CN103996830A - A preparation method of a sulfur-supported graphene aerogel composite material - Google Patents

A preparation method of a sulfur-supported graphene aerogel composite material Download PDF

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CN103996830A
CN103996830A CN201410199522.9A CN201410199522A CN103996830A CN 103996830 A CN103996830 A CN 103996830A CN 201410199522 A CN201410199522 A CN 201410199522A CN 103996830 A CN103996830 A CN 103996830A
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composite
graphene aerogel
sulfur
graphene
solution
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CN201410199522.9A
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蒋永
赵兵
凌学韬
王志轩
陈卢
陆孟娜
陈勇
焦正
吴明红
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上海大学
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a preparation method of a sulfur-supported graphene aerogel composite material, and belongs to the technical field of lithium ion battery cathode materials. The preparation method mainly includes steps of: subjecting a graphene oxide dispersion liquid, ethanol and sulfur/carbon disulfide which are main raw materials to a hydrothermal reaction at 100-200 DEG C for 6-48 h to obtain sulfur-supported graphene aerogel, and obtaining the sulfur-supported graphene aerogel composite material covered by a polymer through a chemical oxidation method. According to a sulfur-supported graphene aerogel cathode prepared by the preparation method, graphene is staggered and connected to form a three-dimensional conductive network, the supramaximal surface area can absorb more sulfur, and covering by the polymer can overcome a problem of volume expansion of sulphur and a problem of material smashing in charge-discharge processes. In addition, the composite material prepared by the preparation method can be directly used as a pole piece, thus omitting tedious processes, such as pulping and coating in traditional electrode preparation. The preparation method is prone to industrial production.

Description

A kind of preparation method of graphene aerogel sulfur loaded composite material

Technical field

The present invention relates to a kind of preparation method of graphene aerogel sulfur loaded composite material, belong to lithium ion battery electrode material and manufacture field.

Background technology

Operating voltage is high because having for lithium rechargeable battery, energy density large (lightweight), memory-less effect, have extended cycle life and the advantage such as pollution-free, in recent years, has become the first-selected power supply of each electronic product.But along with arriving, electronics miniaturization and electric bicycle, electric automobile, the large-scale energy-accumulating power station in mobile Internet epoch enters extensive development and application stage, lithium rechargeable battery has been proposed to the more requirement of height ratio capacity.

In lithium rechargeable battery system, with respect to negative material (as the theoretical specific capacity of graphite and silicium cathode material is respectively 372 mAh/g, 4200 mAh/g), the positive electrode (LiFePO of low specific capacity 4and LiCoO 2theoretical specific capacity is respectively 170 mAh/g, 274 mAh/g) be the principal element of its development of restriction always.Therefore, develop a kind of specific capacity high, have extended cycle life, positive electrode that security performance is high is particularly important.As positive electrode, elemental sulfur has the highest theoretical specific capacity (1675 mAh/g), and theoretical specific energy is 2600 Wh/kg, and in addition, elemental sulfur also has the advantages such as hypotoxicity, memory space be large, cheap.Therefore, elemental sulfur is a kind of positive electrode very with application prospect.

Lithium-sulfur cell system is set forth in the sixties in 20th century the earliest, different from " rocking chair type " lithium rechargeable battery, and the charge and discharge process of lithium-sulfur cell is ring-type S 8molecule changes through a series of Structure and forms, forms the process of soluble poly sulfide and insoluble polysulfide.Two region of discharges of main existence in its discharge process: electrion region (2.4-2.1V), elemental sulfur is reduced into the high valence state polysulfide ion (S that dissolves in electrolyte n 2-, 5≤n≤8); Low pressure discharge region (2.1-1.5 V), in this process, high valence state polysulfide ion is reduced into the lower valency polysulfide ion (S that dissolves in electrolyte n 2-, 3≤n≤4) and be insoluble to the Li of electrolyte 2s 2, Li 2s.Lithium-sulfur cell is in charge and discharge process, the polysulfide ion of the higher valence state that dissolves in electrolyte generating can be diffused into cathode of lithium, directly and lithium metal generation side reaction, generate many lithium sulfides of lower valency, it is anodal that many lithium sulfides of these lower valencies spread back sulphur, generate many lithium sulfides of high valence state, thereby produce, fly shuttle effect.Fly the generation of shuttle effect, directly caused the reduction of utilization efficiency and the corrosion of cathode of lithium, make circulating battery bad stability, coulombic efficiency reduces.In addition, the conductivity of sulphur extremely low (25 ℃ time, Ω=5 * 10 -30s/cm), insoluble Li in charge and discharge process 2s is deposited on negative pole, and cathode of lithium has dendrite to generate, and S is anodal volumetric expansion can occur and cracked, and these all can cause lithium-sulfur cell cyclical stability variation.

In order to overcome the above problems, researcher has envisioned polymer-carbon back-sulphur composite material.Wherein, polymer-Graphene-sulphur is one of the most promising material.Desirable Graphene is the two dimensional crystal that only has an atomic thickness, is the basic structural unit that forms graphite crystal, has specific area (2630 m of super large 2/ g), have unique charge carrier characteristic and transport property, be very potential energy storage material simultaneously.On the one hand, use material with carbon element can improve the conductivity of whole electrode; On the other hand, polymers functionality has unique chain structure, between polymer molecule with chain in the further confinement sulphur of bonded energy and polysulfide.In addition, it is soft that polymer has machinery conventionally, even has self-healing property, and be coated and be more conducive to solve volumetric expansion and material disintegrating problem than pure carbon.This some work in the past few years in existing marked improvement.For lithium-sulfur cell, the design of polymer-Graphene-sulphur composite material can solve the dissolving of volumetric expansion to a certain degree, the transportation of low ion electronics and polysulfide, hoist capacity, the performances such as cycle life.

Summary of the invention

The object of the invention is to, design and construct a kind of stable three-dimensional conductive network, not only form effectively coated, simultaneously but also electronics and ion transfer passage freely can be provided to elemental sulfur, prepared the lithium sulfur battery anode material of height ratio capacity and excellent cycling performance.The invention provides a kind of preparation method of graphene aerogel sulfur loaded composite material, its characteristic feature is to have the graphene aerogel of high-specific surface area and pore structure as the carrier of active material sulphur, in the mode of chemisorbed, be coated and suppress the dissolving of many sulphions, the conducting polymer coating layer of surface deposition is the dissolving of confinement sulphur and polysulfide further, maintain the stable physical structure of sulfur electrode, thereby improve electrochemistry capacitance and the cycle performance of lithium-sulfur cell

For achieving the above object, the present invention adopts following technical scheme.

A preparation method for graphene aerogel sulfur loaded composite material, comprises the steps:

A. the graphene oxide of getting 5 ~ 200mg is scattered in 50mL deionized water, ultrasonic 1 ~ 24h;

B. measure 5 ~ 30mL alcoholic solution and pour in the graphene oxide solution of step a, stir 0.5 ~ 5h;

C. after the mixed liquor of step b disperses completely, adding 3mL mass volume ratio is sulphur/carbon disulfide solution of 5 ~ 100mg/mL, stirs 1 ~ 10h;

D. the solution of step c gained is proceeded to reactor, under the condition of 100 ~ 200 ℃, constant temperature keeps 6 ~ 48h, question response still is down to room temperature cylindric product is taken out, with alcohol and deionized water, soak respectively three times, freezing microtome section, obtains the composite material of graphene aerogel sulfur loaded after dry;

E. the composite material of steps d is immersed in the solution of 0.01 ~ 1mol/L polymer monomer and 1mol/L hydrochloric acid, soak 0.5h;

F. the material of step e is placed in to surface plate, drips oxidant, react 24h, obtain the composite material of the graphene aerogel sulfur loaded of polymer overmold.

Alcoholic solution described in described step b and steps d is absolute ethyl alcohol or isopropyl alcohol.

Polymer monomer described in described step e is aniline monomer, pyrrole monomer or 3,4-ethylene dioxythiophene monomer.

Oxidant described in described step f is ammonium persulfate, hydrogen peroxide, potassium permanganate or potassium bichromate.

Polymer described in described step f is polyaniline, polypyrrole or poly-3,4-ethylene dioxythiophene.

With existing sulphur/graphene composite material, compare, composite material prepared by the present invention possesses following outstanding structure and performance characteristics:

(1) technique is simple, and process prepared by composite material operates at low temperatures, and manufacturing cycle is short; Output is large, and efficiency is high, can scale application.

(2) design feature of the graphene aerogel sulfur loaded composite material of preparing is: graphene aerogel can provide orderly conductive network, and the surface area of its super large can adsorb more sulphur; The polymer on surface has mechanical flexibility conventionally, even has self-healing property, and than coated volumetric expansion and the material disintegrating problem that is more conducive to solve sulphur of pure carbon.

(3) graphene aerogel/sulphur/conducting polymer composite material preparing, can directly be used as pole piece, has saved the loaded down with trivial details techniques such as slurrying in traditional electrode preparation, coating, easily realizes suitability for industrialized production.

(4) chemical property of the graphene aerogel sulfur loaded composite material of preparing by this simple method has obtained large increase, under the current density of 0.2 A/g, after 50 circulations, still can keep the specific capacity of 669 mAh/g, stable cycle performance.

Graphene aerogel sulfur loaded composite material has successfully overcome that sulphur and discharging product poorly conductive thereof make that utilization efficiency is low, poly-sulphur lithium is soluble in electrolyte, causes the problems such as capacity attenuation for electric discharge intermediate product, is a kind of very promising lithium sulfur battery anode material.

Accompanying drawing explanation

Fig. 1 is the XRD collection of illustrative plates of graphene aerogel sulfur loaded composite material.

Fig. 2 is the SEM picture of graphene aerogel sulfur loaded composite material.

Fig. 3 is the TGA picture of graphene aerogel sulfur loaded composite material.

Fig. 4 is the charging and discharging curve of graphene aerogel sulfur loaded composite material.

Fig. 5 is the cycle performance figure of graphene aerogel sulfur loaded composite material.

Embodiment

Below by embodiment, further illustrate method of the present invention.

embodiment 1

One, by traditional known process, prepare graphene oxide

By potassium peroxydisulfate (K 2s 2o 8) 2.5 g, phosphorus pentoxide (P 2o 5) 2.5 g, be dissolved in the 12 mL concentrated sulfuric acids, be heated to 80 ℃; Then 3 g native graphites are added to above-mentioned solution, be incubated 80 ℃, 4.5 hours; Be cooled to room temperature, with after 500 mL deionized water dilutions, standing over night; Filter, with the floating residual acid that goes of 0.2 mm filter; Dry in 60 ℃ of vacuum drying chambers; The pre-oxidation thing obtaining is joined in the concentrated sulfuric acid of 120 mL ice baths, under agitation slowly add 15 g KMnO 4, in the process adding, maintain the temperature at below 20 ℃.Then be that temperature is controlled at 35 ℃ of stirring 2 h.Add 250 mL deionized water dilutions, in dilution, also will in ice bath, make temperature lower than 50 ℃.Stir again 2 h, then add 0.7 L deionized water, and add at once the H of 20 mL30% 2o 2, mixture produces bubble, and color has become glassy yellow by brown, reaction terminating after approximately 0.5 h.Said mixture is filtered, and wash with the 1:10 watery hydrochloric acid of 1 L, filter to remove part metals ion; With 1 L water washing, filter again, to remove unnecessary acid; Above-mentioned solution is dissolved in 1 L water, and then ultrasonic 0.5 h left and right under 100 W ultrasonic powers, obtains graphene oxide solution (GO), and after centrifugation, the product that obtains brownish black at air drying is the graphene oxide needing.

Two, prepare graphene aerogel sulfur loaded composite material

Preparation method's step is as follows:

1) graphene oxide of getting 100 mg is scattered in 50 mL deionized waters, ultrasonic 1 h; The ethanol solution that adds 10 mL, stirs 0.5 h; Adding 3 mL mass volume ratios is sulphur/carbon disulfide solution of 50 mg/mL, stirs 1 h; Solution is proceeded to reactor, and under the condition of 180 ℃, constant temperature keeps 12 h, with alcohol and deionized water, soaks respectively three times, and freezing microtome section, obtains the composite material of graphene aerogel sulfur loaded after dry;

2) graphene aerogel composite material is immersed in the solution of 0.01 mol/L aniline monomer and 1 mol/L hydrochloric acid, soak 0.5 h; Material after soaking is placed in to surface plate, drips hydrogen peroxide, reaction 24 h obtain the composite material of the graphene aerogel sulfur loaded of polyaniline-coated.

make the electric performance test of material:

The product of preparation is directly pressed in to aluminium online, obtain work electrode, take metal lithium sheet as negative pole, take microporous polypropylene membrane as barrier film, with 1 mol/L bis-(trimethyl fluoride sulfonyl) imine lithium (LiTFSI)/1,3-dioxolanes (DOL) is electrolyte with dimethyl ether (DME) (volume ratio 1:1), assembles 2032 type button lithium-sulfur cells in being full of the glove box of argon gas.

As shown in Figure 1, the present invention has successfully prepared graphene aerogel sulfur loaded composite material to the XRD of product as seen from the figure, has also occurred that Graphene is at the broad peak of 25o left and right in figure simultaneously, with document report consistent, the obvious impurity peaks of nothing in compound product.Fig. 2 is ESEM (SEM) photo that makes composite material, can find out that graphene aerogel sulfur loaded composite material is three-dimensional net structure, aperture be 0.5 ~ 1 μ m not etc.Fig. 3 is thermogravimetric analysis (TGA) collection of illustrative plates, and the content that can find out sulphur in composite material is 59.07%.Fig. 4 be composite material at the charging and discharging curve of 1.5 ~ 3.0 V voltage ranges, charging and discharging capacity is respectively 802.8 mAh/g and 760.9 mAh/g.Fig. 5 is the cycle performance figure of this composite material when 0.2 A/g, and the specific capacity obtaining after 50 circulations still has 669 mAh/g, illustrates that this composite material has higher specific capacity and good cyclical stability.

embodiment 2

The preparation method of graphene oxide is with the above embodiments 1.

1) graphene oxide of getting 80 mg is scattered in 50 mL deionized waters, ultrasonic 24 h; The aqueous isopropanol that adds 5 mL, stirs 5 h; Adding 3 mL mass volume ratios is sulphur/carbon disulfide solution of 75 mg/mL, stirs 1.5 h; Solution is proceeded to reactor, and under the condition of 100 ℃, constant temperature keeps 48 h, with alcohol and deionized water, soaks respectively three times, and freezing microtome section, obtains the composite material of graphene aerogel sulfur loaded after dry;

2) graphene aerogel composite material is immersed in the solution of 0.1 mol/L pyrrole monomer and 1 mol/L hydrochloric acid, soak 0.5 h; Material after soaking is placed in to surface plate, drips potassium permanganate, reaction 24 h obtain the composite material of the coated graphene aerogel sulfur loaded of polypyrrole.

embodiment 3

The preparation of graphene oxide is with the above embodiments 1.

1) graphene oxide of getting 200 mg is scattered in 50 mL deionized waters, ultrasonic 12 h; The ethanol solution that adds 25 mL, stirs 2 h; Adding 3 mL mass volume ratios is sulphur/carbon disulfide solution of 100 mg/mL, stirs 1.5 h; Solution is proceeded to reactor, and under the condition of 150 ℃, constant temperature keeps 24 h, with alcohol and deionized water, soaks respectively three times, and freezing microtome section, obtains the composite material of graphene aerogel sulfur loaded after dry;

2) graphene aerogel composite material is immersed in the solution of 0.5 mol/L aniline monomer and 1 mol/L hydrochloric acid, soak 0.5 h; Material after soaking is placed in to surface plate, drips potassium bichromate, reaction 24 h obtain the composite material of the graphene aerogel sulfur loaded of polyaniline-coated.

embodiment 4

The preparation of graphene oxide is with the above embodiments 1.

1) graphene oxide of getting 5 mg is scattered in 50 mL deionized waters, ultrasonic 2 h; The aqueous isopropanol that adds 30 mL, stirs 0.5 h; Adding 3 mL mass volume ratios is sulphur/carbon disulfide solution of 5 mg/mL, stirs 1.5 h; Solution is proceeded to reactor, and under the condition of 200 ℃, constant temperature keeps 6 h, with alcohol and deionized water, soaks respectively three times, and freezing microtome section, obtains the composite material of graphene aerogel sulfur loaded after dry;

2) graphene aerogel composite material is immersed in the solution of 1 mol/L 3,4-ethylene dioxythiophene monomer and 1 mol/L hydrochloric acid, soak 0.5 h; Material after soaking is placed in to surface plate, drips ammonium persulfate, reaction 12 h obtain the composite material of the coated graphene aerogel sulfur loaded of poly-3,4-ethylene dioxythiophene.

Claims (5)

1. a preparation method for graphene aerogel sulfur loaded composite material, is characterized in that, comprises the steps:
A. the graphene oxide of getting 5 ~ 200mg is scattered in 50mL deionized water, ultrasonic 1 ~ 24h;
B. measure 5 ~ 30mL alcoholic solution and pour in the graphene oxide solution of step a, stir 0.5 ~ 5h;
C. after the mixed liquor of step b disperses completely, adding 3mL mass volume ratio is sulphur/carbon disulfide solution of 5 ~ 100mg/mL, stirs 1 ~ 10h;
D. the solution of step c gained is proceeded to reactor, under the condition of 100 ~ 200 ℃, constant temperature keeps 6 ~ 48h, question response still is down to room temperature cylindric product is taken out, with alcohol and deionized water, soak respectively three times, freezing microtome section, obtains the composite material of graphene aerogel sulfur loaded after dry;
E. the composite material of steps d is immersed in the solution of 0.01 ~ 1mol/L polymer monomer and 1mol/L hydrochloric acid, soak 0.5h;
F. the material of step e is placed in to surface plate, drips oxidant, react 24h, obtain the composite material of the graphene aerogel sulfur loaded of polymer overmold.
2. the preparation method of graphene aerogel sulfur loaded composite material according to claim 1, is characterized in that, the alcoholic solution described in described step b and steps d is absolute ethyl alcohol or isopropyl alcohol.
3. the preparation method of graphene aerogel sulfur loaded composite material according to claim 1, is characterized in that, the polymer monomer described in described step e is aniline monomer, pyrrole monomer or 3,4-ethylene dioxythiophene monomer.
4. the preparation method of graphene aerogel sulfur loaded composite material according to claim 1, is characterized in that, the oxidant described in described step f is ammonium persulfate, hydrogen peroxide, potassium permanganate or potassium bichromate.
5. the preparation method of graphene aerogel sulfur loaded composite material according to claim 1, is characterized in that, the polymer described in described step f is polyaniline, polypyrrole or poly-3,4-ethylene dioxythiophene.
CN201410199522.9A 2014-05-12 2014-05-12 A preparation method of a sulfur-supported graphene aerogel composite material CN103996830A (en)

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104157829A (en) * 2014-08-22 2014-11-19 南京中储新能源有限公司 Sulfur carbon composite material based on polyaniline nanotubes and preparation method thereof, and secondary battery
CN104201350A (en) * 2014-08-22 2014-12-10 南京中储新能源有限公司 Secondary battery based on graphene aerogel/sulphur composite material
CN104269578A (en) * 2014-10-13 2015-01-07 南京中储新能源有限公司 Aluminum sulfur battery and preparation method
CN104319363A (en) * 2014-10-08 2015-01-28 南京中储新能源有限公司 Conductive polymer/carbon-sulfur composite electrode and preparation method
CN104525063A (en) * 2014-12-12 2015-04-22 宁波帝杨电子科技有限公司 Graphene aerogel loaded with polyionic liquid-NaBH4-NiCl2 system and preparation method thereof
CN105013809A (en) * 2015-06-03 2015-11-04 西安博纳材料科技有限公司 Application of carbon aerogel to heavy metal contaminated soil restoration
CN105609773A (en) * 2016-02-19 2016-05-25 钟玲珑 Preparation method for sulfur-doped three-dimensional structured positive electrode material of lithium-sulfur battery
CN105967287A (en) * 2016-07-04 2016-09-28 常州大学 Method for removing manganese ions in water through S element decorated graphene electrode
CN105967288A (en) * 2016-07-04 2016-09-28 常州大学 Method for removing hard calcium ions in water through S element modified graphene electrode
CN105984922A (en) * 2016-07-04 2016-10-05 常州大学 Method for removing aluminum ions in water by using S-modified graphene electrode
CN106099061A (en) * 2016-07-14 2016-11-09 中国科学院宁波材料技术与工程研究所 A kind of porous graphene/silicon composite, its preparation method and lithium ion battery
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CN106145285A (en) * 2016-07-04 2016-11-23 常州大学 A kind of grapheme modified electrode of S element removes the method for hardness magnesium ion in water
CN106328896A (en) * 2016-09-29 2017-01-11 成都新柯力化工科技有限公司 Graphene network sulfur electrode material and preparation method thereof
CN106450209A (en) * 2016-10-28 2017-02-22 合肥国轩高科动力能源有限公司 Sulfur-loaded modified graphene aerogel and preparation method and application thereof
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WO2017139938A1 (en) * 2016-02-18 2017-08-24 肖丽芳 Preparation method for graphene/polypyrrole/sulfur composite positive electrode material
CN108172416A (en) * 2018-01-23 2018-06-15 哈尔滨工业大学 The preparation method and applications of three-dimensional carbon aerogels with porous tube wall nanotube
CN108232135A (en) * 2017-12-18 2018-06-29 襄阳华虹高科新材料有限公司 A kind of lithium sulfur battery anode material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101210119A (en) * 2006-12-29 2008-07-02 比亚迪股份有限公司 Silicon-containing composite material and its preparation method and application
CN102447113A (en) * 2011-12-12 2012-05-09 南开大学 Lithium battery with polymer-coated sulfur/carbon composite material as anode
CN103208618A (en) * 2013-04-24 2013-07-17 中国科学院苏州纳米技术与纳米仿生研究所 Carbon-sulfur composite positive electrode material of lithium-ion battery and preparation method of material
CN103208629A (en) * 2013-04-19 2013-07-17 黑龙江大学 Preparation method of polyaniline/active carbon fiber compound electrode material capable of being used as anode and cathode of capacitor simultaneously
CN103326001A (en) * 2013-05-28 2013-09-25 中国科学院苏州纳米技术与纳米仿生研究所 Method for preparing core-shell polymer-nano sulfur particle composite material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101210119A (en) * 2006-12-29 2008-07-02 比亚迪股份有限公司 Silicon-containing composite material and its preparation method and application
CN102447113A (en) * 2011-12-12 2012-05-09 南开大学 Lithium battery with polymer-coated sulfur/carbon composite material as anode
CN103208629A (en) * 2013-04-19 2013-07-17 黑龙江大学 Preparation method of polyaniline/active carbon fiber compound electrode material capable of being used as anode and cathode of capacitor simultaneously
CN103208618A (en) * 2013-04-24 2013-07-17 中国科学院苏州纳米技术与纳米仿生研究所 Carbon-sulfur composite positive electrode material of lithium-ion battery and preparation method of material
CN103326001A (en) * 2013-05-28 2013-09-25 中国科学院苏州纳米技术与纳米仿生研究所 Method for preparing core-shell polymer-nano sulfur particle composite material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FENG WU ET AL.: "Improvement of Rate and Cycle Performance by Rapid Polyaniline Coating of a MWCNT/Sulfur Cathode", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 *
GUANGMIN ZHOU ET AL.: "Fibrous Hybrid of Graphene and Sulfur Nanocrystals for High-Performance Lithium-Sulfur Batteries", 《ACS NANO》 *

Cited By (27)

* Cited by examiner, † Cited by third party
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CN104157829A (en) * 2014-08-22 2014-11-19 南京中储新能源有限公司 Sulfur carbon composite material based on polyaniline nanotubes and preparation method thereof, and secondary battery
CN104319363A (en) * 2014-10-08 2015-01-28 南京中储新能源有限公司 Conductive polymer/carbon-sulfur composite electrode and preparation method
CN104269578A (en) * 2014-10-13 2015-01-07 南京中储新能源有限公司 Aluminum sulfur battery and preparation method
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CN105013809A (en) * 2015-06-03 2015-11-04 西安博纳材料科技有限公司 Application of carbon aerogel to heavy metal contaminated soil restoration
WO2017139938A1 (en) * 2016-02-18 2017-08-24 肖丽芳 Preparation method for graphene/polypyrrole/sulfur composite positive electrode material
CN105609773A (en) * 2016-02-19 2016-05-25 钟玲珑 Preparation method for sulfur-doped three-dimensional structured positive electrode material of lithium-sulfur battery
CN106115870A (en) * 2016-06-28 2016-11-16 常州大学 One-step synthesis method is mixed sulfur graphite alkene aeroge and removes the electro-adsorption of zinc ion
CN106145285A (en) * 2016-07-04 2016-11-23 常州大学 A kind of grapheme modified electrode of S element removes the method for hardness magnesium ion in water
CN105984922A (en) * 2016-07-04 2016-10-05 常州大学 Method for removing aluminum ions in water by using S-modified graphene electrode
CN105967288A (en) * 2016-07-04 2016-09-28 常州大学 Method for removing hard calcium ions in water through S element modified graphene electrode
CN105967287A (en) * 2016-07-04 2016-09-28 常州大学 Method for removing manganese ions in water through S element decorated graphene electrode
CN106115854A (en) * 2016-07-04 2016-11-16 常州大学 A kind of grapheme modified electrode of S element removes the method for arsenic ion in water
CN106115872A (en) * 2016-07-04 2016-11-16 常州大学 A kind of grapheme modified electrode of S element removes the method for iron ion in water
CN106099061B (en) * 2016-07-14 2018-10-09 中国科学院宁波材料技术与工程研究所 A kind of porous graphene/silicon composite, preparation method and lithium ion battery
CN106099061A (en) * 2016-07-14 2016-11-09 中国科学院宁波材料技术与工程研究所 A kind of porous graphene/silicon composite, its preparation method and lithium ion battery
CN106328896B (en) * 2016-09-29 2019-01-04 成都新柯力化工科技有限公司 A kind of graphene network sulfur electrode material and preparation method
CN106328896A (en) * 2016-09-29 2017-01-11 成都新柯力化工科技有限公司 Graphene network sulfur electrode material and preparation method thereof
CN106450209B (en) * 2016-10-28 2019-07-19 合肥国轩高科动力能源有限公司 A kind of modified graphene aeroge of sulfur loaded and preparation method thereof, application
CN106450209A (en) * 2016-10-28 2017-02-22 合肥国轩高科动力能源有限公司 Sulfur-loaded modified graphene aerogel and preparation method and application thereof
CN106890651A (en) * 2017-04-01 2017-06-27 武斌 Three-dimensional grapheme/molybdenum bisuphide aeroge the preparation method of doping tetraethyl orthosilicate
CN106890651B (en) * 2017-04-01 2019-06-25 武斌 Adulterate three-dimensional grapheme/molybdenum disulfide aeroge preparation method of ethyl orthosilicate
CN108232135A (en) * 2017-12-18 2018-06-29 襄阳华虹高科新材料有限公司 A kind of lithium sulfur battery anode material and preparation method thereof
CN108172416B (en) * 2018-01-23 2019-04-12 哈尔滨工业大学 The preparation method and applications of three-dimensional carbon aerogels with porous tube wall nanotube
CN108172416A (en) * 2018-01-23 2018-06-15 哈尔滨工业大学 The preparation method and applications of three-dimensional carbon aerogels with porous tube wall nanotube

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Application publication date: 20140820