CN106876685A - 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
- Publication number
- CN106876685A CN106876685A CN201710242972.5A CN201710242972A CN106876685A CN 106876685 A CN106876685 A CN 106876685A CN 201710242972 A CN201710242972 A CN 201710242972A CN 106876685 A CN106876685 A CN 106876685A
- Authority
- CN
- China
- Prior art keywords
- sulphur
- battery anode
- anode material
- sulfur battery
- lithium
- 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.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of preparation method of lithium sulfur battery anode material of the present invention, it is related to the electrode being made up of active material, it is that one kind completes graphene oxide reduction, boron doping and the step of solvent thermal reaction one, the method that boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material is prepared by one-step method, the sulphur loading content overcome present in prior art in lithium sulfur battery anode material 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 not good.
Description
Technical field
Technical scheme is related to the electrode being made up of active material, specifically a kind of lithium-sulphur cell positive electrode material
The preparation method of material.
Background technology
With lithium ion battery extensively should in portable type electronic product, electric automobile and instant-plugging hybrid electric vehicle
With in the urgent need to exploitation has the lithium ion battery of higher energy density to meet the market demand.At present, the lithium having been commercialized from
Sub- battery theoretical specific capacity is by itself theoretical specific capacity for 300mAh/g is limited, it is clear that can not meet to lithium ion battery reality
The requirement of application quality, and the theoretical specific capacity of new lithium-sulfur cell is about five times of commercial Li-ion batteries theoretical specific capacity
(theoretical specific capacity is 1675mAh/g, and specific energy is 2500Wh/kg), it is considered to be most the high-energy battery of development potentiality it
One.However, the application of existing lithium-sulfur cell still suffers from some key problem, first, elemental sulfur is electronics and ion insulation
Body, room-temperature conductivity is low by (5 × 10-30S·cm-1), it is because the sulphur without ionic state is present thus tired as positive electrode activation
It is difficult；Second, in lithium-sulfur cell active material sulfur materials in itself with final discharging product Li2S is the insulator of electronics and ion, is put
Intermediate product polysulfide in electric process is easily soluble in electrolyte, and these can cause the irreversible loss and appearance of active material
Amount decay；Third, sulphur and final product Li2The density of S is different, and volumetric expansion about 79%, is easily caused Li after sulphur is lithiated2S's
Efflorescence, causes the safety problem of lithium-sulfur cell.Therefore, how to suppress the diffusion of polysulfide, improve sulphur distribution and
Improve the research emphasis that the electric conductivity in sulphur positive pole cyclic process is sulfur-based positive electrode material.
In the prior art, generally sulfur granules and conductive material are combined to solve the above problems, are to pass through elemental sulfur
The method of filling, attachment, mixing, epitaxial growth or cladding is loaded 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
The two dimension that in plain class material, the conductive excellent, specific surface area of Graphene is big, chemical stability, mechanical performance are strong and unique
Porous network geometry plurality of advantages, can shorten electronics and ion transmission path in lithium-sulfur cell, improve the electricity of elemental sulfur
Chemism, so as to improve the cycle performance of active material utilization and battery.On graphene/sulfur composite positive electrode investigation of materials
Prior art in 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 1-METHYLPYRROLIDONE solution
Enter sulfur doping Graphene and form three-dimensional structure lithium sulfur battery anode material with Ketjen black ultrasonic reaction.CN105609733A is reported
The preparation method of the nitrogen co-doped three-dimensional structure lithium sulfur battery anode material of boron, using ammoniacal liquor as nitrogen source, using sodium borohydride as boron
Source prepares the nitrogen co-doped Graphene of boron by hydro-thermal method, adds Ketjen black, boron nitrogen co-doped in 1-METHYLPYRROLIDONE 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, the oxidisability using graphene oxide triggers 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 introducing boric acid, it is Graphene by remaining graphene oxide Restore All then to use dithiothreitol (DTT), forms load
The modified graphene aerogel precursor thing of sulphur, nitrogen is also decomposed into finally by oxygen-free environment sintering by the polymer with nitrogen of boron-doping
Compound forms boron nitrogen-doped graphene.CN103199224B report a kind of lithium sulfur battery anode material preparation method and its
Application method, graphite oxide is prepared using improved Hummer methods, and is uniformly mixed sulphur with graphite oxide by chemically reacting,
The compound of graphite oxide/sulphur reduce as reducing agent with ascorbic acid and obtains graphene/sulfur composite positive electrode material.It is above-mentioned
In the prior art of graphene/sulfur composite positive electrode material, although improve the chemical property of lithium-sulfur cell to a certain extent, but
The common defects of presence are：Only make sulphur and Graphene simple mechanical mixture when carrying out 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 security is poor, cause
Lithium-sulfur cell chemical property is not good.Therefore, improve the microstructure of lithium sulfur battery anode material, improve activity in positive electrode
Material 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.
The content of the invention
The technical problems to be solved by the invention are：A kind of preparation method of lithium sulfur battery anode material is provided, is a kind of
Graphene oxide reduction, boron doping and the step of solvent thermal reaction one are completed, preparing boron doped graphene/sulphur by one-step method is combined
The method of three-dimensional structure lithium sulfur battery anode material, overcomes the sulphur present in prior art in lithium sulfur battery anode material and bears
Load content is few and uneven, and active material load capacity and utilization rate are low in positive electrode, cause lithium-sulfur cell chemical property
Not good defect.
The present invention solves the technical scheme that is used of 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 the step of solvent thermal reaction one, and boron doped graphite is prepared by one-step method
The method of alkene/sulphur complex three-dimensional structures lithium sulfur battery anode material, comprises the following steps that：
The first step, the preparation of graphene oxide：
Graphene oxide is prepared using Hummers methods；
Second step, the preparation of boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material：
Will be according to mass ratio 1:1~10:1~3 ratio weighs graphene oxide obtained in the first step, nanometer sulphur powder and boron
Acid is placed in ball grinder, using planetary ball mill, according to ratio of grinding media to material 2~4:1, under 200~600 revs/min of rotating speed
Ball milling 6~8 hours, obtains the homogeneous mixture of above-mentioned three kinds of materials, is with the mass ratio of deionized water according to the mixture
0.001~0.03:1 ratio, in adding mixture to deionized water, at normal temperatures 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
Under carry out 10~15h of hydro-thermal reaction, the hydrogel deionized water that will be obtained after hydro-thermal reaction cleans 3 repeatedly at 50~90 DEG C
~5 times, by the product after cleaning under conditions of subzero 30~45 DEG C and 10~20Pa of vacuum 10~20h of freeze-drying, system
Obtain boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material, the quality hundred of sulphur in the lithium sulfur battery anode material
Content is divided to be 50.3~79.8%.
A kind of preparation method of above-mentioned lithium sulfur battery anode material, the Hummers methods are existing known technologies.
A kind of preparation method of above-mentioned lithium sulfur battery anode material, involved raw material are used by commercially available
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 of the protrusion of the inventive method are as follows：
(1) in order to solve, active material load capacity in existing lithium sulfur battery anode material is few and active material utilization is low
Problem, to realize improving the active demand of active material load capacity and utilization rate in lithium sulfur battery anode material, the present invention is setting
Proposing for novelty prepares boron doped 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 doped 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 both height,
And the content of active material in positive electrode can be controlled by the ratio of material so that the obtained boron doping stone of the present invention
The weight/mass percentage composition of sulphur may be up to 70% in black alkene/sulphur complex three-dimensional structures lithium sulfur battery anode material, under 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, the structure of carbon/sulphur composite in lithium sulfur battery anode material has been taken into full account
Control problem, controls to ensure that the excellent electrochemical performance of electrode material by the microstructure of composite, i.e., mixed by boron
Miscellaneous method, realizes the regulating microstructure to carbon/sulphur composite.The present invention is by the use of boric acid as boron source and graphite oxide
Alkene prepares three-dimensional boron doped graphene by hydro-thermal method, because boron atom has stronger absorption electronic capability, may replace part
Carbon atom and do not change the crystal structure of Graphene, so as to improve carbon material electric conductivity and to charge and discharge process in it is many
Sulfide produces suction-operated, significantly reduces " the shuttle effect " of polysulfide；C-S keys 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 is by lithium-sulfur cell
The microstructure control of positive electrode, improves the cycle performance of lithium sulfur battery anode material.
(3) compared with 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, it is impossible to provide the pole that sulphur needs into three-dimensional grapheme material internal
Strong energy barrier, causes sulphur to be difficult in the internal structure for enter three-dimensional grapheme material, so that uncontrollable final electrode material
The content of middle active material, sulphur load capacity 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 skill
The process used in art can cause the fault of construction of carbon/sulphur composite：Graphene specific surface energy is high, graphene film interlayer
Reunion can occur causes the reduction of active material load capacity；It is easy that the duct that graphene film interlayer is opened makes to produce in charge and discharge process
The polysulfide for being dissolved in electrolyte easily spreads out therefrom；Directly it is difficult to obtain cycle performance excellent by sulphur and Graphene are compound
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,
It is sulphur source that dithiothreitol (DTT) oxidation product decomposes the elemental sulfur for obtaining, because redox reaction step is complicated, while cannot be real
The quantitative control of existing chemical reaction product so that raw material are decomposed not thoroughly, sulfur content is low in catabolite, purity is low and sulphur is negative
Carry uneven, cause prepared lithium-sulfur cell chemical property poor；The prior art does not consider, cannot quantify control yet and react
The content of final product sulphur, dispersity and carbon/sulphur composite structure, cause prepared lithium-sulfur cell chemical property not
The problem of stabilization；Not only raw material types are various, step of preparation process is complicated in preparation process, production cost is high, are not suitable for rule
The problems such as modelling is produced.
Compared with prior art, the marked improvement of the inventive method is as follows：
(1) in design process of the invention, taken into full account raw material, synthetic method and processing step to scale
Production and the influence of product stability.Using using boric acid as boron source, on the premise of nano sulfur powder is as sulphur source, novelty
The simple ball-milling method of use prepare the presoma of boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material, lead to
Cross one-step method and prepare boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material, raw materials less varieties, technique
Simple and low cost, it is easy to accomplish the batch production of the composite, can meet field of engineering technology to high-performance lithium-sulfur cell
The use requirement of positive electrode.
(2) the inventive method controls the content of sulphur, boron and Graphene in positive electrode by the ratio of raw material, it is ensured that
The microstructure of the dispersity and carbon of sulphur and boron/sulphur composite in Graphene so that prepared lithium-sulphur cell positive electrode
Material not only electrochemical performance, and stability is splendid.
(3) the boron doped graphene prepared by the inventive method/sulphur complex three-dimensional structures lithium sulfur battery anode material, passes through
The control of synthesis technique, as anode slice of lithium ion battery is the lithium-sulfur cell that is assembled into of working electrode electricity under 0.1C with it
The first discharge specific capacity in pond is up to 1390mAh/g；After 0.1C is circulated 100 weeks, the specific discharge capacity of battery can still keep
1050mAh/g；, up to 99.8%, with discharge capacity high and cycle life long, its chemical property is obvious for efficiency for charge-discharge
Better than lithium-sulfur cell performance obtained in above-mentioned prior art.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is that the X of the boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material obtained by embodiment 1 is penetrated
Ray diffraction diagram.
Fig. 2 is the thermogravimetric of the boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material obtained by embodiment 1
Curve map.
Fig. 3 is the scanning of the boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material obtained by embodiment 1
Electron micrograph.
Fig. 4 is the electrification of the boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material 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 methods；
Second step, the preparation of boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material：
Will be according to mass ratio 1:1:1 ratio weighs graphene oxide obtained in the first step, nanometer sulphur powder and boric acid juxtaposition
In ball grinder, using planetary ball mill, according to ratio of grinding media to material 2:1, ball milling 6 hours, obtain under 200 revs/min of rotating speed
The homogeneous mixture of above-mentioned three kinds of materials, is 0.001 according to the mass ratio of the mixture and deionized water:1 ratio, will mix
Thing is added in deionized water, at normal temperatures using ultrasonic disperse instrument 35kHz to above-mentioned graphene oxide, sulphur powder, boric acid with
The mixture of deionized water carries out ultrasonic wave dispersion 1h, obtains graphene oxide, sulphur powder and the mixed uniformly suspension of boric acid, will
Be fitted into the suspension in stainless steel cauldron carries out hydro-thermal reaction 10h at 100 DEG C, the hydrogel that will be obtained after hydro-thermal reaction
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 10Pa
Dry 10h is freezed, boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material, the lithium sulfur battery anode material is obtained
The weight/mass percentage composition of middle sulphur is 50.3%.
Fig. 1 is that the X of the boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material obtained by the present embodiment is penetrated
Ray diffraction diagram.Wherein, respectively illustrate boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material (in figure-▲-
Shown in curve), three-dimensional boron doped graphene composite (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 that boron doped graphene/sulphur complex three-dimensional structures lithium-sulphur cell positive electrode material
The characteristic peak of sulphur is substantially weaker in material, shows that sulphur exists with unformed state in the composite, i.e., sulphur is uniformly dispersed in
Between Graphene grid.
Fig. 2 is the heat of the boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material obtained by the present embodiment
Weight curve map.It can be seen that in boron doped 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, there is big specific surface area, is conducive to the storage of sulphur.
Fig. 3 is sweeping for the boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material obtained by the present embodiment
Retouch electron micrograph.It can be seen that boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material tool
There is the three-dimensional porous network structure of uniqueness, with more fold and high-specific surface area；Composite material surface does not have obvious sulphur
Particle, illustrates that sulphur is dispersed between Graphene grid so that the lithium sulfur battery anode material prepared by the present invention has height
Circulating battery stability.
Fig. 4 is the electricity of the boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material obtained by the present embodiment
Chemical property curve.It may be seen that under 0.1C current densities, the discharge capacity first of the material is up to 1390mAh/g.
Embodiment 2
The first step, the preparation of graphene oxide：
Graphene oxide is prepared using Hummers methods；
Second step, the preparation of boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material：
Will be according to mass ratio 1:5:2 ratio weighs graphene oxide obtained in the first step, nanometer sulphur powder and boric acid juxtaposition
In ball grinder, using planetary ball mill, according to ratio of grinding media to material 3:1, ball milling 7 hours, obtain under 400 revs/min of rotating speed
The homogeneous mixture of above-mentioned three kinds of materials, is 0.01 according to the mass ratio of the mixture and deionized water:1 ratio, will mix
Thing is added in deionized water, at normal temperatures using ultrasonic disperse instrument 50kHz to above-mentioned graphene oxide, sulphur powder, boric acid with
The mixture of deionized water carries out ultrasonic wave dispersion 2h, obtains graphene oxide, sulphur powder and the mixed uniformly suspension of boric acid, will
Be fitted into the suspension in stainless steel cauldron carries out hydro-thermal reaction 12h at 200 DEG C, the hydrogel that will be obtained after hydro-thermal reaction
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 15Pa
Dry 15h is freezed, boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material, the lithium sulfur battery anode material is obtained
The weight/mass percentage composition of middle sulphur is 66.7%.
Embodiment 3
The first step, the preparation of graphene oxide：
Graphene oxide is prepared using Hummers methods；
Second step, the preparation of boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material：
Will be according to mass ratio 1:10:3 ratio weighs graphene oxide obtained in the first step, nanometer sulphur powder and boric acid juxtaposition
In ball grinder, using planetary ball mill, according to ratio of grinding media to material 4:1, ball milling 8 hours, obtain under 600 revs/min of rotating speed
The homogeneous mixture of above-mentioned three kinds of materials, is 0.03 according to the mass ratio of the mixture and deionized water:1 ratio, will mix
Thing is added in deionized water, at normal temperatures using ultrasonic disperse instrument 60kHz to above-mentioned graphene oxide, sulphur powder, boric acid with
The mixture of deionized water carries out ultrasonic wave dispersion 3h, obtains graphene oxide, sulphur powder and the mixed uniformly suspension of boric acid, will
Be fitted into the suspension in stainless steel cauldron carries out hydro-thermal reaction 15h at 300 DEG C, the hydrogel that will be obtained after hydro-thermal reaction
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 20Pa
Dry 20h is freezed, boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material, the lithium sulfur battery anode material is obtained
The weight/mass percentage composition of middle sulphur is 79.8%.
In above-described embodiment, the Hummers methods are existing known technologies, and involved raw material are obtained by commercially available
, 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：It is that one kind adulterates graphene oxide reduction, boron
Completed with the step of solvent thermal reaction one, boron doped graphene/sulphur complex three-dimensional structures lithium-sulphur cell positive electrode material is prepared by one-step method
The method of material, comprises the following steps that：
The first step, the preparation of graphene oxide：
Graphene oxide is prepared using Hummers methods；
Second step, the preparation of boron doped graphene/sulphur complex three-dimensional structures lithium sulfur battery anode material：
Will be according to mass ratio 1:1~10:1~3 ratio weighs graphene oxide obtained in the first step, nanometer sulphur powder and boric acid simultaneously
It is placed in ball grinder, using planetary ball mill, according to ratio of grinding media to material 2~4:1, the ball milling 6 under 200~600 revs/min of rotating speed
~8 hours, obtain the homogeneous mixture of above-mentioned three kinds of materials, according to the mass ratio of the mixture and deionized water for 0.001~
0.03:1 ratio, in adding mixture to deionized water, at normal temperatures using ultrasonic disperse instrument in 35~60kHz to above-mentioned
The mixture of graphene oxide, sulphur powder, boric acid and deionized water carries out ultrasonic wave and disperses 1~3h, obtains graphene oxide, sulphur powder
With the mixed uniformly suspension of boric acid, will be fitted into stainless steel cauldron that hydro-thermal is carried out at 100~300 DEG C is anti-in the suspension
10~15h is answered, the hydrogel deionized water that will be obtained after hydro-thermal reaction is cleaned 3~5 times repeatedly at 50~90 DEG C, will be cleaned
10~the 20h of freeze-drying under conditions of subzero 30~45 DEG C and 10~20Pa of vacuum of product afterwards, is obtained boron doped graphite
Alkene/sulphur complex three-dimensional structures lithium sulfur battery anode material, the weight/mass percentage composition of sulphur is 50.3 in the lithium sulfur battery anode material
~79.8%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710242972.5A CN106876685B (en) | 2017-04-12 | 2017-04-12 | A kind of preparation method of lithium sulfur battery anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710242972.5A CN106876685B (en) | 2017-04-12 | 2017-04-12 | A kind of preparation method of lithium sulfur battery anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106876685A true CN106876685A (en) | 2017-06-20 |
| CN106876685B CN106876685B (en) | 2019-05-14 |
Family
ID=59163045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710242972.5A Active CN106876685B (en) | 2017-04-12 | 2017-04-12 | A kind of preparation method of lithium sulfur battery anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106876685B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732203A (en) * | 2017-10-16 | 2018-02-23 | 河源广工大协同创新研究院 | A kind of preparation method of nano ceric oxide/graphene/sulphur composite |
| CN107732202A (en) * | 2017-10-16 | 2018-02-23 | 河源广工大协同创新研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN107742707A (en) * | 2017-10-16 | 2018-02-27 | 河源广工大协同创新研究院 | A kind of preparation method of nano lanthanum oxide/graphene/sulphur composite |
| CN108172795A (en) * | 2017-12-27 | 2018-06-15 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN109103439A (en) * | 2018-08-30 | 2018-12-28 | 广东工业大学 | A kind of flexible self-supporting lithium sulfur battery anode material, preparation method and its battery |
| CN111740109A (en) * | 2020-06-22 | 2020-10-02 | 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 |
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 |
-
2017
- 2017-04-12 CN CN201710242972.5A patent/CN106876685B/en active Active
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 |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732203A (en) * | 2017-10-16 | 2018-02-23 | 河源广工大协同创新研究院 | A kind of preparation method of nano ceric oxide/graphene/sulphur composite |
| CN107732202A (en) * | 2017-10-16 | 2018-02-23 | 河源广工大协同创新研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN107742707A (en) * | 2017-10-16 | 2018-02-27 | 河源广工大协同创新研究院 | A kind of preparation method of nano lanthanum oxide/graphene/sulphur composite |
| 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 |
| CN108172795A (en) * | 2017-12-27 | 2018-06-15 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium sulfur battery anode 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 |
| CN109103439A (en) * | 2018-08-30 | 2018-12-28 | 广东工业大学 | A kind of flexible self-supporting lithium sulfur battery anode material, preparation method and its battery |
| 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 |
| CN111740109A (en) * | 2020-06-22 | 2020-10-02 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106876685B (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106876685B (en) | A kind of preparation method of lithium sulfur battery anode material | |
| CN103682274B (en) | A kind of graphene/polyaniline/sulphur composite and preparation method thereof | |
| CN104617281B (en) | Method for preparing sodium-ion battery antimony/nitrogen-doped carbon nanosheet negative electrode composite material | |
| CN106784671B (en) | A kind of preparation method of anode material for lithium-ion batteries | |
| CN103199258B (en) | Anode material for lithium-ion batteries, anode preparation method and lithium ion battery | |
| Wu et al. | Fabrication of F-doped, C-coated NiCo2O4 nanocomposites and its electrochemical performances for lithium-ion batteries | |
| Qiu et al. | Biomass-derived, 3D interconnected N-doped carbon foam as a host matrix for Li/Na/K-selenium batteries | |
| CN105006551B (en) | A kind of sodium-ion battery phosphorization tin/Graphene anode material and preparation method thereof | |
| CN104600247B (en) | Sulfur-carbon composite positive electrode material for lithium-sulfur battery and preparation method of sulfur-carbon composite positive electrode material | |
| Wu et al. | Free-standing 3D network-like cathode based on biomass-derived N-doped carbon/graphene/g-C3N4 hybrid ultrathin sheets as sulfur host for high-rate Li-S battery | |
| CN108172795B (en) | Preparation method of lithium-sulfur battery positive electrode material | |
| CN105789584A (en) | Cobalt selenide/carbon sodium ion battery composite negative electrode material as well as preparation method and application of cobalt selenide/carbon-sodium ion battery composite negative electrode material | |
| CN103165869B (en) | Modification mesophase spherule negative material, lithium rechargeable battery and preparation method and application | |
| CN106299270A (en) | Three-dimensional grapheme network structure carrying tin oxide nano-particle and the preparation and application of molybdenum disulfide nano sheet material | |
| CN105826523A (en) | Lithium-sulfur battery positive pole material and preparation method thereof | |
| CN109671935B (en) | Preparation method and application of silicon dioxide/biochar composite material | |
| CN103311541A (en) | Composite cathode material for lithium ion batteries and preparation method thereof | |
| CN110120504A (en) | A kind of phosphorus/tin/carbon compound cathode materials preparation method of richness phosphorus | |
| CN101841039A (en) | Cathode material ferric phosphate doped with metallic ions for lithium ion battery and preparation method thereof | |
| CN113659139A (en) | Vanadium sodium phosphate electrode material of vanadium-position copper-doped composite carbon nanotube and preparation method and application thereof | |
| CN110336048A (en) | A kind of low-load amount ruthenium cladding ZIF-67 derivative and preparation method thereof and the application in lithium-air battery | |
| CN104868118A (en) | Preparation method of sodium ion battery anode FePO4/Graphene composite | |
| CN106992295A (en) | A kind of preparation method of single dispersing α ferric oxide nano pieces | |
| Zhang et al. | Applications of nanocarbons in redox flow batteries | |
| CN105810916B (en) | A kind of SnO2/ graphene/SnO2The preparation method of lithium ion battery negative material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |