CN104269544A - Graphene array composited anode as well as preparation method and application thereof - Google Patents
Graphene array composited anode as well as preparation method and application thereof Download PDFInfo
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- CN104269544A CN104269544A CN201410542825.6A CN201410542825A CN104269544A CN 104269544 A CN104269544 A CN 104269544A CN 201410542825 A CN201410542825 A CN 201410542825A CN 104269544 A CN104269544 A CN 104269544A
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- graphene array
- sulphur
- graphene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a graphene array based carbon and sulfur composited anode. The anode is composited by a graphene array, titanium dioxide and sulfur and has huge specific surface area and excellent electric conductivity, wherein the graphene array is vertically grown on a conductive substrate material and forms a three-dimensional network conductive frame, the active material sulfur is uniformly loaded on the surface and in holes of the conductive frame, and an outer layer is coated with titanium dioxide. Therefore, a prepared secondary aluminum battery has higher specific capacity and good cycle performance, the preparation procedure is simple, and the composited anode is suitable for industrial production.
Description
Technical field
The invention belongs to battery material scientific domain, relate to a kind of carbon sulphur anode composite and preparation thereof of graphene array, also relate to the secondary aluminium cell comprising this anode composite.
Background technology
Along with the fast development of the new powers such as electronics and communication apparatus, electric automobile, wind power generation and photovoltaic generation, the battery performance demand of the mankind to supporting power supply is more and more higher, have that energy is high, cost is low, the life-span is long in the urgent need to exploitation, environmental protection, the electrokinetic cell of battery material aboundresources and reusable edible and energy-storage battery.Secondary aluminium-sulfur battery is a kind of novel battery system with high-energy-density, has very high application potential and commercial value.
The operation principle of secondary aluminium-sulfur battery is the Reversible redox reaction between sulphur and aluminium.At present, the technical bottleneck of aluminium-sulfur battery is that the intermediate poly sulfide that sulfur-based positive electrode material also exists active material loss, poorly conductive, reduction process produce is soluble in electrolyte, the diffusion of partly soluble poly sulfide arrives metallic aluminium negative terminal surface and produce self discharge reaction and be deposited on negative pole and make the problems such as its passivation.Therefore, how to improve the conductivity of material, and solve the problems of dissolution of discharge and recharge intermediate product, improving the cycle performance of battery, is the research emphasis of sulfur-based positive electrode material.
Current resolving ideas is by elemental sulfur and conductive carrier compound.Graphene is a kind of carbon element class material of accurate Colloidal particles, the great specific area had, and the conductivity of superelevation and outstanding heat conductivility are one of desirable energy storage materials.But, because Graphene is very easily reunited, this greatly reduces its surface area as electrode material, seriously reduce its actual specific area and the performance as active ingredient carriers, electrolyte is not only made to be difficult to fully contact with graphenic surface, and the adsorbance of active material is few, utilance is low.Simultaneously, by the restriction of carbon-based material loose structure and surface chemistry, the interaction on sulphur and carbon matrix surface is very weak, cause sulphur skewness in carbon matrix, the composite material shortcoming such as still existence and stability is poor, sulfur content is low and in practical application processing characteristics is limited, only lean on the confinement effect of material with carbon element hole and adsorption effect to be difficult to the loss by dissolution thoroughly suppressing poly sulfide, cycle performance can't reach practical degree.
Summary of the invention
(1) goal of the invention
The object of the invention is to improve above-mentioned technology Problems existing and deficiency, a kind of carbon sulphur anode composite based on graphene array is provided, described anode composite has three-dimensional network conducting matrix grain, uniform load has the active material sulphur of nano-scale therebetween, external sheath has titanium dioxide, its conductivity and stability significantly improve, and the secondary aluminium cell prepared thus has higher specific capacity and good cycle performance.
Graphene array is orderly laminated structure and open bore structure, the three-dimensional network conducting matrix grain of the nano-scale formed, there is the advantages such as specific surface is huge, absorption affinity strong, good stability, electro transfer and charge transfer are fast, the excellent specific property of Graphene itself can be given full play to.The network configuration of its nano-scale has strong absorption confinement effect, with sulphur compound tense, more active material load byte not only can be provided, sulphur is fixed in further absorption, sulphur is connected with conducting matrix grain on nanoscale, greatly promote activity and the utilance of sulphur, but also can fetter and suppress the dissolving of the intermediate products such as Small molecular sulfide, thus slow down the loss of sulphur.There is at Surface coating one deck of sulphurous materials transient metal sulfide or the oxide of ion selectivity, can prevent electrode material from contacting with the direct of electrolyte, suppress phase in version, improve composite structure stability, further reduction polysulfide and reduzate dissolving in the electrolytic solution thereof, certain cushioning effect can also be played to the change in volume of sulphur in charge and discharge process simultaneously, effectively improve the structural stability of electrode, and then improve the cycle performance of battery.
The present invention also aims to provide a kind of method preparing carbon sulphur anode composite based on graphene array.
The present invention also aims to provide a kind of secondary aluminium cell comprising described anode composite.
(2) technical scheme
For achieving the above object, the invention provides following technical scheme:
Based on a carbon sulphur anode composite for graphene array, comprising:
A () graphene array, is characterized in that, described Graphene vertical-growth is on conductive substrates material;
(b) titanium dioxide; With
(c) sulphur.
The carbon sulphur anode composite based on graphene array described in scheme, it is characterized in that, described conductive substrates material includes but not limited to the metals or nonmetal such as carbon fiber, graphite, vitrescence carbon, titanium, nickel, stainless steel, iron, copper, zinc, lead, manganese, cadmium, gold, silver, platinum, tantalum, tungsten, conductive plastics, conductive rubber or highly doped silicon, and conductive substrates material is preferably titanium.
The carbon sulphur anode composite based on graphene array described in scheme, is characterized in that, described sulphur by heat treated mode with nano-scale uniform load in conducting matrix grain surface and hole in.
The carbon sulphur anode composite based on graphene array described in scheme, is characterized in that, described coated by titanium dioxide is in Graphene and sulphur skin.
The carbon sulphur anode composite based on graphene array described in scheme, is characterized in that, comprise 10 ~ 15 wt% Graphenes, 15 ~ 25 wt% titanium dioxide and 60 ~ 70 wt% sulphur.
The preparation method of the carbon sulphur anode composite based on graphene array described in scheme, is characterized in that, comprise the following steps:
Step 1, the preparation of graphene array: by plasma enhanced chemical vapor deposition in conductive substrates superficial growth graphene array;
Step 2, composite sulfur: the graphene array prepared and elemental sulfur are put into tube furnace by a certain percentage, is heated to 155 DEG C and obtains anode composite under inert gas shielding; Or elemental sulfur is heated to molten state, under inert gas shielding, the graphene array prepared is put into wherein, take out after keeping 5 ~ 10h and put into baking oven drying for standby;
Step 3: cladding titanium dioxide: the colloidal sol of preparation containing titanium ion, load prepared in step 2 there is the graphene array of sulphur to be placed in one standing 48h, then vacuumize 24h at 80 DEG C of temperature, form gel, again this gel is calcined 3h at 500 DEG C, form composite material.
A kind of secondary aluminium cell, comprising:
Anode composite described in (a) claim 1;
B () is containing aluminum honeycomb active material;
C () non-water is containing aluminium electrolyte.
Secondary aluminium cell described in scheme, is characterized in that, described containing aluminum honeycomb active material, includes but not limited to: metallic aluminium; Aluminium alloy, comprises the alloy containing at least one element be selected from Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Mn, Sn, Pb, Ma, Ga, In, Cr, Ge and Al.
Secondary aluminium cell described in scheme, is characterized in that, described non-water is organic salt-aluminum halide system containing aluminium electrolyte, and wherein the mol ratio of organic salt and aluminum halide is 1:1.1 ~ 3.0.
Secondary aluminium cell described in scheme, is characterized in that, the cation of described organic salt comprises imidazol ion, pyridinium ion, pyrrolidinium ion, piperidines ion, morpholinium ion, quaternary ammonium salt ion ， quaternary alkylphosphonium salt ion and tertiary sulfosalt ion; The anion of organic salt comprises Cl-, Br-, I-, PF6-, BF4-, CN-, SCN-, and [N (CF3SO2) 2]-, [N (CN) 2]-plasma.
Organic salt described in scheme-aluminum halide system, is characterized in that, described aluminum halide is the one in aluminium chloride, aluminium bromide or silver iodide.
Described in scheme, the preparation method of secondary aluminium cell is as follows: above-mentioned anode composite is dried be cut into 40mm wide × pole piece that the long 0.33mm of 15mm is thick, the barrier film thick with 0.16mm and be wound into battery core with aluminium flake as the negative pole that negative active core-shell material is made and load nickel plating box hat, reinject electrolyte, and secondary aluminium cell is made in sealing.
(3) beneficial effect
The invention provides a kind of based on the carbon sulphur anode composite of graphene array and the application in secondary aluminium cell thereof, compared with the existing technology there is following advantage: graphene array is orderly laminated structure and open bore structure, the three-dimensional network conducting matrix grain of the nano-scale formed, there is the advantages such as specific surface is huge, absorption affinity strong, good stability, electro transfer and charge transfer are fast, the excellent specific property of Graphene itself can be given full play to.The network configuration of its nano-scale has strong absorption confinement effect, with sulphur compound tense, more active material load byte not only can be provided, sulphur is fixed in further absorption, sulphur is connected with conducting matrix grain on nanoscale, greatly promote activity and the utilance of sulphur, but also can fetter and suppress the dissolving of the intermediate products such as Small molecular sulfide, thus slow down the loss of sulphur.The coated of titanium dioxide effectively prevent the direct contact of sulphur with electrolyte, polysulfide and reduzate dissolving in the electrolytic solution thereof can be reduced further, certain cushioning effect can also be played to the change in volume of sulphur in charge and discharge process simultaneously, the structural stability of effective raising electrode, and then the cycle performance improving battery.Owing to eliminating the interpolation of binding agent and conductive agent in electrode production process, can further improve the specific capacity of electrode.In addition owing to having stable three-dimensional conductive skeleton, without the need to adding conductive agent and binding agent in electrode preparation, specific capacity improves further.The secondary aluminium cell prepared thus, cost is low, safety and environmental protection, and specific capacity is high, good stability, and cycle performance is excellent.
(4) embodiment
Be described further below with reference to the technique effect of embodiment to design of the present invention, concrete structure and generation, to understand object of the present invention, characteristic sum effect fully.The following examples describe several execution mode of the present invention, and they are only illustrative, and nonrestrictive.
Embodiment 1
Be placed in the quartz glass tube of tube type resistance furnace using 30 μm of thick nickel collectors as substrate, pass into argon gas and the hydrogen mixed gas of 1000sccm, wherein hydrogen volume ratio is 1%, is warming up to 650 DEG C simultaneously; Regulation voltage is to 10kV, produce stable glow plasma, remove substrate surface impurity, after 10min, pass into 150sccm methane and 1350sccm argon gas, pass into steam simultaneously, control relative humidity 40%, then stop passing into argon gas and hydrogen mixed gas, reaction 20min, after end at reducing atmosphere borehole cooling to room temperature, obtained graphene array.
Embodiment 2
Adopt titanium substrate, enclose iron powder on its surface, be positioned in CVD (Chemical Vapor Deposition) chamber, sealing; In applying magnetic field, substrate transverse direction; magnetic field intensity is 0.01T, passes into 50sccm argon gas 30min to get rid of reaction indoor oxygen, heated substrate to 700 DEG C; then 100sccm methane is passed into; keep 1h, after reaction terminates, stop heating; close methane; under argon shield, be cooled to room temperature, take out product and adopt 1mol/L hydrochloric acid cleaning, dry obtained graphene array.
Embodiment 3
By the graphene array prepared and elemental sulfur in mass ratio 1:10 put into tube furnace, be heated to 155 DEG C, passing under condition of nitrogen gas, keep 10h, form the graphene array that load has sulphur.
Embodiment 4
Elemental sulfur is heated to molten state, under argon shield, the graphene array prepared is put into wherein, take out after keeping 8h, put into baking oven dry at 40 DEG C, form the graphene array that load has sulphur.
Embodiment 5
10ml butyl titanate is slowly instilled in 35ml absolute ethyl alcohol, with magnetic stirring apparatus strong stirring 10min, mix, form yellow clear solution A.4ml glacial acetic acid and 10ml distilled water are added in 35ml absolute ethyl alcohol, vigorous stirring mixes again, and with salt acid for adjusting pH value to pH≤3, under 30 DEG C of water-baths, slowly instills solution A (employing constant pressure funnel) while stirring wherein, obtained light yellow sol.Load there is the graphene array of sulphur to be placed in one standing 48h, then vacuumize 24h at 80 DEG C of temperature, form gel, then this gel is calcined 3h at 500 DEG C, form anode composite.
Embodiment 6
Anode composite prepared by embodiment 1,3,5 is dried be cut into 40mm wide × the thick pole piece of the long 0.33mm of 15mm is as positive pole, the glass fibre thick with 0.16mm be non-to be knitted barrier film and is wound into electric stamen with aluminium flake as the negative pole of negative active core-shell material and load nickel plating box hat, add aluminium chloride-triethylamine hydrochloride ionic liquid again, AA type cylinder secondary aluminium cell 1# is made in sealing.
Adopt and use the same method, prepare secondary aluminium cell 2# with material in embodiment 1,4,5; Secondary aluminium cell 3# is prepared with material in embodiment 2,3,5; Secondary aluminium cell 4# is prepared with material in embodiment 2,4,5.
Embodiment 7
Carry out charge and discharge cycles test to secondary aluminium cell 1#, 2#, 3#, 4# prepared in embodiment 6, carry out charging to 2.5V with 1C, 0.1C discharges, and discharge cut-off voltage is 1.2V.Test result is as following table 1.
Table 1 secondary aluminium cell
Although reference embodiment is to invention has been detailed description, but those skilled in the art is to be understood that, when not departing from the spirit and scope of the present invention described in appended claims and equivalent thereof, various amendment and replacement can be made to it.
Claims (7)
1., based on a carbon sulphur anode composite for graphene array, comprising:
A () graphene array, is characterized in that, described Graphene vertical-growth is on conductive substrates material;
(b) titanium dioxide; With
(c) sulphur.
2. as claimed in claim 1 based on the carbon sulphur anode composite of graphene array, it is characterized in that, described conductive substrates material includes but not limited to the metals or nonmetal such as carbon fiber, graphite, vitrescence carbon, titanium, nickel, stainless steel, iron, copper, zinc, lead, manganese, cadmium, gold, silver, platinum, tantalum, tungsten, conductive plastics, conductive rubber or highly doped silicon, and conductive substrates material is preferably titanium.
3., as claimed in claim 1 based on the carbon sulphur anode composite of graphene array, it is characterized in that, described sulphur by heat treated mode with nano-scale uniform load in conducting matrix grain in surperficial and hole.
4. as claimed in claim 1 based on the carbon sulphur anode composite of graphene array, it is characterized in that, described coated by titanium dioxide is in Graphene and sulphur skin.
5., as claimed in claim 1 based on the carbon sulphur anode composite of graphene array, it is characterized in that, comprise 10 ~ 15 wt% Graphenes, 15 ~ 25 wt% titanium dioxide and 60 ~ 70 wt% sulphur.
6. a preparation method for the carbon sulphur anode composite based on graphene array according to claim 1, is characterized in that, comprise the following steps:
Step 1, the preparation of graphene array: by plasma enhanced chemical vapor deposition in conductive substrates superficial growth graphene array;
Step 2, composite sulfur: the graphene array prepared and elemental sulfur are put into tube furnace by a certain percentage, is heated to 155 DEG C and obtains anode composite under inert gas shielding; Or elemental sulfur is heated to molten state, under inert gas shielding, the graphene array prepared is put into wherein, take out after keeping 5 ~ 10h and put into baking oven drying for standby;
Step 3: cladding titanium dioxide: the colloidal sol of preparation containing titanium ion, load prepared in step 2 there is the graphene array of sulphur to be placed in one standing 48h, then vacuumize 24h at 80 DEG C of temperature, form gel, again this gel is calcined 3h at 500 DEG C, form composite material.
7. a secondary aluminium cell, comprising:
Anode composite described in (a) claim 1;
B () is containing aluminum honeycomb active material;
C () non-water is containing aluminium electrolyte.
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Cited By (3)
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| CN105428593A (en) * | 2015-12-09 | 2016-03-23 | 江苏科技大学 | Safe secondary ion battery and preparation method |
| CN105977461B (en) * | 2016-05-30 | 2018-10-12 | 华南师范大学 | A kind of preparation method of Li-S battery anode composite materials |
| CN113921826A (en) * | 2021-10-09 | 2022-01-11 | 深圳石墨烯创新中心有限公司 | Vertical graphene/nano-silver composite material and preparation method and application thereof |
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