CN106876685B - A kind of preparation method of lithium sulfur battery anode material - Google Patents
A kind of preparation method of lithium sulfur battery anode material Download PDFInfo
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
A kind of preparation method of lithium sulfur battery anode material of the present invention, it is related to the electrode being made of active material, it is a kind of by graphene oxide reduction, boron doping and the completion of one step of solvent thermal reaction, boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material method is prepared by one-step method, the sulphur loading content overcome in lithium sulfur battery anode material existing in the prior art is few and uneven, active material load capacity and utilization rate are low in positive electrode, the defect for causing lithium-sulfur cell chemical property bad.
Description
Technical field
Technical solution of the present invention is related to the electrode being made of active material, specifically a kind of lithium-sulphur cell positive electrode material
The preparation method of material.
Background technique
With lithium ion battery answering in portable electronic product, electric car and instant-plugging hybrid electric vehicle extensively
With there is an urgent need to develop the lithium ion batteries with higher energy density to meet the market demand.Currently, the lithium having been commercialized from
Sub- battery theoretical specific capacity is that 300mAh/g is limited by itself theoretical specific capacity, it is clear that is not able to satisfy to lithium ion battery reality
The requirement of application quality, and the theoretical specific capacity of novel lithium-sulfur cell is about five times of commercial Li-ion batteries theoretical specific capacity
(theoretical specific capacity 1675mAh/g, specific energy 2500Wh/kg), it is considered to be most the high-energy battery of development potentiality it
One.However, there are still some key problems for the application of existing lithium-sulfur cell, first, elemental sulfur is electronics and ion insulation
Body, room-temperature conductivity low (5 × 10-30S·cm-1), since the sulphur of not no ionic state exists, thus it is tired as positive electrode activation
It is difficult；Second, active material sulfur materials itself and final discharging product Li in lithium-sulfur cell2S is the insulator of electronics and ion, is put
Intermediate product polysulfide in electric process is easily soluble in electrolyte, these will cause the irreversible loss and appearance of active material
Amount decaying；Third, sulphur and final product Li2The density of S is different, and volume expansion about 79%, easily leads to Li after sulphur is lithiated2S's
Dusting causes the safety problem of lithium-sulfur cell.For this purpose, how to inhibit the diffusion of polysulfide, improve sulphur distribution and
Improve the research emphasis that the electric conductivity in the cyclic process of sulphur anode is sulfur-based positive electrode material.
In the prior art, it usually solves the above problems sulfur granules and conductive material are compound, is to pass through elemental sulfur
Filling, attachment, mixing, epitaxial growth or cladding method load to high-specific surface area, high porosity and satisfactory electrical conductivity
In the carbon class material of energy, composite positive pole is formed, so as to improve the electric conductivity of sulfur electrode and the cycle performance of battery.In carbon
In plain class material, the conductive excellent, large specific surface area of graphene, chemical stability, the strong and unique two dimension of mechanical performance
Porous network geometry plurality of advantages can shorten electronics and ion transmission path in lithium-sulfur cell, improve the electricity of elemental sulfur
Chemical activity, to improve the cycle performance of active material utilization and battery.About graphene/sulfur composite positive electrode investigation of materials
The prior art also have been reported that: CN105609773A reports a kind of preparation of sulfur doping three-dimensional structure lithium sulfur battery anode material
Method uses hydro-thermal method to generate three-dimensional sulfur doping graphene by sulphur source of benzene sulfonic acid sodium salt, adds in N-Methyl pyrrolidone solution
Enter sulfur doping graphene and Ketjen black ultrasonic reaction forms three-dimensional structure lithium sulfur battery anode material.CN105609733A is reported
The preparation method of the nitrogen co-doped three-dimensional structure lithium sulfur battery anode material of boron, using ammonium hydroxide as nitrogen source, using sodium borohydride as boron
Source prepares the nitrogen co-doped graphene of boron by hydro-thermal method, and it is nitrogen co-doped that Ketjen black, boron are added in N-Methyl pyrrolidone solution
Graphene, sulphur further prepare the nitrogen co-doped three-dimensional structure positive electrode of boron by ultrasonic reaction.CN106450209A is reported
A kind of modified graphene aeroge of sulfur loaded and its preparation method and application utilizes the oxidisability of graphene oxide to cause thiophene
The characteristics of monomer and polymer with nitrogen monomer simultaneous polymerization, forms polythiophene-polymer with nitrogen and is uniformly adhered to graphene oxide
In, while boric acid is introduced, remaining graphene oxide is all then reduced to by graphene using dithiothreitol (DTT), forms load
The modified graphene aerogel precursor object of sulphur is sintered finally by oxygen-free environment the polymer with nitrogen of boron-doping being also decomposed into nitrogen
Compound forms boron nitrogen-doped graphene.CN103199224B report a kind of lithium sulfur battery anode material preparation method and its
Application method prepares graphite oxide using improved Hummer method, and is uniformly mixed sulphur with graphite oxide by chemical reaction,
Graphite oxide/sulphur compound is restored to obtain graphene/sulfur composite positive electrode material using ascorbic acid as reducing agent.It is above-mentioned
The prior art of graphene/sulfur composite positive electrode material, although improving the chemical property of lithium-sulfur cell to a certain extent,
Existing common defects are: carrying out only making sulphur and the simple mechanical mixture of graphene when sulfur doping, cause sulphur loading content few, together
When sulphur load it is uneven, active material load capacity and utilization rate are low in positive electrode, cycle life is low and safety is poor, cause
Lithium-sulfur cell chemical property is bad.Therefore, it improves the microstructure of lithium sulfur battery anode material, improve activity in positive electrode
Substance load capacity and utilization rate are the cycle performances for being effectively improved lithium-sulfur cell, improve lithium sulfur battery anode material electrochemistry
The key of energy.
Summary of the invention
It is a kind of the technical problems to be solved by the present invention are: providing a kind of preparation method of lithium sulfur battery anode material
Graphene oxide reduction, boron doping and one step of hydro-thermal reaction are completed, boron doping graphene/sulphur compound three is prepared by one-step method
The method for tieing up structure lithium sulfur battery anode material overcomes the sulphur load in lithium sulfur battery anode material existing in the prior art
Content is few and uneven, and active material load capacity and utilization rate are low in positive electrode, leads to lithium-sulfur cell chemical property not
Good defect.
The present invention solves technical solution used by the technical problem: a kind of preparation side of lithium sulfur battery anode material
Method is a kind of by graphene oxide reduction, boron doping and the completion of one step of hydro-thermal reaction, passes through one-step method and prepares boron doping graphite
Alkene/sulphur complex three-dimensional structures lithium sulfur battery anode material method, the specific steps are as follows:
The first step, the preparation of graphene oxide:
Graphene oxide is prepared using Hummers method；
Second step, the preparation of boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material:
Graphene oxide made from the first step, nanometer sulphur powder and boron will be weighed according to the ratio of mass ratio 1:1~10:1~3
Acid is placed in ball grinder, using planetary ball mill, according to 2~4:1 of ratio of grinding media to material, under 200~600 revs/min of revolving speed
Ball milling 6~8 hours, the homogeneous mixture of above-mentioned three kinds of substances is obtained, the mass ratio according to the mixture and deionized water is
The ratio of 0.001~0.03:1, adds mixture in deionized water, at normal temperature using ultrasonic disperse instrument 35~
60kHz carries out ultrasonic wave to the mixture of above-mentioned graphene oxide, sulphur powder, boric acid and deionized water and disperses 1~3h, is aoxidized
Graphene, sulphur powder and the mixed uniformly suspension of boric acid will be fitted into stainless steel cauldron at 100~300 DEG C in the suspension
The hydrogel obtained after hydro-thermal reaction is cleaned 3 at 50~90 DEG C with deionized water by lower progress 10~15h of hydro-thermal reaction repeatedly
~5 times, the product after cleaning is freeze-dried 10~20h, system under conditions of subzero 30~45 DEG C and 10~20Pa of vacuum degree
Boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material is obtained, the quality hundred of sulphur in the lithium sulfur battery anode material
Dividing content is 50.3~79.8%.
A kind of preparation method of above-mentioned lithium sulfur battery anode material, the Hummers method are conventionally known technologies.
A kind of preparation method of above-mentioned lithium sulfur battery anode material, related raw material are commercially available, used
Equipment and technique be known to those skilled in the art.
Beneficial effects of the present invention are as follows:
Compared with prior art, the substantive distinguishing features outstanding of the method for the present invention are as follows:
(1) in order to solve, active material load capacity is few in existing lithium sulfur battery anode material and active material utilization is low
Problem, to realize the urgent need for improving active material load capacity and utilization rate in lithium sulfur battery anode material, the present invention is being set
Innovative proposing prepares boron doping graphene/sulphur complex three-dimensional structures lithium-sulphur cell positive electrode material using ball-milling method during meter
The presoma of material further prepares boron doping graphene/sulphur complex three-dimensional structures lithium-sulphur cell positive electrode material by one step hydro thermal method
The novel technological method of material.Graphene oxide is mixed with nano-sulfur by ball-milling method, realizes the uniform mixing of the two height,
And the content of active material in positive electrode can be controlled by the ratio of substance, so that boron doping stone produced by the present invention
The mass percentage of sulphur may be up to 70% in black alkene/sulphur complex three-dimensional structures lithium sulfur battery anode material, at 0.1C, lithium sulphur
The first discharge specific capacity of battery is up to 1390mAh/g, electrochemical performance.
(2) in design process of the invention, carbon in lithium sulfur battery anode material/sulphur composite material structure has been fully considered
Control problem ensure that the excellent electrochemical performance of electrode material by the microstructure control of composite material, i.e., be mixed by boron
Miscellaneous method is realized to carbon/sulphur composite material regulating microstructure.The present invention is using boric acid as boron source and graphite oxide
Alkene prepares three-dimensional boron doping graphene by hydro-thermal method, since boron atom has stronger absorption electronic capability, may replace part
Carbon atom and the crystal structure for not changing graphene, to improve the electric conductivity of carbon material and to more in charge and discharge process
Sulfide generates suction-operated, significantly reduces " the shuttle effect " of polysulfide；C-S key can be formed between sulphur and graphene molecules
Rather than simple physical attachment, and then effectively improve the cycle performance of lithium-sulfur cell.Therefore, the present invention passes through to lithium-sulfur cell
The microstructure of positive electrode controls, and improves the cycle performance of lithium sulfur battery anode material.
(3) compared with the prior art CN105609773A and CN105609733A, the present invention overcomes above-mentioned existing
Sulfur doping method in technology is only to mix two kinds of suspension, can not provide the pole that sulphur enters three-dimensional grapheme material internal needs
Strong energy barrier causes sulphur to be difficult to enter in the internal structure of three-dimensional grapheme material, to be unable to control final electrode material
Content, the sulphur load capacity of middle active material are few, sulphur load is uneven, so as to cause the lithium sulfur battery anode material electricity prepared by it
The problem of pond chemical property difference.
(4) compared with prior art CN105609773A, CN103199224B, the present invention overcomes above-mentioned existing skills
The process used in art will lead to carbon/sulphur composite material fault of construction: graphene specific surface energy is high, graphene film interlayer
Can occur to reunite leads to the reduction of active material load capacity；The open duct of graphene film interlayer makes to generate in charge and discharge process easy
The polysulfide of electrolyte is dissolved in easily from wherein spreading out；Directly by sulphur and graphene it is compound be difficult to obtain cycle performance it is excellent
Different electrode material, so as to cause the problem of the battery performance difference of the lithium sulfur battery anode material prepared by it.
(5) compared with prior art CN106450209A, the present invention overcomes it is above-mentioned in the prior art with polythiophene,
The elemental sulfur that dithiothreitol (DTT) oxidation product decomposes is sulphur source, since redox reaction step is complicated, while can not be real
The quantitative control of existing chemical reaction product, so that raw material decomposition is not thorough, sulfur content is low in decomposition product, purity is low and sulphur is negative
It carries unevenly, causes prepared lithium-sulfur cell chemical property poor；The prior art does not consider, also can not quantitatively control react
Content, dispersity and carbon/sulphur composite structure of final product sulphur, lead to prepared lithium-sulfur cell chemical property not
Stable problem；Not only raw material types are various, step of preparation process is complicated in preparation process, high production cost, are not suitable for rule
The problems such as modelling produces.
Compared with prior art, the marked improvement of the method for the present invention is as follows:
(1) in design process of the invention, fully considered raw material, synthetic method and processing step to scale
The influence of production and product stability.It is using using boric acid as boron source, it is innovative under the premise of nano sulfur powder is as sulphur source
Using simple ball-milling method prepare boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material presoma, lead to
Cross one-step method preparation boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material, raw materials less varieties, technique
It is simple and at low cost, it is easy to accomplish the batch production of the composite material can meet field of engineering technology to high-performance lithium-sulfur cell
The requirement of positive electrode.
(2) the method for the present invention controls the content of sulphur in positive electrode, boron and graphene by the ratio of raw material, guarantees
Dispersity and carbon/sulphur composite material microstructure of sulphur and boron in graphene, so that prepared lithium-sulphur cell positive electrode
Material not only electrochemical performance, and stability is splendid.
(3) graphene of boron doping prepared by the method for the present invention/sulphur complex three-dimensional structures lithium sulfur battery anode material, passes through
The control of synthesis technology, using it as anode slice of lithium ion battery is that the lithium-sulfur cell that working electrode is assembled into is electric at 0.1C
The first discharge specific capacity in pond is up to 1390mAh/g；After 0.1C is recycled 100 weeks, the specific discharge capacity of battery can still be kept
1050mAh/g；Efficiency for charge-discharge is up to 99.8%, and with high discharge capacity and long cycle life, chemical property is obvious
Better than lithium-sulfur cell performance made from the above-mentioned prior art.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is that boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material X obtained by embodiment 1 is penetrated
Ray diffraction diagram.
Fig. 2 is boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material thermogravimetric obtained by embodiment 1
Curve graph.
Fig. 3 is boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material scanning obtained by embodiment 1
Electron micrograph.
Fig. 4 is boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material electrification obtained by embodiment 1
Learn performance curve.
Specific embodiment
Embodiment 1
The first step, the preparation of graphene oxide:
Graphene oxide is prepared using Hummers method；
Second step, the preparation of boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material:
Graphene oxide made from the first step, nanometer sulphur powder and boric acid juxtaposition will be weighed according to the ratio of mass ratio 1:1:1
In ball grinder, using planetary ball mill, according to ratio of grinding media to material 2:1, ball milling 6 hours, are obtained under 200 revs/min of revolving speed
The homogeneous mixture of above-mentioned three kinds of substances, the ratio for being 0.001:1 according to the mixture and the mass ratio of deionized water, will mix
Object is add to deionized water, at normal temperature using ultrasonic disperse instrument 35kHz to above-mentioned graphene oxide, sulphur powder, boric acid with
The mixture of deionized water carries out ultrasonic wave and disperses 1h, obtains graphene oxide, sulphur powder and the mixed uniformly suspension of boric acid, will
Progress hydro-thermal reaction 10h, the hydrogel that will hydro-thermal reaction after obtains 100 DEG C at are fitted into stainless steel cauldron in the suspension
It is cleaned repeatedly at 50 DEG C 3 times with deionized water, the product after cleaning is cold under conditions of subzero 30 DEG C and vacuum degree 10Pa
Dry 10h is lyophilized, boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material, the lithium sulfur battery anode material is made
The mass percentage of middle sulphur is 50.3%.
Fig. 1 is that boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material X obtained by the present embodiment is penetrated
Ray diffraction diagram.Wherein, respectively illustrate boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material (in figure-▲-
Shown in curve), three-dimensional boron doping graphene composite material (in figure-● shown in-curve) and the single-phase sulphur of standard (- ■-curve in figure
It is shown) X ray diffracting spectrum.It can be seen from the figure that boron doping graphene/sulphur complex three-dimensional structures lithium-sulphur cell positive electrode material
The characteristic peak of sulphur is obviously weaker in material, shows that sulphur exists in the composite material with unformed state, i.e., sulphur is uniformly dispersed in
Between graphene grid.
Fig. 2 is boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material heat obtained by the present embodiment
Weight curve graph.It can be seen from the figure that in boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material sulphur quality
Percentage composition about 70% shows that the composite three dimensional structure is excellent, has big specific surface area, be conducive to the storage of sulphur.
Fig. 3 is that boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material obtained by the present embodiment is swept
Retouch electron micrograph.It can be seen from the figure that boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material tool
There is unique three-dimensional porous network structure, there is more fold and high-specific surface area；Composite material surface does not have apparent sulphur
Particle illustrates that sulphur is dispersed between graphene grid, so that lithium sulfur battery anode material prepared by the present invention has height
Circulating battery stability.
Fig. 4 is boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material electricity obtained by the present embodiment
Chemical property curve.It may be seen that the discharge capacity for the first time of the material is up to 1390mAh/g under 0.1C current density.
Embodiment 2
The first step, the preparation of graphene oxide:
Graphene oxide is prepared using Hummers method；
Second step, the preparation of boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material:
Graphene oxide made from the first step, nanometer sulphur powder and boric acid juxtaposition will be weighed according to the ratio of mass ratio 1:5:2
In ball grinder, using planetary ball mill, according to ratio of grinding media to material 3:1, ball milling 7 hours, are obtained under 400 revs/min of revolving speed
The homogeneous mixture of above-mentioned three kinds of substances, the ratio for being 0.01:1 according to the mixture and the mass ratio of deionized water, will mix
Object is add to deionized water, at normal temperature using ultrasonic disperse instrument 50kHz to above-mentioned graphene oxide, sulphur powder, boric acid with
The mixture of deionized water carries out ultrasonic wave and disperses 2h, obtains graphene oxide, sulphur powder and the mixed uniformly suspension of boric acid, will
Progress hydro-thermal reaction 12h, the hydrogel that will hydro-thermal reaction after obtains 200 DEG C at are fitted into stainless steel cauldron in the suspension
It is cleaned repeatedly at 70 DEG C 4 times with deionized water, the product after cleaning is cold under conditions of subzero 40 DEG C and vacuum degree 15Pa
Dry 15h is lyophilized, boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material, the lithium sulfur battery anode material is made
The mass percentage of middle sulphur is 66.7%.
Embodiment 3
The first step, the preparation of graphene oxide:
Graphene oxide is prepared using Hummers method；
Second step, the preparation of boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material:
Graphene oxide made from the first step, nanometer sulphur powder and boric acid juxtaposition will be weighed according to the ratio of mass ratio 1:10:3
In ball grinder, using planetary ball mill, according to ratio of grinding media to material 4:1, ball milling 8 hours, are obtained under 600 revs/min of revolving speed
The homogeneous mixture of above-mentioned three kinds of substances, the ratio for being 0.03:1 according to the mixture and the mass ratio of deionized water, will mix
Object is add to deionized water, at normal temperature using ultrasonic disperse instrument 60kHz to above-mentioned graphene oxide, sulphur powder, boric acid with
The mixture of deionized water carries out ultrasonic wave and disperses 3h, obtains graphene oxide, sulphur powder and the mixed uniformly suspension of boric acid, will
Progress hydro-thermal reaction 15h, the hydrogel that will hydro-thermal reaction after obtains 300 DEG C at are fitted into stainless steel cauldron in the suspension
It is cleaned repeatedly at 90 DEG C 5 times with deionized water, the product after cleaning is cold under conditions of subzero 45 DEG C and vacuum degree 20Pa
Dry 20h is lyophilized, boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material, the lithium sulfur battery anode material is made
The mass percentage of middle sulphur is 79.8%.
In above-described embodiment, the Hummers method is conventionally known technology, and related raw material pass through commercially available obtain
, equipment used and technique are known to those skilled in the art.
Claims (1)
1. a kind of preparation method of lithium sulfur battery anode material, it is characterised in that: be a kind of by graphene oxide reduction, boron doping
It is completed with one step of hydro-thermal reaction, boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material is prepared by one-step method
Method, the specific steps are as follows:
The first step, the preparation of graphene oxide:
Graphene oxide is prepared using Hummers method；
Second step, the preparation of boron doping graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material:
Graphene oxide made from the first step, nanometer sulphur powder and boric acid will be weighed simultaneously according to the ratio of mass ratio 1:1~10:1~3
It is placed in ball grinder, uses planetary ball mill, according to 2~4:1 of ratio of grinding media to material, the ball milling 6 under 200~600 revs/min of revolving speed
~8 hours, obtain the homogeneous mixture of above-mentioned three kinds of substances, according to the mixture and the mass ratio of deionized water be 0.001~
The ratio of 0.03:1, adds mixture in deionized water, uses ultrasonic disperse instrument in 35~60kHz to above-mentioned at normal temperature
Graphene oxide, sulphur powder, boric acid and deionized water mixture carry out ultrasonic wave and disperse 1~3h, obtain graphene oxide, sulphur powder
With the mixed uniformly suspension of boric acid, it is anti-that 100~300 DEG C at progress hydro-thermal will be fitted into stainless steel cauldron in the suspension
10~15h is answered, the hydrogel obtained after hydro-thermal reaction is cleaned 3~5 times repeatedly with deionized water at 50~90 DEG C, will be cleaned
Product afterwards is freeze-dried 10~20h under conditions of subzero 30~45 DEG C and 10~20Pa of vacuum degree, and boron doping graphite is made
Alkene/sulphur complex three-dimensional structures lithium sulfur battery anode material, the mass percentage of sulphur is 50.3 in the lithium sulfur battery anode material
~79.8%.
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| CN107732202B (en) * | 2017-10-16 | 2020-11-03 | 河源广工大协同创新研究院 | Preparation method of lithium-sulfur battery positive electrode material |
| CN107732203B (en) * | 2017-10-16 | 2020-11-03 | 河源广工大协同创新研究院 | Preparation method of nano cerium dioxide/graphene/sulfur composite material |
| CN107742707B (en) * | 2017-10-16 | 2020-08-21 | 河源广工大协同创新研究院 | Preparation method of nano lanthanum oxide/graphene/sulfur composite material |
| CN108172795B (en) * | 2017-12-27 | 2020-05-12 | 肇庆市华师大光电产业研究院 | Preparation method of lithium-sulfur battery positive electrode material |
| CN109103439B (en) * | 2018-08-30 | 2021-09-03 | 广东工业大学 | Flexible self-supporting lithium-sulfur battery positive electrode material, preparation method and battery thereof |
| CN111740109B (en) * | 2020-06-22 | 2021-06-08 | 珠海冠宇电池股份有限公司 | Preparation method of boron and phosphorus doped graphitized carbon-nitrogen compound cathode material activated by KOH |
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| WO2013066448A2 (en) * | 2011-08-08 | 2013-05-10 | Battelle Memorial Institute | Polymer-sulfur composite materials for electrodes in li-s energy storage devices |
| CN103214845A (en) * | 2013-04-26 | 2013-07-24 | 南京理工大学 | Boron doped graphene-polyaniline nanocomposite and preparation method thereof |
| CN104409702A (en) * | 2014-11-21 | 2015-03-11 | 黑龙江科技大学 | Preparation method of N-doped coated graphene micron silicon composite material |
| CN106517162A (en) * | 2016-12-15 | 2017-03-22 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of nitrogen/ sulphur co-doping three-dimensional graphene sponge |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013066448A2 (en) * | 2011-08-08 | 2013-05-10 | Battelle Memorial Institute | Polymer-sulfur composite materials for electrodes in li-s energy storage devices |
| CN103214845A (en) * | 2013-04-26 | 2013-07-24 | 南京理工大学 | Boron doped graphene-polyaniline nanocomposite and preparation method thereof |
| CN104409702A (en) * | 2014-11-21 | 2015-03-11 | 黑龙江科技大学 | Preparation method of N-doped coated graphene micron silicon composite material |
| CN106517162A (en) * | 2016-12-15 | 2017-03-22 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of nitrogen/ sulphur co-doping three-dimensional graphene sponge |
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