CN103035893A - Preparation method of lithiumsulphur battery positive pole material - Google Patents
Preparation method of lithiumsulphur battery positive pole material Download PDFInfo
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- CN103035893A CN103035893A CN2012105353053A CN201210535305A CN103035893A CN 103035893 A CN103035893 A CN 103035893A CN 2012105353053 A CN2012105353053 A CN 2012105353053A CN 201210535305 A CN201210535305 A CN 201210535305A CN 103035893 A CN103035893 A CN 103035893A
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Abstract
The invention discloses a preparation method of a lithiumsulphur battery positive pole material. The preparation method comprises the following steps of: adopting a 'graphite olefine and mesoporous metal-organic frame in-situ composition + sulfur liquid phase infiltration' two-step process to prepare a composite positive pole material of a mesoporous metal-organic frame coated by sulfur and graphite olefine, adopting a graphite olefine and mesoporous metal-organic frame in-situ composition method, coating the graphite olefine in the surface and ducts of the layered porous structure of the mesoporous metal-organic frame, and forming an effective electric conduction network; and adopting a liquid phase infiltration method to effectively regulate and control the sizes of sulfur particles and realize sulfureous selectivity distribution so as to obtain the composite positive pole with distribution uniformity, high conductivity, high capacity sulfur content at low temperature. The preparation method can efficiently improve the distribution of sulfur in a composite material, the electrochemistry property of the composite material is optimized, meanwhile, the preparation process is simple, the preparation method is easy to implement on industry and the positive pole material can be produced in volume.
Description
Technical field
The invention belongs to new energy field, relate to a kind of preparation method of lithium sulfur battery anode material.
Background technology
Along with the development of human society, the becoming increasingly conspicuous of the problems such as energy shortage, environmental pollution, people are to the understanding of chemical power source and require also more and more highlyer, and impelling people constantly to explore new chemical power source is main energy storage system.In recent decades, led the developing direction of high-performance chemical power supply as the battery on basis take lithium metal.Along with the successful commercialization of lithium ion battery, countries in the world are all in the research that steps up to carry out vehicle lithium-ion power battery.But because factors such as energy density, fail safe, prices, conventional lithium ion battery such as cobalt acid lithium, LiMn2O4 and ferric phosphate lithium cell can't satisfy the requirement of electric automobile as power source.
Lithium-sulfur cell is the high-energy density secondary battery that has development potentiality and application prospect.It has height ratio capacity (1675mAh/g) and high-energy-density (2600Wh/g).In addition, sulphur as positive active material in the source, the aspect such as cost and environmental friendliness also shows incomparable advantage.
At present, there are the problems such as cycle performance is poor, the further raising of high rate performance needs in lithium-sulfur cell.And active material sulfur materials itself and final discharging product Li in the lithium-sulfur cell
2S is the insulator of electronics and ion, and the intermediate product polysulfide in the discharge process is soluble in electrolyte, and these can cause irreversible loss and the capacity attenuation of active material.For this reason, the conductivity that how to suppress in the diffusion of polysulfide, the distribution of improving sulphur and the anodal cyclic process of raising sulphur is the research emphasis of sulfenyl positive electrode.
Academia mainly spread and improved positive electrode conductivity and conducted a research around the distribution of improving sulphur, inhibition polysulfide in recent years.On material structure, at first consider it is that elemental sulfur is adsorbed on the porous material parent, such as the material with carbon elements such as porous carbon such as active carbon, carbon nano-tube, Graphene and sulphur is compound, prevent that the polysulfide that course of reaction is produced is dissolved in the electrolyte, by the electrolyte diffusion, help like this to reduce shuttle back and forth effect and self-discharge phenomenon.These new material structures have more or less improved the cyclical stability of electrode.But the general specific area of traditional porous carbon materials is less, aperture size is single, structural integrity is poor, the aperture is difficult to regulation and control, the adsorption capacity of material is limited, cause low, the skewness of sulfur content in the composite positive pole of preparation, be assembled into circulating battery after a few, still have a large amount of active materials from the carbon structure duct, to dissolve, cause the loss of active material, the lithium-sulfur cell energy density is difficult to further improve.Simultaneously, the distribution of the pore structure of porous material and sulphur thereof is very large on the battery performance impact.When only have micropore partially filled sulphur, active matter quality content is low in the composite material, thus the specific capacity of composite material is low, causes the energy density of battery lower.When the duct of porous material and outer surface have all distributed the sulphur of a large amount of insulation, the electrical conductivity of composite material and ion transfer ability then can be subject to obvious restriction, simultaneously, a large amount of sulphur are distributed in the outer surface of material with carbon element, the polysulfide that generates behind this part reaction of Salmon-Saxl easily diffusion shuttles back and forth, cause the irreversible loss of active material, the chemical property of material can not get bringing into play preferably.In addition, the preparation technology of sulphur and porous carbon composite positive pole adopts heat treating process usually.Heat treating process is under inert gas carrier gas protection, under certain heat treating regime, is elevated to 150 ~ 600 ° of C, keeps 1 ~ 20 hour, and cooling can get composite positive pole.But this mode is subjected to the factor affecting such as temperature retention time, air-flow velocity, temperature rate, is difficult to control the content of sulphur, simultaneously because the impact of carrier gas, can cause in the raw material sulfur material in a large number with gas overflowing, causes in the raw material utilance of sulphur low.
Metal-organic framework materials is the periodically material of pore network structure that has that self assembly forms by the complexing of the metal-ligand between multiple tooth organic ligand and metal ion.The duct that metal-organic framework materials not only has special topological structure, internal arrangement rule and has specific dimensions and shape, and its duct has controllability, organic ligand by the stereochemical structure selecting to suit and size can the Effective Regulation metal-organic framework pore structure, size and and specific area, a large amount of functional groups are constructed in the surface characteristic in duct and organic composition meeting, because complexity and the diversity of organic ligand and Action of Metal Ions, in structural design and the application facet of material, for people provide unprecedented opportunities.
Yet the conductivity of metal-organic framework materials and this bi-material of sulphur is all not good, therefore, the conductivity of prepared composite material is not good yet, and this will certainly have a negative impact to the chemical property (such as enclosed pasture efficient, polarization and specific capacity) of lithium sulphur positive electrode.Usually, in cell positive material, add the electric conductivity that a certain amount of conductive agent (such as carbon black and acetylene black etc.) can suitably promote material.But since the conductive agent material usually with particle form exist with positive electrode among, can't uniform fold on the surface of active material, and can not form effective conductive network.With the conductivity of Graphene excellence improve the conductivity of material monolithic, the sulphur component utilance that caused with active component sulphur poorly conductive in the positive electrode that solves lithium-sulfur cell is low, polarization is large and battery capacity that dissolving is caused in electrolyte the decays problem such as too fast.
In sum, this area in the urgent need to the lithium-sulfur cell of developing a kind of simple, high-efficient carrier sulphur simple substance with positive electrode and preparation thereof, reduce the loss late of active material sulphur in the composite material preparation process, improve the space availability ratio of loose structure, so that elemental sulfur can be evenly distributed in the pore structure, effectively improve the distribution of sulphur in composite material when guaranteeing composite material high capacity amount, improve the specific capacity of battery material and high active material utilization, then improve the cycle performance of lithium-sulfur cell.
Summary of the invention
The invention provides a kind of simple, easy to operate lithium sulfur battery anode material process of preparing, can so that elemental sulfur can be evenly distributed in the pore structure, effectively improve the distribution of sulphur in composite material when guaranteeing composite material high capacity amount.
Technical scheme of the present invention is:
(1) original position prepares graphene coated mesoporous metal-organic frame composite material: graphene oxide is mixed with the ratio of 0.5 ~ 2mg/mL with deionized water, with supersonic oscillations to forming homogeneous phase solution; Be that the ratio of mass ratio 1:1 ~ 1:19 adds in the homogeneous phase solution with mesoporous metal-organic framework materials according to Graphene and mesoporous metal-organic framework materials, and stir and form precursor aqueous solution; Be added dropwise to mass percent concentration in the precursor aqueous solution and be 60～80% hydrazine hydrate and mass percent concentration and be the mixed solution of 20～30% ammoniacal liquor, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 1:9 ~ 9:1, and the volume ratio of mixed solution and precursor aqueous solution is 1:200 ~ 1:50; Be back to the generation dark solution 70 ~ 100 ℃ of heating, so that graphene coated is in the surface and duct of the cavernous structure of mesoporous metal-organic frame, washing, filtration, drying, and get final product;
(2) liquid infiltration of sulphur, adding mass ratio in organic solvent is the elemental sulfur of 1:9 ~ 3:1, it is dissolved fully, after forming sulphur-containing solution, add graphene coated mesoporous metal-organic frame composite material, wherein the mass ratio of sulphur and graphene coated mesoporous metal-organic frame composite material is 1:9 ~ 9:1, keep stirring under 10 ~ 90 ° of C conditions of constant temperature, so that sulphur is penetrated in the surface and hierarchical pore structure thereof of described composite material uniformly, by filtering or the unnecessary sulphur-containing solution of centrifugal removal, after vacuumize, obtain lithium sulfur battery anode material.
The present invention above-mentioned by adopting the liquid infiltration of sulphur " Graphene and mesoporous metal-organic frame original position is compound+" two step process prepare sulphur and graphene coated mesoporous metal-organic framework materials composite positive pole, adopt the compound method of Graphene and mesoporous metal-organic frame original position, graphene coated among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, and then is formed conductive network; But and the size of the acting in conjunction Effective Regulation sulfur granules by Graphene and mesoporous metal-organic frame composite material and liquid infiltration and realize the selective distribution of sulphur, and the compound at low temperatures composite positive pole that obtains Uniform Dispersion, high conductivity, high capacity sulfur content.This preparation method can efficiently improve the distribution of sulphur in composite material, optimizes the composite material chemical property, and simultaneously, preparation technology is simple, is easy in industrial enforcement and production in enormous quantities.
The weight content of sulphur is 50% ~ 90% in the described positive electrode.
The ratio that the central hole structure of described mesoporous metal-organic framework materials accounts for whole pore structure is 30% ~ 60%; The specific area of described mesoporous metal-organic framework materials is 1000m
2/ g ~ 4000m
2/ g.
Described mesoporous metal organic framework materials comprises Zn
4O (TPDC)
3(DMF)
12(H
2O)
2, Cu
3(TATAB)
2(H
2O)
38DMF9H
2O, Co
3(OH) (OH
2) (OAc)
3(dcbp), [Cu (H
2O)]
3(ntei) 21DMA10H
2O, Cu
3(H
2O)
3(ttei) 19H
2O22DMF, Fe
3O (H
2O)
3(BTTC)
2XS, Cd
4Na (H
2O)
2(HTDBD)
3(TDBD) 10 (DMF) 6 (EtOH), 3 (H
2O), Cr
3F (H
2O)
3O (BTC)
2NH
2O, [Cr
3(OH) (H
2O)
2(μ
3-O) (O
2C-C
10H
6-CO
2)
3] guest; Guest=H
2O, EtOH, [Cu
3(L) (H
2O)
3)] 8DMSO15DMF3H
2O, Cd
2(bpdc)
34 (DMF), [Cd
3(bpdc)
3(DMF)] 5DMF18H
2O, Tb
16(TATB)
16(DMA)
24(In
3O) (OH) (ADC)
2(IN)
24.67H
2O, (In
3O) (OH) (ADC)
2(NH
2IN)
22.67H
2O, [Zn
4O (2,6-NDC) (BTB)
4/3(DEF)
16(H
2O)
9/2] in one or more.
The mixed proportion of hydrazine hydrate and ammoniacal liquor is for being 1:9 ~ 9:1 in the mixed solution of the ammoniacal liquor of the hydrazine hydrate of described mass percent concentration 60 ~ 80% and mass percent concentration 20 ~ 30%.
The drying means of described graphene coated mesoporous metal-organic framework materials comprises a kind of in vacuumize, forced air drying and the freeze drying.
(1) in the step, graphene oxide and water mix afterwards with supersonic oscillations 0.5～12h to forming homogeneous phase solution with 0.5～2mg/mL's.
(1) in the step, after mixed solution joins precursor aqueous solution, adds hot reflux 12 ~ 24h to generating dark solution at 70 ~ 100 ℃.
(2) in the step, keep stirring 1～12h under 10～90 ° of C conditions of constant temperature.
(2) in the step, vacuum drying temperature is 50～100 ° of C.
Described organic solvent is one or more in benzene, toluene, carbon tetrachloride, carbon disulfide, ethanol, the ether.
A kind of lithium-sulfur cell of the present invention preparation method of positive electrode has the following advantages:
(1) preparation method of the present invention adopts the liquid infiltration of sulphur " Graphene and mesoporous metal-organic frame original position is compound+" two step process to be prepared from, the grapheme material uniform fold of electric conductivity excellence is in the surface and duct of mesoporous metal-organic frame, form effective conductive network, improve material monolithic conductivity, efficiently solve the not good problem of conductivity of metal-organic framework materials and this bi-material of sulphur in the positive electrode of lithium-sulfur cell.
(2) preparation method of the present invention by original position compound must be extremely Graphene and the acting in conjunction of mesoporous metal-organic frame composite material and liquid infiltration, but the size of Effective Regulation sulfur granules also realizes the selective distribution of sulphur, and the compound at low temperatures composite positive pole that obtains Uniform Dispersion, high conductivity, high capacity sulfur content.This preparation method can efficiently improve the distribution of sulphur in composite material, optimizes the composite material chemical property.
(3) the present invention selects the structure of mesoporous metal-organic framework materials and porosity, specific area by control, not only adsorb active material sulphur in the duct of the composite material that forms, secondly, the abundant functional group in surface, duct, can adsorb the more active material sulfur materials of load by key, help simultaneously to suppress sulphur simple substance and the dissolving of polysulfide in electrolyte, be conducive to so fully improve the lithium-sulfur cell cycle performance and keep higher active substances in cathode materials utilance.
(4) the present invention so that elemental sulfur can be evenly distributed in the pore structure, effectively improves the distribution of sulphur in composite material by effective proportioning of each composition in the technique and effective control of parameter when guaranteeing composite material high capacity amount.Preparation technology's simple possible of the present invention is fit to suitability for industrialized production.
(5) raw material sources are extensive.
In sum, the present invention adopts the preparation method of the liquid infiltration of sulphur " graphene coated mesoporous metal-organic frame original position is compound+" two step process, grapheme material has promoted the electric conductivity of mesoporous metal-organic framework materials and composites greatly, utilized the larger mesoporous metal-organic framework materials of specific area to adsorb the simple substance sulphur granule that liquid infiltration disperses, under lower reaction temperature and simple experiment condition, the sulphur of having realized obtaining absorption is more, the good result of more uniform particle, but the utilance of the composite positive pole Effective Raise sulphur simple substance of preparing and the cycle performance of battery, industrialization prospect is good.
Description of drawings
Fig. 1 is the SEM figure of the composite positive pole one that obtains by embodiment 1
Fig. 2 is sulphur content Butut in the composite positive pole that obtains by embodiment 1
Fig. 3 is the thermogravimetric curve figure of the composite positive pole one that obtains by embodiment 1
Fig. 4 is 50 the discharge capacity curve charts of lithium-sulfur cell that obtain by embodiment 1.
Fig. 5 is the lithium-sulfur cell first charge-discharge platform figure that obtains by embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but is not restricted to the protection range of invention.The content of sulphur and the data of distribution situation please are provided in each embodiment.
Embodiment 1
Select mesoporous metal organic frame Cr
3F (H
2O)
3O (BTC)
2NH
2The compound preparation graphene coated of O original position mesoporous metal-organic framework materials, selected mesoporous metal organic frame Cr
3F (H
2O)
3O (BTC)
2NH
2The specific area of O is 2700m
2The ratio that/g, the central hole structure of this material account for whole pore structure is 40%.Graphene oxide (GO) is mixed with the ratio of 2mg/mL with water, use supersonic oscillations 0.5h, to forming homogeneous phase solution, to prepare mesoporous metal-organic framework materials according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:5 adds in the solution and stirs 0.5h and form precursor aqueous solution, the mixed solution that dropwise adds the ammoniacal liquor of the hydrazine hydrate of mass concentration 80% and mass concentration 25% in the precursor aqueous solution according to the ratio of volume ratio 1:200, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 9:1, add hot reflux 12h at 70 ℃, generate dark solution, so that graphene coated is among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely obtain graphene coated mesoporous metal-organic framework materials, washing, filter, dry.The elemental sulfur that adds mass ratio and be 1:3 in carbon disulfide dissolves fully, be that the ratio of 9:1 adds mesoporous metal-organic framework materials in reaction solution according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio, keeping under 55 ° of C conditions of constant temperature, stir 12h, so that sulphur is penetrated in the surface and hierarchical pore structure thereof of graphene coated mesoporous metal-organic framework materials material uniformly, adopt the method for filtering to remove organic solvent, obtain lithium sulfur battery anode material after 60 ° of C vacuumizes.The SEM pattern as shown in Figure 1.Fig. 2 is the distribution map of EDS scanning sulfur content.As can be seen from Fig., sulphur is evenly distributed in whole composite material.The actual sulfur content that calculates composite material one by thermogravimetric analysis is 87.9wt%, as shown in Figure 3.
Composite positive pole one, conductive black, the Kynoar (PVDF) of embodiment 1 gained are evenly mixed according to the mass ratio of 80:10:10, and be dispersed in the water of certain mass (85wt% of siccative quality), then be coated on the aluminum foil current collector, dry rear compressing tablet obtains a kind of lithium-sulphur cell positive electrode sheet.
The battery assembling with test is: positive plate is struck out the electrode slice that diameter is 10mm, take metal lithium sheet as negative pole, is 1M LiTFSI/DOL:DME (1:1) at electrolyte, is assembled into the CR2025 button cell in being full of the glove box of argon gas.(25 ℃) carry out the constant current charge-discharge test with 0.1C under room temperature, and discharging and recharging cut-ff voltage is 1.5 ~ 3.0V.Discharge platform is normal, has demonstrated the typical charge and discharge platform of lithium-sulfur cell.First discharge specific capacity is 1339.2mAh/g, and specific capacity is 650.5mAh/g after 50 circulations.Such as Fig. 4, shown in 5, discharge platform is normal, and the cyclical stability of battery is improved.
Select mesoporous metal organic frame Cu
3(TATAB)
2(H
2O)
38DMF9H
2The compound preparation graphene coated of O original position mesoporous metal-organic framework materials, selected mesoporous metal organic frame Cr
3F (H
2O)
2O (BDC)
3NH
2The specific area of O is 1600m
2The ratio that/g, the central hole structure of this material account for whole pore structure is 35%.Graphene oxide (GO) is mixed with the ratio of 0.5mg/mL with water, use supersonic oscillations 1h, to forming homogeneous phase solution, to prepare mesoporous metal-organic framework materials according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:2 adds in the solution and stirs 1h and form precursor aqueous solution, the mixed solution that dropwise adds the ammoniacal liquor of the hydrazine hydrate of mass concentration 80% and mass concentration 20% in the precursor aqueous solution according to the ratio of volume ratio 1:50, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 8:2, add hot reflux 18h at 100 ℃, generate dark solution, so that graphene coated is among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely obtain graphene coated mesoporous metal-organic framework materials, washing, filter, dry.The elemental sulfur that adds mass ratio and be 1:1 in toluene dissolves fully, be that the ratio of 8:2 adds mesoporous metal-organic framework materials in reaction solution according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio, keeping under 25 ° of C conditions of constant temperature, stir 12h, so that sulphur is penetrated in the surface and hierarchical pore structure thereof of graphene coated mesoporous metal-organic framework materials material uniformly, adopt method centrifugal and that filter to remove organic solvent, obtain lithium sulfur battery anode material two after 60 ° of C vacuumizes, the actual sulfur content of material is 75.3wt%.
Embodiment 3
Select mesoporous metal organic frame Cr
3F (H
2O)
3O (BTC)
2NH
2The compound preparation graphene coated of O original position mesoporous metal-organic framework materials, selected mesoporous metal organic frame Cr
3F (H
2O)
3O (BTC)
2NH
2The specific area of O is 2700m
2The ratio that/g, the central hole structure of this material account for whole pore structure is 40%.Graphene oxide (GO) is mixed with the ratio of 2mg/mL with water, use supersonic oscillations 0.5h, to forming homogeneous phase solution, to prepare mesoporous metal-organic framework materials according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:5 adds in the solution and stirs 2h and form precursor aqueous solution, the mixed solution that dropwise adds the ammoniacal liquor of the hydrazine hydrate of mass concentration 60% and mass concentration 28% in the precursor aqueous solution according to the ratio of volume ratio 1:100, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 1:9, add hot reflux 12h at 80 ℃, generate dark solution, so that graphene coated is among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely obtain graphene coated mesoporous metal-organic framework materials, washing, filter, dry.The elemental sulfur that adds mass ratio and be 1:3 in toluene dissolves fully, be that the ratio of 9:1 adds mesoporous metal-organic framework materials in reaction solution according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio, keeping under 35 ° of C conditions of constant temperature, stir 2h, so that sulphur is penetrated in the surface and hierarchical pore structure thereof of graphene coated mesoporous metal-organic framework materials material uniformly, adopt method centrifugal and that filter to remove organic solvent, obtain lithium sulfur battery anode material three after 55 ° of C vacuumizes, the actual sulfur content of material is 85.8wt%
Embodiment 4
Select mesoporous metal organic frame [Cr
3(OH) (H
2O)
2(μ
3-O) (O
2C-C
10H
6-CO
2)
3] H
2The compound preparation graphene coated of O original position mesoporous metal-organic framework materials, selected mesoporous metal organic frame [Cr
3(OH) (H
2O)
2(μ
3-O) (O
2C-C
10H
6-CO
2)
3] H
2The specific area of O is 2100m
2The ratio that/g, the central hole structure of this material account for whole pore structure is 45%.Graphene oxide (GO) is mixed with the ratio of 2mg/mL with water, use supersonic oscillations 2h, to forming homogeneous phase solution, to prepare mesoporous metal-organic framework materials according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:3 adds in the solution and stirs 2h and form precursor aqueous solution, the mixed solution that dropwise adds the ammoniacal liquor of the hydrazine hydrate of mass concentration 60% and mass concentration 25% in the precursor aqueous solution according to the ratio of volume ratio 1:50, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 9:1, add hot reflux 12h at 80 ℃, generate dark solution, so that graphene coated is among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely obtain graphene coated mesoporous metal-organic framework materials, washing, filter, dry.The elemental sulfur that adds mass ratio and be 1:3 in carbon disulfide dissolves fully, be that the ratio of 7:3 adds mesoporous metal-organic framework materials in reaction solution according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio, keeping under 35 ° of C conditions of constant temperature, stir 24h, so that sulphur is penetrated in the surface and hierarchical pore structure thereof of graphene coated mesoporous metal-organic framework materials material uniformly, adopt method centrifugal and that filter to remove organic solvent, obtain lithium sulfur battery anode material four after the vacuumize under 65 ° of C, sulfur content is 65.3wt%.
Embodiment 5
Select mesoporous metal organic frame Cr
3F (H
2O)
3O (BTC)
2NH
2The compound preparation graphene coated of O original position mesoporous metal-organic framework materials, selected mesoporous metal organic frame Cr
3F (H
2O)
3O (BTC)
2NH
2The specific area of O is 2700m
2The ratio that/g, the central hole structure of this material account for whole pore structure is 40%.Graphene oxide (GO) is mixed with the ratio of 1mg/mL with water, use supersonic oscillations 2h, to forming homogeneous phase solution, to prepare mesoporous metal-organic framework materials according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:4 adds in the solution and stirs 2h and form precursor aqueous solution, the mixed solution that dropwise adds the ammoniacal liquor of the hydrazine hydrate of mass concentration 70% and mass concentration 20% in the precursor aqueous solution according to the ratio of volume ratio 1:150, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 1:1, add hot reflux 12h at 100 ℃, generate dark solution, so that graphene coated is among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely obtain graphene coated mesoporous metal-organic framework materials, washing, filter, dry.The elemental sulfur that adds mass ratio and be 1:2 in carbon disulfide dissolves fully, be that the ratio of 9:1 adds mesoporous metal-organic framework materials in reaction solution according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio, keeping under 35 ° of C conditions of constant temperature, stir 24h, so that sulphur is penetrated in the surface and hierarchical pore structure thereof of graphene coated mesoporous metal-organic framework materials material uniformly, adopt method centrifugal and that filter to remove organic solvent, obtain lithium sulfur battery anode material five after the vacuumize under 65 ° of C, sulfur content is 87.2wt%.
Embodiment 6
Select mesoporous metal organic frame [Cu (H
2O)]
3(ntei) 21DMA10H
2The compound preparation graphene coated of O original position mesoporous metal-organic framework materials, selected mesoporous metal organic frame [Cu (H
2O)]
3(ntei) 21DMA10H
2The specific area of O is 4000m
2The ratio that/g, the central hole structure of this material account for whole pore structure is 32%.Graphene oxide (GO) is mixed with the ratio of 0.5mg/mL with water, use supersonic oscillations 2h, to forming homogeneous phase solution, to prepare mesoporous metal-organic framework materials according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:4 adds in the solution and stirs 4h and form precursor aqueous solution, the mixed solution that dropwise adds the ammoniacal liquor of the hydrazine hydrate of mass concentration 80% and mass concentration 25% in the precursor aqueous solution according to the ratio of volume ratio 1:200, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 9:1, add hot reflux 24h at 70 ℃, 80% the hydrazine hydrate solution that dropwise adds 5ul in the solution, add hot reflux 24h at 80 ℃, generate dark solution, so that graphene coated is among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely obtain graphene coated mesoporous metal-organic framework materials, washing, filter, dry.The elemental sulfur that adds mass ratio and be 1:1 in carbon disulfide dissolves fully, be that the ratio of 7:3 adds mesoporous metal-organic framework materials in reaction solution according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio, keeping under 45 ° of C conditions of constant temperature, stir 24h, so that sulphur is penetrated in the surface and hierarchical pore structure thereof of graphene coated mesoporous metal-organic framework materials material uniformly, adopt method centrifugal and that filter to remove organic solvent, obtain lithium sulfur battery anode material six after 60 ° of C vacuumizes, sulfur content is 64.2wt%.
Embodiment 7
Select mesoporous metal organic frame [Cu (H
2O)]
3(ntei) 21DMA10H
2The compound preparation graphene coated of O original position mesoporous metal-organic framework materials, selected mesoporous metal organic frame [Cu (H
2O)]
3(ntei) 21DMA10H
2The specific area of O is 3000m
2The ratio that/g, the central hole structure of this material account for whole pore structure is 40%.Graphene oxide (GO) is mixed with the ratio of 2mgmL with water, use supersonic oscillations 2h, to forming homogeneous phase solution, to prepare mesoporous metal-organic framework materials according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:2 adds in the solution and stirs 2h and form precursor aqueous solution, the mixed solution that dropwise adds the ammoniacal liquor of the hydrazine hydrate of mass concentration 60% and mass concentration 25% in the precursor aqueous solution according to the ratio of volume ratio 1:50, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 1:1, add hot reflux 24h at 100 ℃, 80% the hydrazine hydrate solution that dropwise adds 20ul in the solution, add hot reflux 24h at 80 ℃, generate dark solution, so that graphene coated is among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely obtain graphene coated mesoporous metal-organic framework materials, washing, filter, dry.The elemental sulfur that adds mass ratio and be 1:2 in carbon disulfide dissolves fully, be that the ratio of 7:3 adds mesoporous metal-organic framework materials in reaction solution according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio, keeping under 30 ° of C conditions of constant temperature, stir 24h, so that sulphur is penetrated in the surface and hierarchical pore structure thereof of graphene coated mesoporous metal-organic framework materials material uniformly, adopt method centrifugal and that filter to remove organic solvent, obtain lithium sulfur battery anode material six after the vacuumize under 60 ° of C, sulfur content is 65.2wt%.
Claims (10)
1. the preparation method of a lithium sulfur battery anode material is characterized in that: comprise the steps:
(1) original position prepares graphene coated mesoporous metal-organic frame composite material: graphene oxide is mixed with the ratio of 0.5 ~ 2mg/mL with deionized water, with supersonic oscillations to forming homogeneous phase solution; Be that the ratio of mass ratio 1:1 ~ 1:19 adds in the homogeneous phase solution with mesoporous metal-organic framework materials according to Graphene and mesoporous metal-organic framework materials, and stir and form precursor aqueous solution; Be added dropwise to mass percent concentration in the precursor aqueous solution and be 60～80% hydrazine hydrate and mass percent concentration and be the mixed solution of 20～30% ammoniacal liquor, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 1:9 ~ 9:1, and the volume ratio of mixed solution and precursor aqueous solution is 1:200 ~ 1:50; Be back to the generation dark solution 70 ~ 100 ℃ of heating, so that graphene coated is in the surface and duct of the cavernous structure of mesoporous metal-organic frame, washing, filtration, drying namely get graphene coated mesoporous metal-organic frame composite material;
(2) liquid infiltration of sulphur, adding mass ratio in organic solvent is the elemental sulfur of 1:9 ~ 3:1, it is dissolved fully, after forming sulphur-containing solution, add graphene coated mesoporous metal-organic frame composite material, wherein the mass ratio of sulphur and graphene coated mesoporous metal-organic frame composite material is 1:9 ~ 9:1, keep stirring under 10 ~ 90 ° of C conditions of constant temperature, so that sulphur is penetrated in the surface and hierarchical pore structure thereof of described composite material uniformly, by filtering or the unnecessary sulphur-containing solution of centrifugal removal, after vacuumize, obtain lithium sulfur battery anode material.
2. the preparation method of a kind of lithium sulfur battery anode material according to claim 1, it is characterized in that: the weight content of sulphur is 50% ~ 90% in the described positive electrode.
3. the preparation method of a kind of lithium sulfur battery anode material according to claim 1, it is characterized in that: the ratio that the central hole structure of described mesoporous metal-organic framework materials accounts for whole pore structure is 30% ~ 60%; The specific area of described mesoporous metal-organic framework materials is 1000m
2/ g ~ 4000m
2/ g.
4. the preparation method of a kind of lithium sulfur battery anode material according to claim 1, it is characterized in that: described mesoporous metal organic framework materials comprises Zn
4O (TPDC)
3(DMF)
12(H
2O)
2, Cu
3(TATAB)
2(H
2O)
38DMF9H
2O, Co
3(OH) (OH
2) (OAc)
3(dcbp), [Cu (H
2O)]
3(ntei) 21DMA10H
2O, Cu
3(H
2O)
3(ttei) 19H
2O22DMF, Fe
3O (H
2O)
3(BTTC)
2XS, Cd
4Na (H
2O)
2(HTDBD)
3(TDBD) 10 (DMF) 6 (EtOH), 3 (H
2O), Cr
3F (H
2O)
3O (BTC)
2NH
2O, [Cr
3(OH) (H
2O)
2(μ
3-O) (O
2C-C
10H
6-CO
2)
3] guest; Guest=H
2O, EtOH, [Cu
3(L) (H
2O)
3)] 8DMSO15DMF3H
2O, Cd
2(bpdc)
34 (DMF), [Cd
3(bpdc)
3(DMF)] 5DMF18H
2O, Tb
16(TATB)
16(DMA)
24(In
3O) (OH) (ADC)
2(IN)
24.67H
2O, (In
3O) (OH) (ADC)
2(NH
2IN)
22.67H
2O, [Zn
4O (2,6-NDC) (BTB)
4/3(DEF)
16(H
2O)
9/2] in one or more.
5. the preparation method of a kind of lithium sulfur battery anode material according to claim 1 is characterized in that: stir 0.5 ~ 2h in mesoporous metal-organic framework materials adding homogeneous phase solution.
6. the preparation method of a kind of lithium sulfur battery anode material according to claim 1 is characterized in that: in (1) step, after mixed solution joins precursor aqueous solution, add hot reflux 12 ~ 24h at 70 ~ 100 ℃.
7. the preparation method of a kind of lithium sulfur battery anode material according to claim 1 is characterized in that: in (1) step, described drying comprises a kind of in vacuumize, forced air drying and the freeze drying.
8. the preparation method of a kind of lithium sulfur battery anode material according to claim 1 is characterized in that: in (2) step, described organic solvent is one or more in benzene, toluene, carbon tetrachloride, carbon disulfide, ethanol, the ether.
9. the preparation method of a kind of lithium sulfur battery anode material according to claim 1 is characterized in that: in (2) step, keep stirring 1 ~ 12h under 10 ~ 90 ° of C conditions of constant temperature.
10. the preparation method of a kind of lithium sulfur battery anode material according to claim 1 is characterized in that: in (2) step, vacuum drying temperature is 50 ~ 100 ° of C.
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