CN106450197A - Graphene/oxide based electrode material and lithium-sulfur battery comprising electrode material - Google Patents
Graphene/oxide based electrode material and lithium-sulfur battery comprising electrode material Download PDFInfo
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Abstract
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a graphene/oxide based electrode material. The electrode material comprises a compound formed by nano-Fe2O3 and a graphene porous macrostructure, and nano-sulfur loaded on the compound. Compared with the prior art, a graphene carbonaceous conductive substrate and an elementary substance of sulfur in the nano-Fe2O3/graphene porous macrostructure interact to a certain degree, importantly, a Fe2O3 nano-particle forms a strong chemical bond with sulfur and multi-sulfur, the dissolution of multi-sulfur is effectively limited, the shuttling effect is reduced, a proper amount of the Fe2O3 nano-particle also improves the activity of reaction kinetics, and the utilization ratio of an active substance is improved, so that the specific capacity and the high-rate cycling stability of a lithium-sulfur battery are improved.
Description
Technical field
The invention belongs to lithium-sulfur cell technical field, particularly relate to a kind of electrode material based on graphene/oxide and
Comprise the lithium-sulfur cell of this electrode material.
Background technology
Lithium-sulfur cell, because there is the problems such as effect of shuttling back and forth of sulphur poorly conductive and Volume Changes, polysulfide, have impact on it
Actual application.Additionally, how to improve lithium-sulfur cell specific capacity and cyclicity, it is still necessary to carry out deeper into research.And carbonaceous
Material has the advantage such as regulatable specific surface area and abundant pore structure, good electric conductivity, easy processing because of it, may be used for
Lithium-sulfur cell solves its problem existing.Wherein, Graphene have that excellent electric conductivity, specific surface area be big, chemical stability with
Strong, the unique two-dimentional porous network geometry of mechanical performance, can realize the advantages such as core shell structure cladding simplely, profit
With the modified lithium-sulphur cell positive electrode of Graphene, electronics in lithium-sulfur cell can be shortened and, with from sub transmission path, improve the electricity of elemental sulfur
Chemism, limits the diffusion of polysulfide, improves the performance of lithium-sulfur cell.
But, Graphene is as apolar substance, more weak to the adsorption capacity of polarity polysulfide, and the metal oxygen of polarity
Compound such as TiO2、MnO2Deng having very strong adsorption capacity to polysulfide, but these metal oxides are non-conductive, therefore use
Graphene and the composite of metal oxide are a kind of ideal choses as the electrode material of lithium-sulfur cell.
But, the TiO of report at present2、MnO2Deng these, all to there are some for metal oxides of lithium-sulfur cell respective
Problem, such as：Preparation technology is comparatively laborious, product structure is difficult to control to, high in cost of production.
In view of this, select a kind of low cost, simple synthetic method easy-regulating, sulphur and polysulfide are had very by force mutually
The oxide of active force, preparation is that we need to pay attention to based on the graphene-based composite of this oxide, and is derived from
A kind of lithium-sulfur cell with height ratio capacity and long circulating stability.
Therefore, it is desirable to provide a kind of electrode material based on graphene/oxide and comprise this electrode material
Lithium-sulfur cell, this electrode material can weaken the problems such as effect of shuttling back and forth of polysulfide, promote the conversion of many sulphur, use this electrode
The lithium-sulfur cell of material has high specific capacity and long cyclical stability.
Content of the invention
An object of the present invention is：For the deficiencies in the prior art, and provide a kind of based on graphene/oxide
Electrode material and the lithium-sulfur cell comprising this electrode material, the effect etc. of shuttling back and forth that this electrode material can weaken polysulfide is asked
Topic, promotes the conversion of many sulphur, uses the lithium-sulfur cell of this electrode material to have high specific capacity and long cyclical stability.
A kind of electrode material based on graphene/oxide, described electrode material includes by nanometer Fe2O3Many with Graphene
The compound that hole macroscopic body is formed and the nano-sulfur being carried on described compound, its preparation method comprises the following steps：
S1, adds FeCl under agitation in the graphene oxide hydrosol3The aqueous solution, continues stirring 1h-3h, mixing
Obtaining homodisperse mixed liquor after Jun Yun, then adding ammoniacal liquor in mixed liquor, regulation pH is 9-11, obtains mixed solution
M1；
S2, in the mixed solution M1 obtaining hydrazine hydrate solution instillation S1 under agitation so that hydrazine hydrate and oxidation
The mass ratio of Graphene is (5-9)：10, after dropping finishes, continue stirring 0.5h-3h, obtain mixed solution M2；Dropping continues
Time is 1h-3h；
S3, the mixed solution M2 obtaining S2 are placed in hydrothermal reaction kettle, in the resistance furnace that temperature is 130 DEG C-190 DEG C
Constant temperature 3h-10h, reaction cools down after completing, and removes aqueous phase and obtains the graphene-based hydrogel of columnar three-dimensional, is received after desolvation
Rice Fe2O3/ Graphene porous macroscopic (Fe-PGM)；Wherein, the method for desolvation includes being lyophilized, dries and drying etc..
S4, the nanometer Fe that S3 is obtained2O3/ Graphene porous macroscopic and nano-sulfur powder are according to (1-3)：The mass ratio of 3 enters
Row is sufficiently mixed, and is placed in hot melt under the argon gas atmosphere of 130 DEG C-180 DEG C and processes 9h-15h, obtains electrode material (Fe-PGM-S).
In the method, hydrazine hydrate is as reducing agent, and graphene oxide can effectively be reduced into Graphene, general feelings
Under condition, in order to obtain best reduction effect, reduction temperature is arranged on 70～100 DEG C, but temperature is more than 130 DEG C here, because of
This hydrazine hydrate, in addition to reduction, at high temperature also can promote graphene sheet layer closely to overlap in water-heat process, is formed
The three-dimensional net structure more compacting.And the sulphur simple substance that the three-dimensional net structure compacting is follow-up hot melt state provides effective storage
Deposit space so that sulphur simple substance can be evenly distributed on nanometer Fe2O3In/Graphene porous macroscopic (Fe-PGM), and provide abundant
Ion, electron propagation ducts.
In the present invention, nanometer Fe2O3/ Graphene porous macroscopic (Fe-PGM) is the compound using one-step method to obtain, phase
Ratio is for the product being distributed to obtain in graphene dispersing solution by nano-metal-oxide, by the compound of one-step synthesis method,
On the one hand oxide crystalline structure therein and size can be regulated and controled by synthesis condition, can obtain according to different demands
Obtain corresponding oxide；On the other hand, when using one-step method, Fe3+First adsorb on graphene oxide, by hydro-thermal process
After, the Fe on lamella3+It is transformed into Fe2O3Nano particle, Fe2O3Compound more stable and uniform in Graphene.
And the present invention uses fusion method sulfur-loaded, add graphene/nanometer gold compared to by nano-sulfur, surfactant
Being incubated in genus oxide mixed dispersion liquid again, quickly cooling down the product obtaining, the fusion method sulfur-loaded of the present invention does not has surface to live
Property agent, i.e. do not introduce other materials, it is to avoid pollute, additionally the surface to Graphene and oxide for the surfactant has one
Fixed impact, this may produce impact to the chemical property of follow-up lithium-sulfur cell, and the present invention is simple to operate.
The oxide using in the present invention is Fe2O3, it has easily preparation in situ, low cost, nontoxic advantage, in addition
Fe2O3It is also a kind of good catalyst, in the reaction can the carrying out of effective catalytic reaction.
Improving based on a kind of of the electrode material of graphene/oxide as the present invention, nano-sulfur accounts for the total of electrode material
The 5wt.%-85wt.% of quality, nanometer Fe2O3Account for the 1wt.%-35wt.% of the gross mass of electrode material.
Improve based on a kind of of the electrode material of graphene/oxide as the present invention, the specific surface area of described compound
For 200m2/ g～1000m2/g.
Improve based on a kind of of the electrode material of graphene/oxide as the present invention, the described graphene oxide hydrosol
Preparation method be：Weigh graphite oxide powder, add in deionized water, ultrasonic 1h-3h, i.e. can get homodisperse oxidation
The Graphene hydrosol.
Improve based on a kind of of the electrode material of graphene/oxide as the present invention, the described graphene oxide hydrosol
Concentration be 0.5mg/mL-5mg/mL.
Improve based on a kind of of the electrode material of graphene/oxide as the present invention, described FeCl3The concentration of the aqueous solution
For 5mg/mL-15mg/mL.
Improve based on a kind of of the electrode material of graphene/oxide as the present invention, the concentration of described hydrazine hydrate solution
For 60mg/mL-100mg/mL.
Improving based on a kind of of the electrode material of graphene/oxide as the present invention, in S4, the particle diameter of nano-sulfur powder is
10nm-500nm.
Relative to prior art, the present invention uses the method for hydro-thermal process-hydrazine hydrate reduction to synthesize to have abundant hole
Nanometer Fe with high specific surface area2O3/ Graphene porous macroscopic (Fe-PGM), after using fusion method sulfur loaded, prepares nanometer
Fe2O3/ graphene-sulfur hybrid material (Fe-PGM-S).Nanometer Fe2O3Graphene carbonaceous conduction in/Graphene porous macroscopic
There is certain interaction in matrix and sulphur simple substance, it is important that Fe2O3Nano particle forms strong chemical bond with sulphur and many sulphur,
The dissolving of many sulphur be can effectively limit, effect of shuttling back and forth, appropriate Fe reduced2O3Nano particle can also improve kinetics and live
Property, improve the utilization rate of active material, thus improve specific capacity and the high rate cyclic stability of lithium-sulfur cell.
A kind of lithium-sulfur cell of offer is provided, including positive pole, negative pole, barrier film and electrolyte, institute
Stating positive pole to include plus plate current-collecting body and participate in the positive electrode active materials of electrochemical reaction, described positive electrode active materials is institute of the present invention
The electrode material stated.
Wherein, negative pole includes negative current collector and participates in the negative active core-shell material of electrochemical reaction, described negative electrode active material
Material is at least one in lithium, lithium alloy, lithium carbon and silica-base material.
Relative to prior art, the lithium-sulfur cell of the present invention has high specific capacity and long cyclical stability.Put into practice table
Bright：With the Fe-PGM-S of the present invention as positive pole, lithium piece is negative pole, and when being assembled into lithium-sulfur cell, this battery fills under 0.3C multiplying power
During electric discharge, discharge capacity can reach 1571.2mAh/g first, and the cyclical stability under high magnification is high, i.e. at 2C times
Under rate, initial discharge capacity, up to 697.5mAh/g, remains within 360.5mAh/g through 500 weeks circulation later stage capacity, often
The capacitance loss rate in week is only 0.080%；Under 5C multiplying power, discharge capacity is up to 613.9mAh/g first, follows through 1000 circles
Ring capacity is 309.3mAh/g, and the capacitance loss often enclosing is only 0.049%.
Brief description
Fig. 1 is the forming process schematic diagram of electrode material in the present invention.
Fig. 2 a and Fig. 2 b is the nanometer Fe of embodiment 1 preparation2O3The SEM figure of/Graphene porous macroscopic (Fe-PGM)；
Fig. 2 c and Fig. 2 d is the nanometer Fe of embodiment 1 preparation2O3The SEM figure of/graphene-sulfur hybrid material (Fe-PGM-S)；
Fig. 3 a is that the lithium-sulfur cell of comparative example 3 (prepared by the electrode material using comparative example 1) is at 0.3C, 0.5C, 1C, 2C
With the charging and discharging curve under 5C multiplying power, Fig. 3 b is that embodiment 2 (prepared by the electrode material using embodiment 1) lithium-sulfur cell exists
Charging and discharging curve under 0.3C, 0.5C, 1C, 2C and 5C multiplying power；
Fig. 4 is cycle performance curve under 2C and 5C multiplying power for the lithium-sulfur cell of embodiment 2 and comparative example 3, wherein, Fig. 4 a
For the lithium-sulfur cell of embodiment 2 and the comparative example 3 cycle performance curve under 2C multiplying power, Fig. 4 b is embodiment 2 and comparative example 3
Cycle performance curve under 5C multiplying power for the lithium-sulfur cell.
Detailed description of the invention
Below in conjunction with the accompanying drawings and detailed description of the invention, the present invention and Advantageous Effects thereof are described in detail, but,
The detailed description of the invention of the present invention is not limited to this.
Embodiment 1
Present embodiments providing a kind of electrode material based on graphene/oxide, described electrode material includes by nanometer
Fe2O3The compound being formed with Graphene porous macroscopic and the nano-sulfur being carried on described compound, wherein, nano-sulfur accounts for electricity
The 60wt.% of the gross mass of pole material, nanometer Fe2O3Account for the 15wt.% of the gross mass of electrode material, the specific surface area of compound
For 800m2/g.
Its preparation method comprises the following steps：
S1, adds the FeCl of 10mg/mL under agitation in the graphene oxide hydrosol that concentration is 2mg/mL3Water
Solution, continues stirring 2h, obtains homodisperse mixed liquor after mixing, and (quality is divided then to add ammoniacal liquor in mixed liquor
Number is 28%), regulation pH is 10, obtains mixed solution M1；
Wherein, the preparation method of the graphene oxide hydrosol is：Weigh graphite oxide powder, add in deionized water, super
Sound 2h, i.e. can get the homodisperse graphene oxide hydrosol.
The hydrazine hydrate solution of 80mg/mL is slowly dropped in the mixed solution M1 that S1 obtains by S2 under agitation so that
Hydrazine hydrate is 7 with the mass ratio of graphene oxide：10, after dropping finishes, continue stirring 2h, obtain mixed solution M2；
S3, the mixed solution M2 obtaining S2 are placed in hydrothermal reaction kettle, constant temperature in the resistance furnace that temperature is 180 DEG C
6h, reaction cools down after completing, and opens inner bag removal aqueous phase and obtains the graphene-based hydrogel of columnar three-dimensional, by columnar three-dimensional Graphene
After based aquagel takes out, more lyophilized obtain nanometer Fe2O3/ Graphene porous macroscopic (Fe-PGM), its SEM schemes such as Fig. 2 a and 2b
Shown in.
S4, the nanometer Fe that S3 is obtained2O3/ Graphene porous macroscopic and particle diameter be 10nm-500nm nano-sulfur powder by
According to 2：The mass ratio of 3 is sufficiently mixed, and is placed in hot melt under the argon gas atmosphere of 155 DEG C and processes 12h, obtains electrode material (Fe-
PGM-S), its SEM schemes as illustrated in figures 2 c and 2d.
The forming process of Fe-PGM and Fe-PGM-S is as it is shown in figure 1, by FeCl3The aqueous solution, ammoniacal liquor and hydrazine hydrate add stone
After in the ink alkene hydrosol, then through hydro-thermal reaction, the graphene-based hydrogel of columnar three-dimensional can be obtained, then must after lyophilized
To nanometer Fe2O3/ Graphene porous macroscopic (Fe-PGM), then after sulphur powder is loaded into Fe-PGM by fusion method, i.e. obtain electricity
Pole material (Fe-PGM-S).
Embodiment 2
Present embodiments providing a kind of electrode material based on graphene/oxide, described electrode material includes by nanometer
Fe2O3The compound being formed with Graphene porous macroscopic and the nano-sulfur being carried on described compound, wherein, nano-sulfur accounts for electricity
The 50wt.% of the gross mass of pole material, nanometer Fe2O3Account for the 20wt.% of the gross mass of electrode material, the specific surface area of compound
For 500m2/g.
Its preparation method comprises the following steps：
S1, adds the FeCl of 8mg/mL under agitation in the graphene oxide hydrosol that concentration is 3mg/mL3Water
Solution, continues stirring 1h, obtains homodisperse mixed liquor after mixing, and (quality is divided then to add ammoniacal liquor in mixed liquor
Number is 28%), regulation pH is 9.5, obtains mixed solution M1；
Wherein, the preparation method of the graphene oxide hydrosol is：Weigh graphite oxide powder, add in deionized water, super
Sound 1.5h, i.e. can get the homodisperse graphene oxide hydrosol.
The hydrazine hydrate solution of 70mg/mL is slowly dropped in the mixed solution M1 that S1 obtains by S2 under agitation so that
Hydrazine hydrate is 8 with the mass ratio of graphene oxide：10, after dropping finishes, continue stirring 1h, obtain mixed solution M2；
S3, the mixed solution M2 obtaining S2 are placed in hydrothermal reaction kettle, constant temperature in the resistance furnace that temperature is 160 DEG C
8h, reaction cools down after completing, and opens inner bag removal aqueous phase and obtains the graphene-based hydrogel of columnar three-dimensional, by columnar three-dimensional Graphene
After based aquagel takes out, more lyophilized obtain nanometer Fe2O3/ Graphene porous macroscopic (Fe-PGM).
S4, the nanometer Fe that S3 is obtained2O3/ Graphene porous macroscopic and particle diameter be 10nm-500nm nano-sulfur powder by
According to 1：The mass ratio of 2 is sufficiently mixed, and is placed in hot melt under the argon gas atmosphere of 170 DEG C and processes 10h, obtains electrode material (Fe-
PGM-S).
Embodiment 3
Present embodiments providing a kind of electrode material based on graphene/oxide, described electrode material includes by nanometer
Fe2O3The compound being formed with Graphene porous macroscopic and the nano-sulfur being carried on described compound, wherein, nano-sulfur accounts for electricity
The 40wt.% of the gross mass of pole material, nanometer Fe2O3Account for the 12wt.% of the gross mass of electrode material, the specific surface area of compound
For 700m2/g.
Its preparation method comprises the following steps：
S1, adds the FeCl of 12mg/mL under agitation in the graphene oxide hydrosol that concentration is 4mg/mL3Water
Solution, continues stirring 3h, obtains homodisperse mixed liquor after mixing, and (quality is divided then to add ammoniacal liquor in mixed liquor
Number is 28%), regulation pH is 10.5, obtains mixed solution M1；
Wherein, the preparation method of the graphene oxide hydrosol is：Weigh graphite oxide powder, add in deionized water, super
Sound 2.5h, i.e. can get the homodisperse graphene oxide hydrosol.
The hydrazine hydrate solution of 90mg/mL is slowly dropped in the mixed solution M1 that S1 obtains by S2 under agitation so that
Hydrazine hydrate is 6 with the mass ratio of graphene oxide：10, after dropping finishes, continue stirring 2.5h, obtain mixed solution M2；
S3, the mixed solution M2 obtaining S2 are placed in hydrothermal reaction kettle, constant temperature in the resistance furnace that temperature is 145 DEG C
10h, reaction cools down after completing, and opens inner bag removal aqueous phase and obtains the graphene-based hydrogel of columnar three-dimensional, by columnar three-dimensional graphite
After thiazolinyl hydrogel takes out, then dry and obtain nanometer Fe2O3/ Graphene porous macroscopic (Fe-PGM).
S4, the nanometer Fe that S3 is obtained2O3/ Graphene porous macroscopic and particle diameter be 10nm-500nm nano-sulfur powder by
According to 1：The mass ratio of 3 is sufficiently mixed, and is placed in hot melt under the argon gas atmosphere of 140 DEG C and processes 15h, obtains electrode material (Fe-
PGM-S).
Embodiment 4
Present embodiments providing a kind of electrode material based on graphene/oxide, described electrode material includes by nanometer
Fe2O3The compound being formed with Graphene porous macroscopic and the nano-sulfur being carried on described compound, wherein, nano-sulfur accounts for electricity
The 70wt.% of the gross mass of pole material, nanometer Fe2O3Accounting for the 5wt.% of the gross mass of electrode material, the specific surface area of compound is
400m2/g.
Its preparation method comprises the following steps：
S1, adds the FeCl of 7mg/mL under agitation in the graphene oxide hydrosol that concentration is 1.5mg/mL3
The aqueous solution, continues stirring 2h, obtains homodisperse mixed liquor, then add ammoniacal liquor (quality in mixed liquor after mixing
Fraction is 28%), regulation pH is 10, obtains mixed solution M1；
Wherein, the preparation method of the graphene oxide hydrosol is：Weigh graphite oxide powder, add in deionized water, super
Sound 2h, i.e. can get the homodisperse graphene oxide hydrosol.
The hydrazine hydrate solution of 90mg/mL is slowly dropped in the mixed solution M1 that S1 obtains by S2 under agitation so that
Hydrazine hydrate is 9 with the mass ratio of graphene oxide：10, after dropping finishes, continue stirring 1h, obtain mixed solution M2；
S3, the mixed solution M2 obtaining S2 are placed in hydrothermal reaction kettle, constant temperature in the resistance furnace that temperature is 175 DEG C
4h, reaction cools down after completing, and opens inner bag removal aqueous phase and obtains the graphene-based hydrogel of columnar three-dimensional, by columnar three-dimensional Graphene
After based aquagel takes out, more lyophilized obtain nanometer Fe2O3/ Graphene porous macroscopic (Fe-PGM).
S4, the nanometer Fe that S3 is obtained2O3/ Graphene porous macroscopic and particle diameter be 10nm-500nm nano-sulfur powder by
According to 2.5：The mass ratio of 3 is sufficiently mixed, and is placed in hot melt under the argon gas atmosphere of 165 DEG C and processes 14h, obtains electrode material (Fe-
PGM-S).
Embodiment 5
Present embodiments providing a kind of electrode material based on graphene/oxide, described electrode material includes by nanometer
Fe2O3The compound being formed with Graphene porous macroscopic and the nano-sulfur being carried on described compound, wherein, nano-sulfur accounts for electricity
The 55wt.% of the gross mass of pole material, nanometer Fe2O3Account for the 25wt.% of the gross mass of electrode material, the specific surface area of compound
For 900m2/g.
Its preparation method comprises the following steps：
S1, adds the FeCl of 11mg/mL under agitation in the graphene oxide hydrosol that concentration is 3.5mg/mL3
The aqueous solution, continues stirring 2.5h, obtains homodisperse mixed liquor, then add ammoniacal liquor (matter in mixed liquor after mixing
Amount fraction is 28%), regulation pH is 10, obtains mixed solution M1；
Wherein, the preparation method of the graphene oxide hydrosol is：Weigh graphite oxide powder, add in deionized water, super
Sound 2.5h, i.e. can get the homodisperse graphene oxide hydrosol.
The hydrazine hydrate solution of 75mg/mL is slowly dropped in the mixed solution M1 that S1 obtains by S2 under agitation so that
Hydrazine hydrate is 7.5 with the mass ratio of graphene oxide：10, after dropping finishes, continue stirring 1.5h, obtain mixed solution M2；
S3, the mixed solution M2 obtaining S2 are placed in hydrothermal reaction kettle, constant temperature in the resistance furnace that temperature is 185 DEG C
5h, reaction cools down after completing, and opens inner bag removal aqueous phase and obtains the graphene-based hydrogel of columnar three-dimensional, by columnar three-dimensional Graphene
After based aquagel takes out, then drying obtains nanometer Fe2O3/ Graphene porous macroscopic (Fe-PGM).
S4, the nanometer Fe that S3 is obtained2O3/ Graphene porous macroscopic and particle diameter be 10nm-500nm nano-sulfur powder by
According to 1.2：The mass ratio of 3 is sufficiently mixed, and is placed in hot melt under the argon gas atmosphere of 145 DEG C and processes 11h, obtains electrode material (Fe-
PGM-S).
Comparative example 1
This comparative example provides a kind of electrode material based on Graphene, and described electrode material includes Graphene porous macroscopic view
Body and the nano-sulfur being carried on described Graphene porous macroscopic.
Its preparation method comprises the following steps：
The hydrazine hydrate solution of 80mg/mL is slowly dropped into the graphene oxide that concentration is 1mg/mL by S1 under agitation
In the hydrosol so that hydrazine hydrate is 7 with the mass ratio of graphene oxide：10, after dropping finishes, continue stirring 2h, to mixing
Adding ammoniacal liquor (mass fraction is 28%) in liquid, regulation pH is 10, obtains mixed solution；
S2, the mixed solution obtaining S1 is placed in hydrothermal reaction kettle, constant temperature 6h in the resistance furnace that temperature is 180 DEG C,
Reaction cools down after completing, and opens inner bag removal aqueous phase and obtains the graphene-based hydrogel of columnar three-dimensional, and columnar three-dimensional is graphene-based
After hydrogel takes out, more lyophilized obtain Graphene porous macroscopic.
S3, the black alkene porous macroscopic obtaining S2 and particle diameter are that the nano-sulfur powder of 10nm-500nm is according to 2：The quality of 3
Ratio is sufficiently mixed, and is placed in hot melt under the argon gas atmosphere of 155 DEG C and processes 12h, obtains electrode material (PGM-S).
Comparative example 2
As different from Example 1：In S3, the temperature of hydro-thermal reaction is 80 DEG C, and the specific surface area of compound is 100m2/g.
Embodiment 6
Present embodiments providing a kind of lithium-sulfur cell, including positive pole, negative pole, barrier film and electrolyte, described positive pole just includes
Pole collector and the positive electrode active materials participating in electrochemical reaction, described positive electrode active materials is the electrode material of embodiment 1.Tool
Body, using the Fe-PGM-S of embodiment 1 as the positive electrode active materials of lithium-sulfur cell, lithium metal as negative pole, PP (polypropylene
Film) it is barrier film and 1M LiTFSI (DOL:DMC(1:1), 0.5wt.%LiNO3) it is electrolyte, it is assembled into 2032 type buttons half
Battery, carries out electrochemical property test with the PGM-S of comparative example 1 (comparative example 3) as a comparison, studies metal oxide to material
The impact of material chemical property, voltage range is 1.7～2.8V.
This battery carries out under 0.3C, 0.5C, 1C, 2C and 5C charge-discharge test, and Fig. 3 is corresponding charging and discharging curve.
Under the discharge-rate of 0.3C, the discharge capacity first of Fe-PGM-S positive pole is 1571.2mAh/g, has and well discharges first
Capacity, higher than the 1190.8mAh/g of PGM-S.As discharge-rate improves to 0.5C, 1C, 2C and 5C, putting of Fe-PGM-S positive pole
Capacitance is above the corresponding discharge capacity of PGM-S and Fe-PGM-2-S, and under the high magnification of 5C, its discharge curve still has
Having two obvious platforms, discharge capacity reaches 565.3mAh/g.
Being circulated performance test to the new battery being assembled as above, Fig. 4 is lithium-sulfur cell following under 2C and 5C
Ring stability.Under 2C multiplying power, initial discharge capacity, up to 697.5mAh/g, still maintains through 500 weeks circulation later stage capacity
At 360.5mAh/g, capacitance loss rate weekly is only 0.080%；Under 5C multiplying power, discharge capacity is up to 613.9mAh/ first
G, is 309.3mAh/g through 1000 circle circulation volumes, and the capacitance loss often enclosing is only 0.049%.
As another contrast, using the electrode material of comparative example 2 as positive electrode active materials (comparative example 4), according to above-mentioned
Method is assembled into 2032 type button half-cells, and carries out above-mentioned electrochemical property test, and result shows：Use embodiment 1
The lithium-sulfur cell of electrode material has higher discharge capacity first, more preferable high rate performance and cyclical stability.
Embodiment 7-10
As different from Example 6, the positive electrode active materials of the used in battery of embodiment 7-10 is respectively embodiment enforcement
The Fe-PGM-S of example 2-5, remaining simultaneously embodiment 6, repeat no more here.
This battery is carried out under 0.3C, 0.5C, 1C, 2C and 5C charge-discharge test, tests it under each multiplying power first
Discharge capacity, acquired results is shown in Table 1；
Performance test is circulated to the new battery being assembled as above, calculates after 1000 circle circulation volumes and often enclose
Capacitance loss, acquired results is shown in Table 1.
Table 1：Embodiment 6-10, the charge-discharge test of comparative example 3 and 4 and cycle performance test result.
As can be seen from the above table：The lithium-sulfur cell based on the electrode material of graphene/oxide using the present invention has
High specific capacity and long cyclical stability.
By with comparative example 3, it has been found that：Compared to the graphene-sulfur electrode material of oxide-free, use the present invention
Electrode material there is higher specific capacity and longer cyclical stability；By the comparison with comparative example 4, it has been found that adopt
The setting of the temperature reduced with hydrazine hydrate is also highly important, when temperature is low, uses the lithium-sulfur cell of this electrode material
Specific capacity and cycle performance all poor.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limiting, embodiment of above is only for explaining claims.Right protection scope of the present invention is not limited to specification.Appoint
How those familiar with the art is in the technical scope of present disclosure, the change that can readily occur in or replacement,
It is included within protection scope of the present invention.
Claims (10)
1. the electrode material based on graphene/oxide, it is characterised in that described electrode material includes by nanometer Fe2O3With
The compound that Graphene porous macroscopic is formed and the nano-sulfur being carried on described compound, its preparation method includes following step
Suddenly：
S1, adds FeCl under agitation in the graphene oxide hydrosol3The aqueous solution, continues stirring 1h-3h, mixes
After obtain homodisperse mixed liquor, in mixed liquor, then add ammoniacal liquor, regulation pH is 9-11, obtains mixed solution M1；
S2, in the mixed solution M1 obtaining hydrazine hydrate solution instillation S1 under agitation so that hydrazine hydrate and graphite oxide
The mass ratio of alkene is (5-9)：10, after dropping finishes, continue stirring 0.5h-3h, obtain mixed solution M2；
S3, the mixed solution M2 obtaining S2 are placed in hydrothermal reaction kettle, constant temperature in the resistance furnace that temperature is 130 DEG C-190 DEG C
3h-10h, reaction cools down after completing, and removes aqueous phase and obtains the graphene-based hydrogel of columnar three-dimensional, obtains nanometer after desolvation
Fe2O3/ Graphene porous macroscopic；
S4, the nanometer Fe that S3 is obtained2O3/ Graphene porous macroscopic and nano-sulfur powder are according to (1-3)：The mass ratio of 3 fills
Divide mixing, be placed in hot melt under the argon gas atmosphere of 130 DEG C-180 DEG C and process 9h-15h, obtain electrode material.
2. the electrode material based on graphene/oxide according to claim 1, it is characterised in that：Nano-sulfur accounts for electrode
The 5wt.%-85wt.% of the gross mass of material, nanometer Fe2O3Account for the 1wt.%-35wt.% of the gross mass of electrode material.
3. the electrode material based on graphene/oxide according to claim 1, it is characterised in that：Described compound
Specific surface area is 200m2/ g～1000m2/g.
4. the electrode material based on graphene/oxide according to claim 1, it is characterised in that：Described graphite oxide
The preparation method of the alkene hydrosol is：Weigh graphite oxide powder, add in deionized water, ultrasonic 1h-3h, i.e. can get and uniformly divide
The graphene oxide hydrosol dissipating.
5. the electrode material based on graphene/oxide according to claim 1 or 4, it is characterised in that：Described oxidation stone
The concentration of the ink alkene hydrosol is 0.5mg/mL-5mg/mL.
6. the electrode material based on graphene/oxide according to claim 1, it is characterised in that：Described FeCl3Water-soluble
The concentration of liquid is 5mg/mL-15mg/mL.
7. the electrode material based on graphene/oxide according to claim 1, it is characterised in that：Described hydrazine hydrate is molten
The concentration of liquid is 60mg/mL-100mg/mL.
8. the electrode material based on graphene/oxide according to claim 1, it is characterised in that：Nano-sulfur powder in S4
Particle diameter be 10nm-500nm.
9. a lithium-sulfur cell, including positive pole, negative pole, barrier film and electrolyte, described positive pole includes plus plate current-collecting body and participates in electricity
The positive electrode active materials of chemical reaction, it is characterised in that：Described positive electrode active materials is the electricity described in any one of claim 1-8
Pole material.
10. lithium-sulfur cell according to claim 9, it is characterised in that：Described negative pole includes negative current collector and participates in electricity
The negative active core-shell material of chemical reaction, described negative active core-shell material is at least in lithium, lithium alloy, lithium carbon and silica-base material
Kind.
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| PCT/CN2016/109013 WO2018072275A1 (en) | 2016-10-19 | 2016-12-08 | Graphene/oxide-based electrode material, and lithium-sulfur battery comprising same |
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