite electrode and secondary cell | |
| CN101958414B (en) | Method for preparing anode of lithium sulfur battery | |
| CN104638219A (en) | Composite diaphragm for lithium-selenium battery and preparation method of composite diaphragm | |
| CN102315462B (en) | Electrode used for vanadium redox flow battery and preparation method for electrode | |
| CN110649266A (en) | Lithium ion battery based on carbon nanotube film and preparation method thereof | |
| CN104882607A (en) | Anima bone base type graphene lithium ion battery negative electrode material and preparation method thereof | |
| CN103219491A (en) | Copper sulfide anode and preparation method thereof | |
| CN107834005A (en) | Preparation method of lithium-selenium battery composite diaphragm | |
| CN108682813A (en) | A kind of preparation method and application of Si-C composite material | |
| CN109802094A (en) | A kind of low temperature ferric phosphate lithium cell and preparation method thereof | |
| CN104600296A (en) | Preparation method of Se-C positive electrode composite material of lithium-selenium battery | |
| CN102623676A (en) | Composite material for positive pole of lithium-sulfur battery, and positive pole and battery both made of same | |
| CN103456926A (en) | Preparation methods of silicon-graphene composite material and lithium ion battery | |
| CN105609720A (en) | Preparation method and application of NiPC@CNTs/S composite material | |
| CN109449376B (en) | Composite lithium metal electrode and preparation method thereof | |
| WO2018059180A1 (en) | High-power, high-energy chemical power supply and preparation method therefor | |
| CN103078095A (en) | Method for preparing tin dioxide/graphene-compounded anode material of lithium ion battery | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN103943373A (en) | Application of graphdiyne in metal ion batteries and super-capacitors | |
| CN104022269B (en) | A kind of native graphite and MnO composite high-performance electrode 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 | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20110928 |