CN102509803A - Preparation method of carbon-coated sulfur anode material of lithium sulfur secondary battery - Google Patents
Preparation method of carbon-coated sulfur anode material of lithium sulfur secondary battery Download PDFInfo
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- CN102509803A CN102509803A CN2011103444161A CN201110344416A CN102509803A CN 102509803 A CN102509803 A CN 102509803A CN 2011103444161 A CN2011103444161 A CN 2011103444161A CN 201110344416 A CN201110344416 A CN 201110344416A CN 102509803 A CN102509803 A CN 102509803A
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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
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- 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 carbon coating method of sulfur as a lithium sulfur secondary battery anode material, comprising the following steps: dissolving carbohydrate and additive in stroke solution or collosol; adding element sulfur of the lithium sulfur secondary battery anode material into the mixture and ultrasonically dispersing the sulfur, forming a layer of carbohydrate solution or collosol thin layer on the surface of sulfur particles, sealing the reaction liquid at high pressure to perform the hydrothermal reaction, naturally cooling the reaction liquid, cleaning, filtering and drying the cooled reaction liquid to obtain the carbon-coated sulfur anode material of the lithium sulfur secondary battery. Because the precursor of the carbon source uses the solvent or collosol, the carbon is uniformly distributed on the surface of the sulfur particle and closely combined with the surface of the sulfur particle, so as to facilitate the increase in the conductive performance of the sulfur anode material and prevent the sulfur and the discharge products from being dissolved by electrolyte, thereby increasing the cycle capacity stability of the lithium sulfur battery. Because the hydrothermal reaction is performed to carbonize sulfur, the carbonization temperature is relatively low, the operation is easy; furthermore the production cost is reduced and the energy saving and environmental protection are facilitated.
Description
Technical field
The present invention relates to the lithium-sulfur rechargeable battery field of material preparation, be specifically related to a kind of carbon method for coating of lithium-sulfur rechargeable battery anode material sulphur.
Background technology
Along with the demand of growing portable type electronic product, the secondary rechargeable battery of high-energy-density becomes research emphasis gradually.The at present commercial theoretical specific capacity that is the lithium ion secondary rechargeable battery of positive electrode with the sour lithium of cobalt is 275mAh/g; Actual have only 130 ~ 140mAh/g; And be that the theoretical specific capacity of the lithium-sulfur rechargeable battery of positive electrode can reach 1675 mAh/g sulphur with sulphur, theoretical specific energy 2600Whkg-1 is because sulphur is cheap and easy to get; Environmental friendliness, the lithium-sulfur rechargeable battery that sulphur is made the commercialization positive electrode will improve the performance of lithium secondary battery greatly.But sulphur is nonmetal, and conductivity is low, and invertibity is poor, and capability retention is low, and discharging product lithium sulfide is soluble in electrolyte solution, reduces the conductivity and the active material utilization of solution, and cycle performance of battery is descended.Researchers mainly set about from inorganic sulfide compound, organic polysulfide or polymer and with compound this three aspect of various material with carbon elements (activated carbon, CNT, porous carbon, ordered mesopore carbon etc.).What wherein utilization efficiency and specific capacity were all higher is the composite material of sulphur and carbon.For example C. Lai at high temperature makes the porous carbon sulfur loaded of high-specific surface area with polyacrylonitrile, and with the current density of 40mA/g, first discharge specific capacity is 1155mAh/g, and circulating after 84 times is 745mAh/g [1]; It is 1279 mAh/g that Wang Weikun etc. have prepared the first discharge specific capacity that mesoporous hard carbon material obtained under the current density of 500mA/g; But 100 the later capacity attenuations that circulate are 613 mAh/g, and high temperature and the exacting terms [2] of this method arts demand.Can see that when specific capacity improved, cycle performance was still unstable, and technology is also very complicated, energy consumption is higher.If a kind of easy not harsh method can be arranged at sulphur coated with uniform carbon, can improve the electric conductivity of sulphur, prevent the solution loss of sulphur in electrolyte, improve the electrode activity and the cyclic reversibility of sulfur electrode.Common surperficial method for coating is to coat organic substance at particle surface, and calcining forms and coats product under reducing atmosphere then.But sulphur is at high temperature calcined and can be gasified, and therefore this method is not suitable for the carbon coating of sulphur.
Summary of the invention
The carbon that order of the present invention is to provide a kind of sulphur surface evenly to be coated by carbon and electric conductivity has obviously improved coats the preparation method of sulphur positive electrode; This clad structure can obviously improve sulphur and discharging product thereof by the shortcoming of electrolyte dissolving; And improve the conductivity of sulphur, improve the cyclical stability of sulphur.
The object of the invention is realized through following technical proposals:
The carbon method for coating that a kind of lithium-sulfur rechargeable battery sulphur is anodal; Comprise the steps: carbohydrate and additive are mixed back water dissolving formation solution or colloidal sol, add sulphur simple substance, ultrasonic dispersion; Fall reactant liquor and under condition of high voltage, carry out hydro-thermal reaction; Reaction back natural cooling alternately washs, filters with organic solvent and deionized water, and drying obtains the sulphur positive electrode that carbon coats; Wherein said additive is N-polyvinylpyrrolidone (PVP), cetrimonium bronmide (CTAB), polyethylene glycol or dodecyl sodium sulfate (SDS).
Said carbohydrate is preferably glucose, sucrose, and cyclodextrin, the mixture of one or more in the starch, concentration of aqueous solution are 0.1-2mol/L.
The concentration of said additive is preferably 0.01-1mol/L.
Said sulphur positive electrode is preferably sulphur simple substance.
The time of said ultrasonic dispersion is preferably 0.5-3h.
The temperature of said hydro-thermal reaction is preferably 150-200 ° of C, and the reaction time is preferably 2-30h, and reaction pH is preferably 3 ~ 12.
Organic solvent used in the said washing process is preferably absolute ethyl alcohol, acetone, butanols or carbon tetrachloride.
The preparation principle that carbon of the present invention coats the sulphur positive electrode is: with sulphur and solution or the mixing of colloidal sol shape carbohydrate, utilize the low-temperature hydrothermal reaction, the carbohydrate carbonization is become carbon.Because sulphur still is being dispersed in solid granulates under this temperature and pressure in the middle of the carbohydrate colloidal sol, so carbonisation can coat sulphur.Because the carbon source precursor adopts solution or colloidal sol, covers the positive electrode particle surface easily, after the carbonization the positive electrode surface distributed evenly, combine closely.Through the adjustment reactant ratio, reaction time, temperature, pH value can obtain best product in the experimentation.
Compared with prior art, the present invention has following beneficial effect:
1. after the present invention was coated with sulphur with carbon, the electrode reaction of sulphur was all carried out in the carbon shell inside that coats, and carbon has sizable specific area again simultaneously, and carbon is conductive agent, can protect positive electrode not dissolved by electrolyte again.
2. the present invention carries out carbon and coats under the low-temperature hydrothermal condition, and temperature low (140-200 ° of C), power consumption are low, do not need inert gas shielding simultaneously;
3. because the carbon source precursor adopts carbohydrate colloidal sol, sulphur is covered its surface by the carbon source precursor easily under the dispersion of surfactant, and after the carbonization, carbon is even in the sulphur surface distributed, in conjunction with closely, helps improving the electric conductivity of sulphur.Behind the sulphur coated with carbon, chemical property and stable cycle performance property are obviously improved;
4. preparation method's step of electrode material is simple and clear among the present invention, and easy operating is not high to equipment requirements, is convenient to the operation and the control of control by technical workers, and is with low cost, and business-like prospect is arranged;
5. carbon coats environmental friendliness in the preparation process of sulphur positive electrode among the present invention, and no poisonous and harmful intermediate product generation meets modern industry to requirement on environmental protection.
Embodiment
Come further to explain the present invention below in conjunction with embodiment, but embodiment does not do any type of qualification to the present invention.
Embodiment 1
0.005mol glucose and 0.001molPVP are put into the 50ml deionized water, stir, all dissolve until glucose and PVP, control pH value is 7, adds 0.05mol sulphur afterwards, ultrasonic dispersion 0.5h.Mixture is moved into autoclave and sealing, and 160 ° of C react 10h down.Question response thing natural cooling alternately washs 3 times with ethanol and deionized water, suction filtration, and freeze-day with constant temperature 24h under 90 ° of C had both got target product again.After carbon coated sulphur, the discharge capacity of sulfur electrode was 1025mAh/g, and circulating after 50 times is 815mAh/g.
Embodiment 2
0.1mol glucose and 0.01molPVP are put into the 50ml deionized water, stir, all dissolve until glucose and PVP, control pH value is 7, adds 0.5mol sulphur afterwards, ultrasonic dispersion 3h.Mixture is moved into autoclave and sealing, and 180 ° of C react 10h down.Question response thing natural cooling alternately washs 3 times with ethanol and deionized water, suction filtration, and freeze-day with constant temperature 24h under 90 ° of C had both got target product again.After carbon coated sulphur, the discharge capacity of sulfur electrode was 1170mAh/g, and circulating after 50 times is 975mAh/g.
Embodiment 3
0.025mol glucose and 0.005molCTAB are put into the 50ml deionized water, stir, all dissolve until glucose and PVP, control pH value is 7, adds 0.1mol sulphur afterwards, ultrasonic dispersion 1h.Mixture is moved into autoclave and sealing, and 180 ° of C react 10h down.Question response thing natural cooling alternately washs 3 times with ethanol and deionized water, suction filtration, and freeze-day with constant temperature 24h under 90 ° of C had both got target product again.After carbon coated sulphur, the discharge capacity of sulfur electrode was 1260mAh/g, and circulating after 50 times is 1170mAh/g.
Embodiment 4
0.03mol glucose and 0.01molPVP polyethylene glycol are put into the 50ml deionized water, stir, all dissolve until glucose and PVP, control pH value 9 adds 0.3mol sulphur, ultrasonic dispersion 0.5h afterwards.Mixture is moved into autoclave and sealing, and 180 ° of C react 2h down.Question response thing natural cooling alternately washs 3 times with ethanol and deionized water, suction filtration, and freeze-day with constant temperature 24h under 90 ° of C had both got target product again.
Embodiment 5
0.03mol glucose and 0.005molSDS are put into the 50ml deionized water, stir, all dissolve until glucose and PVP, control pH value is 5, adds 0.5mol sulphur afterwards, ultrasonic dispersion 1h.Mixture is moved into autoclave and sealing, and 160 ° of C react 30h down.Question response thing natural cooling alternately washs 3 times with ethanol and deionized water, suction filtration, and freeze-day with constant temperature 24h under 90 ° of C had both got target product again.
Embodiment 6
0.03mol glucose and 0.005mol polyethylene glycol are put into the 50ml deionized water, stir, all dissolve until glucose and PVP, control pH value is 12, adds 0.5mol sulphur afterwards, ultrasonic dispersion 1h.Mixture is moved into autoclave and sealing, and 160 ° of C react 10h down.Question response thing natural cooling alternately washs 3 times with ethanol and deionized water, suction filtration, and freeze-day with constant temperature 24h under 90 ° of C had both got target product again.
Embodiment 7
0.03mol glucose and 0.005molSDS are put into the 50ml deionized water, stir, all dissolve until glucose and PVP, control pH value is 3, adds 0.5mol sulphur afterwards, ultrasonic dispersion 1h.Mixture is moved into autoclave and sealing, and 160 ° of C react 10h down.Question response thing natural cooling alternately washs 3 times with ethanol and deionized water, suction filtration, and freeze-day with constant temperature 24h under 90 ° of C had both got target product again.
Claims (7)
1. the carbon method for coating of a lithium-sulfur rechargeable battery anode material sulphur; It is characterized in that comprising the steps: carbohydrate and additive are mixed back water dissolving formation solution or colloidal sol, add sulphur simple substance, ultrasonic dispersion; Fall reactant liquor and under condition of high voltage, carry out hydro-thermal reaction; Reaction back natural cooling alternately washs, filters with organic solvent and deionized water, and drying obtains the sulphur positive electrode that carbon coats; Wherein said additive is the N-polyvinylpyrrolidone, cetrimonium bronmide, polyethylene glycol or dodecyl sodium sulfate.
2. the carbon method for coating of lithium-sulfur rechargeable battery anode material sulphur according to claim 1 is characterized in that said carbohydrate is a glucose, sucrose, and cyclodextrin, the mixture of one or more in the starch, concentration of aqueous solution are 0.1-2mol/L.
3. the carbon method for coating of lithium-sulfur rechargeable battery anode material sulphur according to claim 1, the concentration that it is characterized in that said additive is 0.01-1mol/L.
4. the carbon method for coating of lithium-sulfur rechargeable battery anode material sulphur according to claim 1 is characterized in that said sulphur positive electrode is a sulphur simple substance.
5. the carbon method for coating of lithium-sulfur rechargeable battery anode material sulphur according to claim 1, the time that it is characterized in that said ultrasonic dispersion is 0.5-3h.
6. the carbon method for coating of lithium-sulfur rechargeable battery anode material sulphur according to claim 1, the temperature that it is characterized in that said hydro-thermal reaction is 140-200 ° of C, and the reaction time is preferably 2-30h, and reaction pH is preferably 3 ~ 12.
7. the carbon method for coating of lithium-sulfur rechargeable battery anode material sulphur according to claim 1 is characterized in that organic solvent used in the said washing process is absolute ethyl alcohol, acetone, butanols or carbon tetrachloride.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811726A (en) * | 2013-12-17 | 2014-05-21 | 广西科技大学 | Preparation method of hollow structure coated positive electrode material |
| CN105958030A (en) * | 2016-06-28 | 2016-09-21 | 常州大学 | Preparation method of positive electrode material of lithium-sulphur battery |
| CN108565431A (en) * | 2018-04-24 | 2018-09-21 | 中国矿业大学 | A method of preparing lithium ion battery silicon-carbon compound cathode materials by carbon source of konjaku flour |
| CN110380014A (en) * | 2019-04-26 | 2019-10-25 | 中国航发北京航空材料研究院 | A kind of preparation method of the composite anode material for lithium sulfur battery of high stability |
| CN110492169A (en) * | 2019-08-15 | 2019-11-22 | 中山大学 | All solid state lithium-sulfur cell of a kind of welded type integration and preparation method thereof |
| CN111663148A (en) * | 2020-06-11 | 2020-09-15 | 中南大学 | Method for preventing elemental sulfur from adhering to electrode surface in process of electrocatalytic reduction of sulfur dioxide |
| CN113764635A (en) * | 2021-08-18 | 2021-12-07 | 广东东岛新能源股份有限公司 | One-step hydrothermal preparation method and application of sulfur-carbon composite material |
| WO2023283168A1 (en) * | 2021-07-06 | 2023-01-12 | 33 Tech, Inc. | Lithium-rich nickel manganese oxide battery cathode materials and methods |
| WO2023133106A1 (en) * | 2022-01-04 | 2023-07-13 | Straus Materials Inc. | Microwave-processed, ultra-rapid quenched lithium-rich lithium manganese nickel oxide and methods of making the same |
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| CN1843941A (en) * | 2006-05-12 | 2006-10-11 | 清华大学 | Method for preparing anode material of lithium-iron disulphide battery |
| CN101894943A (en) * | 2010-04-20 | 2010-11-24 | 华南师范大学 | Method for coating lithium ion battery anode material with carbon |
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2011
- 2011-11-04 CN CN2011103444161A patent/CN102509803A/en active Pending
Patent Citations (2)
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| CN1843941A (en) * | 2006-05-12 | 2006-10-11 | 清华大学 | Method for preparing anode material of lithium-iron disulphide battery |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103811726A (en) * | 2013-12-17 | 2014-05-21 | 广西科技大学 | Preparation method of hollow structure coated positive electrode material |
| CN103811726B (en) * | 2013-12-17 | 2016-04-13 | 广西科技大学 | A kind of preparation method of hollow-core construction clad anode material |
| CN105958030A (en) * | 2016-06-28 | 2016-09-21 | 常州大学 | Preparation method of positive electrode material of lithium-sulphur battery |
| CN108565431A (en) * | 2018-04-24 | 2018-09-21 | 中国矿业大学 | A method of preparing lithium ion battery silicon-carbon compound cathode materials by carbon source of konjaku flour |
| CN110380014A (en) * | 2019-04-26 | 2019-10-25 | 中国航发北京航空材料研究院 | A kind of preparation method of the composite anode material for lithium sulfur battery of high stability |
| CN110492169A (en) * | 2019-08-15 | 2019-11-22 | 中山大学 | All solid state lithium-sulfur cell of a kind of welded type integration and preparation method thereof |
| CN110492169B (en) * | 2019-08-15 | 2022-12-23 | 中山大学 | Welding type integrated all-solid-state lithium-sulfur battery and preparation method thereof |
| CN111663148A (en) * | 2020-06-11 | 2020-09-15 | 中南大学 | Method for preventing elemental sulfur from adhering to electrode surface in process of electrocatalytic reduction of sulfur dioxide |
| CN111663148B (en) * | 2020-06-11 | 2021-06-25 | 中南大学 | Method for preventing elemental sulfur from adhering to electrode surface in process of electrocatalytic reduction of sulfur dioxide |
| WO2023283168A1 (en) * | 2021-07-06 | 2023-01-12 | 33 Tech, Inc. | Lithium-rich nickel manganese oxide battery cathode materials and methods |
| CN113764635A (en) * | 2021-08-18 | 2021-12-07 | 广东东岛新能源股份有限公司 | One-step hydrothermal preparation method and application of sulfur-carbon composite material |
| WO2023133106A1 (en) * | 2022-01-04 | 2023-07-13 | Straus Materials Inc. | Microwave-processed, ultra-rapid quenched lithium-rich lithium manganese nickel oxide and methods of making the same |
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Application publication date: 20120620 |