CN103035893B - Preparation method of lithiumsulphur battery positive pole material - Google Patents
Preparation method of lithiumsulphur battery positive pole material Download PDFInfo
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- CN103035893B CN103035893B CN201210535305.3A CN201210535305A CN103035893B CN 103035893 B CN103035893 B CN 103035893B CN 201210535305 A CN201210535305 A CN 201210535305A CN 103035893 B CN103035893 B CN 103035893B
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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, becoming increasingly conspicuous of the problem such as energy shortage, environmental pollution, people are to the understanding of chemical power source and require also more and more higher, and impelling people constantly to explore new chemical power source is main energy storage system.In recent decades, the battery based on lithium metal has led the developing direction of high performance chemical electric power source.Along with the successful commercialization of lithium ion battery, the research carrying out vehicle lithium-ion power battery is all being stepped up in countries in the world.But due to factors such as energy density, fail safe, prices, traditional lithium-ion battery as sour in cobalt lithium, LiMn2O4 and ferric phosphate lithium cell cannot meet the requirement of electric automobile as power source.
Lithium-sulfur cell is the high-energy density secondary battery having development potentiality and application prospect.It has height ratio capacity (1675mAh/g) and high-energy-density (2600Wh/g).In addition, sulphur also shows incomparable advantage as positive active material in source, cost and environmental friendliness etc.
At present, there is cycle performance difference in lithium-sulfur cell, high rate performance needs the problems such as further raising.And active material sulfur materials itself and final discharging product Li in lithium-sulfur cell
2s is the insulator of electronics and ion, and the intermediate product polysulfide in discharge process is soluble in electrolyte, and these can cause irreversible loss and the capacity attenuation of active material.For this reason, how to suppress the diffusion of polysulfide, improve the research emphasis that the distribution of sulphur and the conductivity improved in the cyclic process of sulphur positive pole are sulfur-based positive electrode materials.
In recent years academia mainly around improve sulphur distribution, suppress polysulfide diffusion and improve positive electrode conductivity and conduct a research.On material structure, first consider it is be adsorbed on by elemental sulfur on porous material parent, such as by porous carbon as material with carbon element and sulphur compounds such as active carbon, carbon nano-tube, Graphenes, the polysulfide preventing course of reaction from producing is dissolved in electrolyte, spread by electrolyte, contribute to minimizing like this and to shuttle back and forth effect and self-discharge phenomenon.These new material structure more or less improve 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, aperture is difficult to regulation and control, the limited sorption capacity of material, cause that the sulfur content in the composite positive pole of preparation is low, skewness, be assembled into circulating battery after a few, still have a large amount of active material can dissolve from carbon structure duct, cause the loss of active material, lithium-sulfur cell energy density is difficult to improve further.Meanwhile, the pore structure of porous material and the distribution of sulphur thereof affect very large on battery performance.When only having celled portion to be filled with sulphur, in composite material, active matter quality content is low, 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 all distributed the sulphur of a large amount of insulation, the electrical conductivity of composite material and ion transport capability then can be subject to obvious restriction, simultaneously, a large amount of sulphur is distributed in the outer surface of material with carbon element, the polysulfide generated after this part reaction of Salmon-Saxl easily spreads and shuttles back and forth, cause the irreversible loss of active material, the chemical property of material can not get good performance.In addition, the preparation technology of sulphur and porous carbon composite positive pole adopts heat treating process usually.Heat treating process is that under certain heat treating regime, be elevated to 150 ~ 600 ° of C, keep 1 ~ 20 hour, cooling can obtain composite positive pole under inert gas carrier protection.But this mode affects by factors such as temperature retention time, air-flow velocity, temperature rates, be difficult to the content controlling sulphur, simultaneously due to the impact of carrier gas, sulfur material in raw material can be caused in a large number with gas overflowing, to cause the utilance of sulphur in raw material low.
Metal-organic framework materials is the material with non-periodic pore network configuration that self assembly is formed by the complexing of the metal-ligand between multiple tooth organic ligand and metal ion.Metal-organic framework materials not only has special topological structure, internal arrangement rule and has the duct of specific dimensions and shape, and its duct has controllability, by select stereochemical structure and the size be suitable for organic ligand can the pore structure of Effective Regulation metal-organic framework, size and and specific area, the surface characteristic in duct and organic composition can construct a large amount of functional group, due to complexity and the diversity of organic ligand and Action of Metal Ions, in structural design and the application aspect of material, for people provide unprecedented opportunities.
But 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 of lithium sulphur positive electrode (as coulombic efficiency, polarization and specific capacity).Usually, in cell positive material, add the electric conductivity that a certain amount of conductive agent (as carbon black and acetylene black etc.) suitably can promote material.But due to conductive agent material usually exist in granular form with positive electrode among, cannot uniform fold on the surface of active material, and effective conductive network can not be formed.The problems such as the conductivity improving material monolithic by the conductivity of Graphene excellence, the sulphur component utilance caused with active component sulphur poorly conductive in the positive electrode solving lithium-sulfur cell are low, polarization dissolving institute greatly and in the electrolytic solution causes battery capacity decay too fast.
In sum, this area is in the urgent need to developing a kind of positive material for lithium-sulfur battery and preparation thereof of simple, high-efficient carrier sulphur simple substance, reduce the loss late of active material sulphur in composite material preparation process, improve the space availability ratio of loose structure, elemental sulfur can be evenly distributed in pore structure, sulphur distribution in the composite is effectively improved while ensureing 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, elemental sulfur can be made to be evenly distributed in pore structure, while ensureing composite material high capacity amount, effectively improve sulphur distribution in the composite.
Technical scheme of the present invention is:
(1) original position prepares graphene coated mesoporous metal-organic frame composite material: mixed with the ratio of 0.5 ~ 2mg/mL with deionized water by graphene oxide, by supersonic oscillations to forming homogeneous phase solution; Mesoporous metal-organic framework materials is added in homogeneous phase solution according to the ratio that Graphene and mesoporous metal-organic framework materials are mass ratio 1:1 ~ 1:19, and stirs formation precursor aqueous solution; Be added dropwise in precursor aqueous solution mass percent concentration be 60 ~ 80% hydrazine hydrate and mass percent concentration be the mixed solution of the ammoniacal liquor of 20 ~ 30%, 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 generation dark solution 70 ~ 100 DEG C of heating, make graphene coated in the surface and duct of the cavernous structure of mesoporous metal-organic frame, washing, filtration, drying, to obtain final product;
(2) liquid infiltration of sulphur, add the elemental sulfur that mass ratio is 1:9 ~ 3:1 in organic solvent, it is made to dissolve completely, 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, stir under keeping constant temperature 10 ~ 90 ° of C conditions, in the surface making sulphur penetrate into described composite material uniformly and hierarchical pore structure thereof, by the sulphur-containing solution filtered or centrifugal segregation is unnecessary, after vacuumize, obtain lithium sulfur battery anode material.
The present invention prepares sulphur and graphene coated mesoporous metal-organic framework materials composite positive pole by adopting above-mentioned " liquid infiltration of Graphene and mesoporous metal-organic frame In-situ reaction+sulphur " two step process, adopt the method for Graphene and mesoporous metal-organic frame In-situ reaction, by graphene coated among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, and then form conductive network; And by the acting in conjunction of Graphene and mesoporous metal-organic frame composite material and liquid infiltration can Effective Regulation sulfur granules size and realize the selective distribution of sulphur, and compound obtains dispersed, high conductivity, high capacity sulfur content composite positive pole at low temperatures.This preparation method efficiently can improve sulphur distribution in the composite, optimizes composite material chemical property, and meanwhile, preparation technology is simple, is easy to industrially implement and produce in enormous quantities.
In described positive electrode, the weight content of sulphur is 50% ~ 90%.
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.
In the mixed solution of the hydrazine hydrate of described mass percent concentration 60 ~ 80% and the ammoniacal liquor of mass percent concentration 20 ~ 30%, the mixed proportion of hydrazine hydrate and ammoniacal liquor is for being 1:9 ~ 9:1.
The drying means of described graphene coated mesoporous metal-organic framework materials comprises the one in vacuumize, forced air drying and freeze drying.
(1) in step, graphene oxide and water with 0.5 ~ 2mg/mL mix afterwards with supersonic oscillations 0.5 ~ 12h to forming homogeneous phase solution.
(1), in step, after mixed solution joins precursor aqueous solution, hot reflux 12 ~ 24h is added to generating dark solution at 70 ~ 100 DEG C.
(2), in step, under keeping constant temperature 10 ~ 90 ° of C conditions, 1 ~ 12h is stirred.
(2), in step, vacuum drying temperature is 50 ~ 100 ° of C.
Described organic solvent is one or more in benzene, toluene, carbon tetrachloride, carbon disulfide, ethanol, ether.
The preparation method of a kind of positive material for lithium-sulfur battery of the present invention, has the following advantages:
(1) preparation method of the present invention adopts " liquid infiltration of Graphene and mesoporous metal-organic frame In-situ reaction+sulphur " 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, the conductivity improving material monolithic, efficiently solve lithium-sulfur cell positive electrode in the not good problem of the conductivity of metal-organic framework materials and this bi-material of sulphur.
(2) preparation method of the present invention must the acting in conjunction of Graphene extremely and mesoporous metal-organic frame composite material and liquid infiltration by In-situ reaction, can Effective Regulation sulfur granules size and realize the selective distribution of sulphur, and compound obtains dispersed, high conductivity, high capacity sulfur content composite positive pole at low temperatures.This preparation method efficiently can improve sulphur distribution in the composite, optimizes composite material chemical property.
(3) the present invention is by controlling structure and porosity, the specific area of selecting mesoporous metal-organic framework materials, the duct of the composite material formed not only is adsorbed active material sulphur, secondly, the functional group that channel surfaces is abundant, the more active material sulfur materials of key absorption carriage can be passed through, contribute to suppressing sulphur simple substance and polysulfide dissolving in the electrolytic solution simultaneously, be conducive to so fully improving lithium-sulfur cell cycle performance and keeping higher active substances in cathode materials utilance.
(4) the present invention is by effective proportioning of each composition and effective control of parameter in technique, and elemental sulfur can be evenly distributed in pore structure, effectively improves sulphur distribution in the composite while ensureing composite material high capacity amount.Preparation technology's simple possible of the present invention, is applicable to suitability for industrialized production.
(5) raw material sources are extensive.
In sum, the present invention adopts the preparation method of " liquid infiltration of graphene coated mesoporous metal-organic frame In-situ reaction+sulphur " two step process, grapheme material improves the electric conductivity of mesoporous metal-organic framework materials and composites greatly, make use of the larger mesoporous metal-organic framework materials of specific area to adsorb the simple substance sulphur granule of liquid phase diffuse, under lower reaction temperature and simple experiment condition, achieve the sulphur obtaining absorption more, the good result of more uniform particle, the composite positive pole prepared effectively can improve the utilance of sulphur simple substance and the cycle performance of battery, industrialization prospect is good.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the composite positive pole one obtained by embodiment 1
Fig. 2 is sulphur content Butut in the composite positive pole obtained by embodiment 1
Fig. 3 is the thermogravimetric curve figure of the composite positive pole one obtained by embodiment 1
Fig. 4 is lithium-sulfur cell 50 the discharge capacity curve charts obtained by embodiment 1.
Fig. 5 is the lithium-sulfur cell first charge-discharge platform figure obtained 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 data of the Content and distribution situation of sulphur are please provided in embodiments.
Embodiment 1
Select mesoporous metal organic frame Cr
3f (H
2o)
3o (BTC)
2nH
2o In-situ reaction prepares graphene coated mesoporous metal-organic framework materials, selected mesoporous metal organic frame Cr
3f (H
2o)
3o (BTC)
2nH
2the specific area of O is 2700m
2/ g, the ratio that the central hole structure of this material accounts 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 add in solution and stir 0.5h according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:5 form precursor aqueous solution by preparing mesoporous metal-organic framework materials, dropwise add the mixed solution of the hydrazine hydrate of mass concentration 80% and the ammoniacal liquor of mass concentration 25% according to the ratio of volume ratio 1:200 in precursor aqueous solution, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 9:1, hot reflux 12h is added at 70 DEG C, generate dark solution, make graphene coated among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely graphene coated mesoporous metal-organic framework materials is obtained, washing, filter, dry.In carbon disulfide, add mass ratio is that the elemental sulfur of 1:3 dissolves completely, the ratio being 9:1 according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio adds mesoporous metal-organic framework materials in reaction solution, under maintenance constant temperature 55 ° of C conditions, stir 12h, in the surface making sulphur penetrate into graphene coated mesoporous metal-organic framework materials material uniformly and hierarchical pore structure thereof, adopt the method for filtering to remove organic solvent, after 60 ° of C vacuumizes, obtain lithium sulfur battery anode material.SEM pattern as shown in Figure 1.Fig. 2 is the distribution map that EDS scans sulfur content.As can be seen from Fig., sulphur is evenly distributed in whole composite material.The actual sulfur content being calculated composite material one by thermogravimetric analysis is 87.9wt%, as shown in Figure 3.
The composite positive pole one of embodiment 1 gained, conductive black, Kynoar (PVDF) are compared Homogeneous phase mixing according to the quality of 80:10:10, and be dispersed in the water of certain mass (85wt% of siccative quality), then be coated in aluminum foil current collector, after dry, compressing tablet obtains a kind of lithium-sulphur cell positive electrode sheet.
Battery assembling with test is: positive plate being struck out the electrode slice that diameter is 10mm, take metal lithium sheet as negative pole, is 1M LiTFSI/DOL:DME (1:1), is assembled into CR2025 button cell in the glove box being full of argon gas at electrolyte.Under room temperature, (25 DEG C) carry out constant current charge-discharge test with 0.1C, and discharge and recharge cut-ff voltage is 1.5 ~ 3.0V.Discharge platform is normal, shows the typical charge and discharge platform of lithium-sulfur cell.First discharge specific capacity is 1339.2mAh/g, and after 50 circulations, specific capacity is 650.5mAh/g.As Fig. 4, shown in 5, discharge platform is normal, and the cyclical stability of battery is improved.
Embodiment 2
Select mesoporous metal organic frame Cu
3(TATAB)
2(H
2o)
38DMF9H
2o In-situ reaction prepares graphene coated mesoporous metal-organic framework materials, selected mesoporous metal organic frame Cr
3f (H
2o)
2o (BDC)
3nH
2the specific area of O is 1600m
2/ g, the ratio that the central hole structure of this material accounts 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 add in solution and stir 1h according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:2 form precursor aqueous solution by preparing mesoporous metal-organic framework materials, dropwise add the mixed solution of the hydrazine hydrate of mass concentration 80% and the ammoniacal liquor of mass concentration 20% according to the ratio of volume ratio 1:50 in precursor aqueous solution, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 8:2, hot reflux 18h is added at 100 DEG C, generate dark solution, make graphene coated among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely graphene coated mesoporous metal-organic framework materials is obtained, washing, filter, dry.In toluene, add mass ratio is that the elemental sulfur of 1:1 dissolves completely, the ratio being 8:2 according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio adds mesoporous metal-organic framework materials in reaction solution, under maintenance constant temperature 25 ° of C conditions, stir 12h, in the surface making sulphur penetrate into graphene coated mesoporous metal-organic framework materials material uniformly and hierarchical pore structure thereof, method that is centrifugal and that filter is adopted 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
2o In-situ reaction prepares graphene coated mesoporous metal-organic framework materials, selected mesoporous metal organic frame Cr
3f (H
2o)
3o (BTC)
2nH
2the specific area of O is 2700m
2/ g, the ratio that the central hole structure of this material accounts 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 add in solution and stir 2h according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:5 form precursor aqueous solution by preparing mesoporous metal-organic framework materials, dropwise add the mixed solution of the hydrazine hydrate of mass concentration 60% and the ammoniacal liquor of mass concentration 28% according to the ratio of volume ratio 1:100 in precursor aqueous solution, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 1:9, hot reflux 12h is added at 80 DEG C, generate dark solution, make graphene coated among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely graphene coated mesoporous metal-organic framework materials is obtained, washing, filter, dry.In toluene, add mass ratio is that the elemental sulfur of 1:3 dissolves completely, the ratio being 9:1 according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio adds mesoporous metal-organic framework materials in reaction solution, under maintenance constant temperature 35 ° of C conditions, stir 2h, in the surface making sulphur penetrate into graphene coated mesoporous metal-organic framework materials material uniformly and hierarchical pore structure thereof, method that is centrifugal and that filter is adopted 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
2o In-situ reaction prepares graphene coated 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
2/ g, the ratio that the central hole structure of this material accounts 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 add in solution and stir 2h according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:3 form precursor aqueous solution by preparing mesoporous metal-organic framework materials, dropwise add the mixed solution of the hydrazine hydrate of mass concentration 60% and the ammoniacal liquor of mass concentration 25% according to the ratio of volume ratio 1:50 in precursor aqueous solution, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 9:1, hot reflux 12h is added at 80 DEG C, generate dark solution, make graphene coated among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely graphene coated mesoporous metal-organic framework materials is obtained, washing, filter, dry.In carbon disulfide, add mass ratio is that the elemental sulfur of 1:3 dissolves completely, the ratio being 7:3 according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio adds mesoporous metal-organic framework materials in reaction solution, under maintenance constant temperature 35 ° of C conditions, stir 24h, in the surface making sulphur penetrate into graphene coated mesoporous metal-organic framework materials material uniformly and hierarchical pore structure thereof, method that is centrifugal and that filter is adopted to remove organic solvent, obtain lithium sulfur battery anode material four after vacuumize under 65 ° of C, sulfur content is 65.3wt%.
Embodiment 5
Select mesoporous metal organic frame Cr
3f (H
2o)
3o (BTC)
2nH
2o In-situ reaction prepares graphene coated mesoporous metal-organic framework materials, selected mesoporous metal organic frame Cr
3f (H
2o)
3o (BTC)
2nH
2the specific area of O is 2700m
2/ g, the ratio that the central hole structure of this material accounts 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 add in solution and stir 2h according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:4 form precursor aqueous solution by preparing mesoporous metal-organic framework materials, dropwise add the mixed solution of the hydrazine hydrate of mass concentration 70% and the ammoniacal liquor of mass concentration 20% according to the ratio of volume ratio 1:150 in precursor aqueous solution, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 1:1, hot reflux 12h is added at 100 DEG C, generate dark solution, make graphene coated among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely graphene coated mesoporous metal-organic framework materials is obtained, washing, filter, dry.In carbon disulfide, add mass ratio is that the elemental sulfur of 1:2 dissolves completely, the ratio being 9:1 according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio adds mesoporous metal-organic framework materials in reaction solution, under maintenance constant temperature 35 ° of C conditions, stir 24h, in the surface making sulphur penetrate into graphene coated mesoporous metal-organic framework materials material uniformly and hierarchical pore structure thereof, method that is centrifugal and that filter is adopted to remove organic solvent, obtain lithium sulfur battery anode material five after vacuumize under 65 ° of C, sulfur content is 87.2wt%.
Embodiment 6
Select mesoporous metal organic frame [Cu (H
2o)]
3(ntei) 21DMA10H
2o In-situ reaction prepares graphene coated mesoporous metal-organic framework materials, selected mesoporous metal organic frame [Cu (H
2o)]
3(ntei) 21DMA10H
2the specific area of O is 4000m
2/ g, the ratio that the central hole structure of this material accounts 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 add in solution and stir 4h according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:4 form precursor aqueous solution by preparing mesoporous metal-organic framework materials, dropwise add the mixed solution of the hydrazine hydrate of mass concentration 80% and the ammoniacal liquor of mass concentration 25% according to the ratio of volume ratio 1:200 in precursor aqueous solution, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 9:1, hot reflux 24h is added at 70 DEG C, , the hydrazine hydrate solution of 80% of 5ul is dropwise added in solution, hot reflux 24h is added at 80 DEG C, generate dark solution, make graphene coated among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely graphene coated mesoporous metal-organic framework materials is obtained, washing, filter, dry.In carbon disulfide, add mass ratio is that the elemental sulfur of 1:1 dissolves completely, the ratio being 7:3 according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio adds mesoporous metal-organic framework materials in reaction solution, under maintenance constant temperature 45 ° of C conditions, stir 24h, in the surface making sulphur penetrate into graphene coated mesoporous metal-organic framework materials material uniformly and hierarchical pore structure thereof, method that is centrifugal and that filter is adopted 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
2o In-situ reaction prepares graphene coated mesoporous metal-organic framework materials, selected mesoporous metal organic frame [Cu (H
2o)]
3(ntei) 21DMA10H
2the specific area of O is 3000m
2/ g, the ratio that the central hole structure of this material accounts 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 add in solution and stir 2h according to the ratio of Graphene and mesoporous metal-organic framework materials mass ratio 1:2 form precursor aqueous solution by preparing mesoporous metal-organic framework materials, dropwise add the mixed solution of the hydrazine hydrate of mass concentration 60% and the ammoniacal liquor of mass concentration 25% according to the ratio of volume ratio 1:50 in precursor aqueous solution, wherein the mixing quality ratio of hydrazine hydrate and ammoniacal liquor is 1:1, hot reflux 24h is added at 100 DEG C, the hydrazine hydrate solution of 80% of 20ul is dropwise added in solution, hot reflux 24h is added at 80 DEG C, generate dark solution, make graphene coated among the surface and duct of the level cavernous structure of mesoporous metal-organic frame, namely graphene coated mesoporous metal-organic framework materials is obtained, washing, filter, dry.In carbon disulfide, add mass ratio is that the elemental sulfur of 1:2 dissolves completely, the ratio being 7:3 according to sulphur and graphene coated mesoporous metal-organic framework materials mass ratio adds mesoporous metal-organic framework materials in reaction solution, under maintenance constant temperature 30 ° of C conditions, stir 24h, in the surface making sulphur penetrate into graphene coated mesoporous metal-organic framework materials material uniformly and hierarchical pore structure thereof, method that is centrifugal and that filter is adopted to remove organic solvent, obtain lithium sulfur battery anode material six after vacuumize under 60 ° of C, sulfur content is 65.2wt%.
Claims (10)
1. a preparation method for lithium sulfur battery anode material, is characterized in that: comprise the steps:
(1) original position prepares graphene coated mesoporous metal-organic frame composite material: mixed with the ratio of 0.5 ~ 2mg/mL with deionized water by graphene oxide, by supersonic oscillations to forming homogeneous phase solution; Mesoporous metal-organic framework materials is added in homogeneous phase solution according to the ratio that Graphene and mesoporous metal-organic framework materials are mass ratio 1:1 ~ 1:19, and stirs formation precursor aqueous solution; Be added dropwise in precursor aqueous solution mass percent concentration be 60 ~ 80% hydrazine hydrate and mass percent concentration be the mixed solution of the ammoniacal liquor of 20 ~ 30%, 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 generation dark solution 70 ~ 100 DEG C of heating, make graphene coated in the surface and duct of the cavernous structure of mesoporous metal-organic frame, washing, filtration, drying, obtain graphene coated mesoporous metal-organic frame composite material;
(2) liquid infiltration of sulphur: add elemental sulfur in organic solvent, the mass ratio of elemental sulfur and organic solvent is 1:9 ~ 3:1, it is made to dissolve completely, 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, stir under keeping constant temperature 10 ~ 90 DEG C of conditions, in the surface making sulphur penetrate into described composite material uniformly and hierarchical pore structure thereof, by the sulphur-containing solution filtered or centrifugal segregation is unnecessary, 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, is characterized in that: in described positive electrode, the weight content of sulphur is 50% ~ 90%.
3. the preparation method of a kind of lithium sulfur battery anode material according to claim 1, 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, 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: mesoporous metal-organic framework materials adds stirring 0.5 ~ 2h in 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 DEG C.
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 the one in vacuumize, forced air drying and 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, and described organic solvent is one or more in benzene, toluene, carbon tetrachloride, carbon disulfide, ethanol, 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, under keeping constant temperature 10 ~ 90 DEG C of conditions, stirs 1 ~ 12h.
10. the preparation method of a kind of lithium sulfur battery anode material according to claim 1, is characterized in that: in (2) step, and vacuum drying temperature is 50 ~ 100 DEG C.
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| CN109935812A (en) * | 2019-03-13 | 2019-06-25 | 河源广工大协同创新研究院 | A kind of novel lithium sulfur battery anode material and preparation method thereof |
| 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 |
| CN112117453B (en) * | 2020-10-16 | 2022-08-09 | 肇庆市华师大光电产业研究院 | Novel lithium-sulfur battery positive electrode composite material and preparation method thereof |
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| CN105453309B (en) * | 2011-05-03 | 2018-06-29 | 上海交通大学 | Positive electrode comprising graphene for Li-S batteries and preparation method thereof |
| CN102244236A (en) * | 2011-06-10 | 2011-11-16 | 北京理工大学 | Method for preparing lithium-enriched cathodic material of lithium ion battery |
| CN102368553B (en) * | 2011-10-13 | 2013-04-17 | 上海交通大学 | Sulfur-base composite material containing graphene and preparation method thereof |
| CN102544489B (en) * | 2012-01-09 | 2014-12-10 | 上海交通大学 | Method for preparing graphene-coated olivine type lithium ferric phosphate composite material |
| CN102751494A (en) * | 2012-07-09 | 2012-10-24 | 广州市香港科大霍英东研究院 | Preparation method of novel porous skeleton MIL-101(Cr)@S/graphene composite material for cathode of lithium sulfur battery |
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