CN106654236A - Sulfur-doped three-dimensional porous graphene/sulfur composite positive electrode material and preparation method and application thereof - Google Patents
Sulfur-doped three-dimensional porous graphene/sulfur composite positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a sulfur-doped three-dimensional porous graphene/sulfur composite positive electrode material and a preparation method and an application thereof. The sulfur-doped three-dimensional porous graphene/sulfur composite positive electrode material is composed of elemental sulfur deposited on a surface of a three-dimensional carbon skeleton of sulfur-doped three-dimensional porous graphene in situ; and the preparation method comprises the steps of first adding sodium bisulfate to a graphene oxide dispersion to react, then adding sodium sulfide to react under a partially neutral condition, carrying out liquid-solid separation, and performing freeze-drying on a solid product, thereby obtaining the sulfur-doped three-dimensional porous graphene/sulfur composite positive electrode material. A sulfur-doped amount of the composite positive electrode material is large, a sulfur loading capacity is controllable, a load is uniform and a utilization rate of an active substance sulfur is high; the sulfur-doped three-dimensional porous graphene/sulfur composite positive electrode material has the advantages of high specific capacity, high energy density, high stability and the like; and the cycle performance of a lithium-sulfur battery is greatly improved.
Description
Technical field
The present invention relates to a kind of lithium sulfur battery anode material, the three-dimensional porous Graphene/sulfur of more particularly to a kind of sulfur doping is multiple
Positive electrode and preparation method thereof and application of the composite positive pole in inner galvanic battery are closed, belongs to lithium-sulfur cell field.
Background technology
With lithium ion battery extensively should in portable type electronic product, electric automobile and instant-plugging hybrid electric vehicle
With the battery in the urgent need to developing higher energy density.It is restricted as anode material for lithium-ion batteries specific capacity is improved, lithium
The energy density of ion battery is difficult to further increase considerably.Energy is improved by increasing the voltage platform of positive electrode simultaneously
Density can bring safety issue again.Positive electrode is gone to into " conversion reaction chemism " from " deintercalation mechanism ", it is expected to obtain
The material of height ratio capacity and specific energy.Elemental sulfur is one of most promising positive electrode, and sulfur reacts generation completely with lithium metal
Li2S, cell reaction are S+2Li=Li2S, is bielectron course of reaction, is not related to the deintercalation reaction of lithium ion.Due to dividing for sulfur
Son amount is low, and the theoretical specific capacity of sulfur is up to 1675mAh/g (almost LiFePO410 times), and theoretical specific energy is then up to
2600Wh/Kg.Additionally, elemental sulfur is in nature rich reserves, low toxicity, cheap, therefore elemental sulfur is that one kind has suction very much
The positive electrode of gravitation.
But, sulfur positive electrode also faces some challenges, mainly includes：(1) many lithium sulfides of intermediate product are in the electrolytic solution
Dissolving.In cyclic process, intermediate product long-chain lithium polysulphides (Li2S4To Li2S8) ether electrolyte can be dissolved into easily
In.During this phenomenon will cause electrode, active substance is persistently reduced, and a portion will still be dissolved in electrolysis in electric discharge terminal
Positive electrode surface can not deposit again in liquid.Therefore, this is by guiding discharge capacity low and capacity rapid decay.The dissolving of many lithium sulfides
Still the reason for causing shuttle effect simultaneously, causes a large amount of self discharges, coulombic efficiency and cycle performance to reduce, irreversible appearance occurs
Amount decay.(2) elemental sulfur is low with the electrical conductivity of discharging product lithium sulfide.S electrical conductivity (5 × 10-30S/cm, 25 DEG C), Li2S/
Li2S2Electrical conductivity (～10-30S/cm), the utilization rate of sulfur is caused there was only 50-70% or so.(3) sulfur is produced during physics and chemistry
Enormousness deformation.From orthorhombic system α-S (ρ1=2.03g/cm3) it is converted into the Li of antifluorite structure2S(ρ2=1.66g/cm3),
Volumetric expansion is big, destroys electrode structure, have impact on cyclical stability.
In order to solve these problems of sulfur electrode, at present typically by elemental sulfur load (filling, attachment, mixing, extension life
Long, cladding etc.) in the carbon class material with high-specific surface area, high porosity and excellent conductive performance feature, form compound
Positive electrode, to limit the various negative effects that polysulfide in cyclic process dissolves in electrolyte and thus causes.Wherein, sulfur takes
There is good conductivity, bigger serface for three-dimensional porous Graphene, between them, natural conductive mesh can be barricaded as with bridge
Network, is conducive to electronics conduction and lithium ion diffusion, in addition, element sulphur has to polysulfide during sulfur replaces three-dimensional porous class Graphene
There is stronger chemical adsorptivity, can effectively suppress the migration of polysulfide, while it has larger spatial joint clearance, to stable electricity
Pole structure produces positive meaning, and such as China Patent Publication No. CN201610092807.1 discloses a kind of sulfur doping three dimensional structure
The preparation method of lithium sulfur battery anode material, graphite oxide is added to the water ultrasound, forms graphene oxide suspension；Step
(2) benzene sulfonic acid sodium salt is added in graphene oxide suspension, carries out hydro-thermal reaction, obtain three-dimensional sulfur doping Graphene；Step
(3) taking the three-dimensional sulfur doping Graphene that step (2) obtains and ultrasonic reaction in N-Methyl pyrrolidone being added to Ketjen black formed
Suspension；Elemental sulfur is added to ultrasound in N-Methyl pyrrolidone by step (4), to form suspension until elemental sulfur is completely dissolved
Liquid；Two kinds of suspension mixing that step (4) and step (3) are obtained by step (5), stir, then slow under agitation
Distilled water is added, the lithium sulfur battery anode material of three dimensional structure is obtained.But there is following defect in the method：1. preparation flow is multiple
It is miscellaneous, reaction need to point multistep carry out, 2. its severe reaction conditions, need to react, high energy consumption at high temperature under high pressure, be not suitable for industrial metaplasia
Produce, need to 3. adopt a large amount of organic solvents, pollute environment, the method sulfur loaded for 4. being separated out using elemental sulfur dissolving again, its load capacity
It is difficult to control to, sulfur is easily reunited, it is difficult to obtain nano-sulfur, sulfur distribution is uneven, and 5. which adopts organic sulfonic acid as sulfiding reagent, cost
Height, sulfur doping rate are low.
Therefore, how to shorten preparation flow, improve the substitution amount of sulfur in three-dimensional grapheme, after improvement combination process makes to be combined
Sulfur distribution is more uniform, improves specific energy, high rate performance and the cycle life of lithium-sulfur cell, is to still need at present make great efforts asking for solution
Topic.
The content of the invention
Sulfur doping and load for sulfur doping three-dimensional grapheme of the prior art/sulfur composite positive pole generally existing
Amount is low, and energy density is low, and cycle performance is poor, and the shortcomings of preparation flow is long, it is offer one that first purpose of the invention is
Plant sulfur doping amount big, load capacity is controllable, and Load Balanced, stable sulfur doping three-dimensional porous Graphene/sulfur composite.
Another object of the present invention be provide that a kind of step is simple, flow process is short, reaction condition is gentle, low cost,
The method for preparing the sulfur doping three-dimensional grapheme/sulfur composite positive pole that can be mass-produced.
It is to provide the sulfur doping three-dimensional grapheme/sulfur composite positive pole in lithium sulfur that third object of the present invention is
Application in battery, prepares lithium-sulfur cell as positive electrode, and with height ratio capacity, energy density is high, high stability etc.
Advantage, can substantially improve the cycle performance of lithium-sulfur cell.
In order to realize foregoing invention purpose, the invention provides a kind of three-dimensional porous graphene/sulfur composite positive electrode of sulfur doping
Material, the composite positive pole are deposited on the three-dimensional carbon skeleton surface of the three-dimensional porous Graphene of sulfur doping and are constituted by elemental sulfur.
The three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping of the present invention is with the three-dimensional porous Graphene of sulfur doping as bone
Frame, elemental sulfur in-situ deposition is on the three-dimensional carbon skeleton surface of the three-dimensional porous Graphene of sulfur doping.The three-dimensional porous Graphene of sulfur doping
With the three-dimensional porous carbon structure being mutually communicated so as to higher porosity and bigger specific surface area, considerably increase
The load capacity (weight content reaches 30～90%) of elemental sulfur and with elemental sulfur contact area, improve electron transfer rate and reaction
Area.And the doping of elemental sulfur can be barricaded as natural conductive network with bridge, electronics conduction and lithium ion is conducive to spread.Sulfur doping
The whole three-dimensional porous carbon structure skeleton of three-dimensional porous Graphene, maintains material with carbon element ion transport capability and electric conductivity, is whole
Individual positive pole provides effective conductive network and lithium ion mobility passage.On the three-dimensional carbon skeleton of the three-dimensional porous Graphene of sulfur doping
The pore network for having substantial amounts of nanoscale sulphur simple substance deposition, nanoscale inhibits the dissolving of many lithium sulfides to spread loss.Therefore,
In the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping, sulfur doping not only improves the electrical conductivity of Graphene with deposition, improves
Material high rate performance, and chemical bond is formed between many lithium sulfides, the shuttle to suppressing polysulfide has greatly help, favorably
In the raising of lithium-sulfur cell cyclical stability, the utilization ratio of active substances in cathode materials sulfur is substantially increased, be conducive to lithium sulfur
The raising of circulating battery stability.
Preferred scheme, the quality percentage of element sulphur in the three-dimensional porous graphene/sulfur composite positive electrode material of the sulfur doping
It is 30%～90% than content；Preferably 50～90%；More preferably 70～90%.Three-dimensional porous Graphene/the sulfur of sulfur doping is multiple
The amount for closing sulfur loaded in positive electrode is controllable, and can reach higher load capacity, can reach 90% or so, solves existing
There is low-sulfur content problem in the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping.
More preferably scheme, in the three-dimensional porous Graphene of the sulfur doping, sulfur doping amount atom accounting is 0.2%～8%；
Preferably 3～8%；More preferably 5～8%.In the three-dimensional porous Graphene of sulfur doping, the doping of sulfur is higher, far above existing skill
Level in art.
Present invention also offers a kind of side for preparing the described three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping
Method, the method are, in graphene oxide dispersion, to be initially charged sodium sulfite, are reacted at a temperature of 50 DEG C～100 DEG C, then plus
Enter sodium sulfide, react under the conditions of pH is for 6.5～7.5, solid-liquor separation, solid product are obtained final product through lyophilization.
Technical scheme, it is critical only that the sulfur doping reagent as graphene oxide using sodium sulfite, can
Sulfur is doped to graphene oxide under gentle reaction condition, the three-dimensional porous stone of the higher sulfur doping of sulfur doping amount can be obtained
Black alkene, while sodium sulfite is also as oxidant, can carry out redox reaction with sodium sulfide, generate elemental sulfur, to oxygen
Graphite alkene carries out in-situ deposition sulfur, makes elemental sulfur uniform deposition on the three-dimensional carbon skeleton surface of graphene oxide, and passes through
The method deposit elemental sulfur, with react it is controllable the characteristics of, the load capacity of elemental sulfur can be regulated and controled.The solution of the present invention can be with one
Pot method prepares the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping, and hinge structure enormously simplify processing step, and
Reaction condition is gentle, without the need for the high-temperature and high-pressure conditions of hydro-thermal reaction, meets the requirement of large-scale production.
Preferred scheme, the graphene oxide in graphene oxide dispersion are 1 with the mass ratio of sodium sulfite:2～
1:15。
More preferably scheme, in the graphene oxide dispersion, the concentration of graphene oxide is 2mg/L～10mg/L.
Preferred scheme, the quality of graphene oxide and sodium sulfide 1 in the graphene oxide dispersion:5～10.
Preferred scheme, after adding sodium sulfite, the time reacted at a temperature of 50 DEG C～100 DEG C is 0.5～10 little
When.
Preferred scheme, after adding sodium sulfide, pH be time for reacting under the conditions of 6.5～7.5 be 0.5～10 hour.
Present invention also offers the described application for preparing the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping, will
Which is applied to lithium-sulfur cell.
The three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping of the present invention is used as positive active material and conductive charcoal
Black, Kynoar (PVDF) etc. uniformly mixes, and adds appropriate NMP and makes slurry (solid content is 80wt%), is coated in aluminum
On paper tinsel collector, after vacuum drying, lithium-sulphur cell positive electrode piece is obtained；Lithium sulfur electricity is assembled into negative pole, electrolyte etc. further
Pond.
Hinge structure, the Advantageous Effects that technical scheme is brought：
1st, the three-dimensional porous graphene/sulfur composite positive electrode material sulfur doping amount of sulfur doping of the invention and sulfur load capacity are big and can
Control, and Load Balanced, as can effectively suppress polysulfide dissolving in the electrolytic solution, active matter during lithium sulfur battery anode material
Matter utilization efficiency is high.In overcoming prior art, the three-dimensional porous graphene/sulfur composite positive electrode material load sulfur content of sulfur doping is low and negative
Carry uneven shortcoming.
2nd, when the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping of the invention is as lithium sulfur battery anode material,
Active substance utilization efficiency is high, and with height ratio capacity, energy density is high, the advantages of high stability, can substantially improve lithium-sulfur cell
Cycle performance.
3rd, the three-dimensional porous graphene/sulfur composite positive electrode material One-step Synthesis of sulfur doping of the invention, processing step are significantly simple
Change, it is possible to achieve sulfur doping amount and load capacity it is controllable, organic solvent need not be adopted, be conducive to environmental protection, and reaction condition is gentle,
Using raw material sources it is wide, inexpensively, low cost is adapted to industrialized production.
Description of the drawings
【Fig. 1】The sulfur obtained for embodiment 1 replaces the SEM figures of three-dimensional porous graphene/sulfur composite positive electrode material.Can from figure
To find out, sulfur is evenly distributed in whole composite positive pole.
【Fig. 2】The discharge curve first of the class graphene carbon material/sulfur composite positive pole obtained for embodiment 1.
【Fig. 3】The class graphene carbon material/sulfur composite positive pole obtained for embodiment 1 is under 0.5C electric current densities
100 circle cycle performance figures.
【Fig. 4】The discharge curve first of the class graphene carbon material/sulfur composite positive pole obtained for embodiment 2.
【Fig. 5】The class graphene carbon material/sulfur composite positive pole obtained for embodiment 2 is under 0.5C electric current densities
100 circle cycle performance figures.
【Fig. 6】The discharge curve first of the class graphene carbon material/sulfur composite positive pole obtained for embodiment 3.
【Fig. 7】The class graphene carbon material/sulfur composite positive pole obtained for embodiment 3 is under 0.5C electric current densities
100 circle cycle performance figures.
【Fig. 8】The discharge curve first of the class graphene carbon material/sulfur composite positive pole obtained for embodiment 4.
【Fig. 9】The class graphene carbon material/sulfur composite positive pole obtained for embodiment 4 is under 0.5C electric current densities
100 circle cycle performance figures.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but is not limited to the protection domain invented.
Embodiment 1
By 400mL concentration for 2mg/L graphene oxide dispersion ultrasound 2 hours after, stirring add 1.6g bisulfites
Sodium, is warming up to 50 DEG C and is kept for 2 hours, takes out a small amount of reacted solution, after repeatedly washing, by x-ray photoelectron power spectrum
Characterized, as a result shown that the doping atom accounting of sulfur is 0.2%.Add quality be 4g sodium sulfide to after above-mentioned reaction
Solution in, and stir 0.5 hour.By above-mentioned solution sucking filtration and make to be washed with deionized water 3 times, filter cake is transferred to into lyophilization
Drying in machine is obtained the three-dimensional porous Graphene of sulfur doping/sulfur composite for 24 hours, tests to obtain its actual sulfur by thermogravimetric
Content is 35wt.%.The composite positive pole of gained, conductive black, Kynoar (PVDF) are according to 8:1:1 mass ratio is equal
Even mixing, and slurry (solid content is 80wt%) in being dispersed in the NMP of certain mass, is made, it is then coated with aluminum foil current collector
On, obtain a kind of lithium-sulphur cell positive electrode piece after being vacuum dried at 60 DEG C.
Battery assembling test is：Positive plate is struck out into the electrode slice of a diameter of 10mm, with metal lithium sheet as negative pole, electrolysis
Liquid is 1M LiTFSI/DOL:DME(1:1) CR2025 button cells are assembled in the glove box full of argon,.At room temperature
(25 DEG C) carry out constant current charge-discharge test with the electric current density of 0.5C (837mA/g), and discharge and recharge blanking voltage is 1.5～3.0V.
As shown in Figures 2 and 3,1180mAh/g, after 100 circulations, specific capacity keeps 950mAh/g, maintains 80.5% capacity respectively
Conservation rate.
Embodiment 2
By 400mL concentration for 5mg/L graphene oxide dispersion ultrasound 2 hours after, stirring add 4g sodium sulfitees,
It is warming up to 50 DEG C and is kept for 2 hours, takes out a small amount of reacted solution, after repeatedly washing, carried out by x-ray photoelectron power spectrum
Characterize, as a result show that the doping atom accounting of sulfur is 3%.Add quality be 7g sodium sulfide to above-mentioned reacted solution
In, and stir 0.5 hour.By above-mentioned solution sucking filtration and make to be washed with deionized water 3 times, filter cake is transferred in freezer dryer and is done
The three-dimensional porous Graphene of sulfur doping/sulfur composite is obtained within dry 24 hours, by thermogravimetric test its actual sulfur content is
52.1wt.%.The composite positive pole of gained, conductive black, Kynoar (PVDF) are according to 8:1:1 mass ratio is uniformly mixed
Close, and in being dispersed in the NMP of certain mass, make slurry (solid content is 80wt%), be then coated with aluminum foil current collector,
At 60 DEG C be vacuum dried after obtain a kind of lithium-sulphur cell positive electrode piece.
Battery assembling test is：Positive plate is struck out into the electrode slice of a diameter of 10mm, with metal lithium sheet as negative pole, electrolysis
Liquid is 1M LiTFSI/DOL:DME(1:1) CR2025 button cells are assembled in the glove box full of argon,.At room temperature
(25 DEG C) carry out constant current charge-discharge test with the electric current density of 0.5C (837mA/g), and discharge and recharge blanking voltage is 1.5～3.0V.
As shown in Figure 4 and Figure 5,1066mAh/g, after 100 circulations, specific capacity keeps 830mAh/g, maintains 80.95% appearance respectively
Amount conservation rate.
Embodiment 3
By 400mL concentration for 2mg/L graphene oxide dispersion ultrasound 2 hours after, stirring add 6g sodium sulfitees,
It is warming up to 50 DEG C and is kept for 2 hours, takes out a small amount of reacted solution, after repeatedly washing, carried out by x-ray photoelectron power spectrum
Characterize, as a result show that the doping atom accounting of sulfur is 5%.Add quality be 8g sodium sulfide to above-mentioned reacted solution
In, and stir 0.5 hour.By above-mentioned solution sucking filtration and make to be washed with deionized water 3 times, filter cake is transferred in freezer dryer and is done
The three-dimensional porous Graphene of sulfur doping/sulfur composite is obtained within dry 24 hours, by thermogravimetric test its actual sulfur content is
73.2wt.%.The composite positive pole of gained, conductive black, Kynoar (PVDF) are according to 8:1:1 mass ratio is uniformly mixed
Close, and in being dispersed in the NMP of certain mass, make slurry (solid content is 80wt%), be then coated with aluminum foil current collector,
At 60 DEG C be vacuum dried after obtain a kind of lithium-sulphur cell positive electrode piece.
Battery assembling test is：Positive plate is struck out into the electrode slice of a diameter of 10mm, with metal lithium sheet as negative pole, electrolysis
Liquid is 1M LiTFSI/DOL:DME(1:1) CR2025 button cells are assembled in the glove box full of argon,.At room temperature
(25 DEG C) carry out constant current charge-discharge test with the electric current density of 0.5C (837mA/g), and discharge and recharge blanking voltage is 1.5～3.0V.
As shown in Figure 6 and Figure 7,959mAh/g, after 100 circulations, specific capacity keeps 712mAh/g, maintains 74.2% capacity respectively
Conservation rate.
Embodiment 4
By 400mL concentration for 10mg/L graphene oxide dispersion ultrasound 2 hours after, stirring add 40g bisulfites
Sodium, is warming up to 90 DEG C and is kept for 2 hours, takes out a small amount of reacted solution, after repeatedly washing, by x-ray photoelectron power spectrum
Characterized, as a result shown that the doping atom accounting of sulfur is 8%.Add quality be 40g sodium sulfide to after above-mentioned reaction
Solution in, and stir 0.5 hour.By above-mentioned solution sucking filtration and make to be washed with deionized water 3 times, filter cake is transferred to into lyophilization
Drying in machine is obtained the three-dimensional porous Graphene of sulfur doping/sulfur composite for 24 hours, tests to obtain its actual sulfur by thermogravimetric
Content is 90.2wt.%.The composite positive pole of gained, conductive black, Kynoar (PVDF) are according to 8:1:1 mass ratio
It is uniform to mix, and slurry (solid content is 80wt%) in being dispersed in the NMP of certain mass, is made, it is then coated with aluminum foil current collector
On, obtain a kind of lithium-sulphur cell positive electrode piece after being vacuum dried at 60 DEG C.
Battery assembling test is：Positive plate is struck out into the electrode slice of a diameter of 10mm, with metal lithium sheet as negative pole, electrolysis
Liquid is 1M LiTFSI/DOL:DME(1:1) CR2025 button cells are assembled in the glove box full of argon,.At room temperature
(25 DEG C) carry out constant current charge-discharge test with the electric current density of 0.5C (837mA/g), and discharge and recharge blanking voltage is 1.5～3.0V.
As shown in Figure 8 and Figure 9,691mAh/g, after 100 circulations, specific capacity keeps 442mAh/g, maintains 63.8% capacity respectively
Conservation rate.
Claims (10)
1. the three-dimensional porous graphene/sulfur composite positive electrode material of a kind of sulfur doping, it is characterised in that：By elemental sulfur in-situ deposition in sulfur
Adulterate three-dimensional porous Graphene three-dimensional carbon skeleton surface constitute.
2. the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping according to claim 1, it is characterised in that：It is described
In the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping, the mass percentage content of element sulphur is 30%～90%.
3. the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping according to claim 1 and 2, it is characterised in that：Institute
In stating the three-dimensional porous Graphene of sulfur doping, sulfur doping amount atom accounting is 0.2%～8%.
4. the method for preparing the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping described in any one of claims 1 to 3,
It is characterized in that：In graphene oxide dispersion, sodium sulfite is initially charged, is reacted at a temperature of 50 DEG C～100 DEG C, then plus
Enter sodium sulfide, react under the conditions of pH is for 6.5～7.5, solid-liquor separation, solid product are obtained final product through lyophilization.
5. the method for preparing the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping according to claim 4, its feature
It is：Graphene oxide in graphene oxide dispersion is 1 with the mass ratio of sodium sulfite:2～1:15.
6. the method for preparing the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping according to claim 5, its feature
It is：In the graphene oxide dispersion, the concentration of graphene oxide is 2mg/L～10mg/L.
7. the method for preparing the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping according to claim 4, its feature
It is：In the graphene oxide dispersion, graphene oxide and the mass ratio of sodium sulfide are 1:5～10.
8. the method for preparing the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping according to claim 4, its feature
It is：After adding sodium sulfite, the time reacted at a temperature of 50 DEG C～100 DEG C is 0.5～10 hour.
9. the method for preparing the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping according to claim 4, its feature
It is：After adding sodium sulfide, pH be the time reacted under the conditions of 6.5～7.5 be 0.5～10 hour.
10. the application for preparing the three-dimensional porous graphene/sulfur composite positive electrode material of sulfur doping described in any one of claims 1 to 3,
It is characterized in that：It is applied to lithium-sulfur cell.
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| CN107591254A (en) * | 2017-09-08 | 2018-01-16 | 南陵县生产力促进中心 | A kind of ultracapacitor graphene/Na2S composite nano materials and preparation method thereof |
| CN109950479A (en) * | 2017-12-21 | 2019-06-28 | 中国科学院上海硅酸盐研究所 | A kind of three-dimensional porous structure graphene/sulfur composite positive electrode material and preparation method thereof |
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| CN109671934A (en) * | 2018-12-18 | 2019-04-23 | 清远佳致新材料研究院有限公司 | The preparation method of energy storage device cathode, energy storage device cathode, energy storage device, energy-storage system, electrical equipment |
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| CN109904388A (en) * | 2019-03-07 | 2019-06-18 | 南京邮电大学 | A kind of preparation method of the flexibility line array containing sulfur electrode |
| CN109904388B (en) * | 2019-03-07 | 2021-11-26 | 南京邮电大学 | Preparation method of flexible linear array sulfur-containing electrode |
| CN110350175A (en) * | 2019-07-11 | 2019-10-18 | 安徽师范大学 | A kind of composite material of the graphene-supported sulphur of porous carbon@, preparation method and applications |
| CN110350175B (en) * | 2019-07-11 | 2022-08-30 | 安徽师范大学 | Porous carbon @ graphene sulfur-loaded composite material, preparation method and application thereof |
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