CN104269539A - Vertical-orientated graphene-sulphur composite cathode and preparation method thereof and secondary aluminum battery - Google Patents
Vertical-orientated graphene-sulphur composite cathode and preparation method thereof and secondary aluminum battery Download PDFInfo
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- CN104269539A CN104269539A CN201410519437.6A CN201410519437A CN104269539A CN 104269539 A CN104269539 A CN 104269539A CN 201410519437 A CN201410519437 A CN 201410519437A CN 104269539 A CN104269539 A CN 104269539A
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- graphene
- sulfur
- vertical orientated
- anode composite
- orientated 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
- 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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- 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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- 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 composite cathode for a secondary aluminum battery and a preparation method of the composite cathode. The composite cathode is formed by compounding vertical-orientated graphene and a sulphur-containing active substance, and has a three-dimensional network conductive framework, a conductive agent and a binding agent do not need to be added in a preparation process, procedures are simple and the cost is low. By adopting the composite cathode, the specific capacity, the stability and cyclicity of the secondary aluminum battery can be effectively improved.
Description
Technical field
The invention belongs to battery material scientific domain, relate to a kind of vertical orientated graphene-sulfur anode composite and preparation method thereof.The invention still further relates to a kind of secondary aluminium cell of this anode composite of application.
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, in the urgent need to exploitation electrokinetic cell and energy-storage battery.The theoretical volume specific capacity of aluminium is 8050mAh/cm
3, be 4 times of lithium, and chemical activity being stablized, is desirable negative material; The theoretical volume specific capacity of sulphur is 3467mAh/cm
3, be one of positive electrode that known energy density is the highest.The secondary cell formed with aluminium and sulphur is a kind of aboundresources, pollution-free, cheap, energy density is high, the energy storage system of use safety, is representative and the direction of secondary cell.
The electrical insulating property of sulphur causes the utilance of sulphur positive active material low, and the discharge and recharge of secondary aluminium-sulfur battery to react the Small molecular sulfur-based compound intermediate product produced soluble in electrolyte, thus cause irreversible loss and the capacity attenuation of active material, cause the self-discharge rate of battery high, cycle life is short, have impact on its large-scale application.In order to overcome the defect that elemental sulfur exists, normally elemental sulfur is loaded in the carbon-based material with high-specific surface area, high porosity and excellent conductive performance at present, form composite positive pole, to limit the various negative effects that sulfur-based compound in cyclic process dissolves in electrolyte and causes thus.
Graphene be a kind of by carbon atom according to sp
2the hexangle type of hybridized orbit composition is the two dimensional surface nano-carbon material of honeycomb lattice, only has a carbon atom thickness.Desirable single-layer graphene specific area is up to 2630m
2/ g, electron mobility is more than 20000cm
2/ Vs, also higher than carbon nano-tube, it also has high mechanical strength simultaneously, is one of desirable energy storage material.But for electrode material, Graphene is very easily reunited in preparation process, seriously reduce its actual specific area and the performance as active ingredient carriers, to be at present that disordered layer is folded be mostly piled up in substrate surface to disclosed Graphene electrodes material.In addition, the adding of inert matter conductive agent and binding agent in electrode, the energy density of electrode is also made significantly to be cut down.
Summary of the invention
(1) goal of the invention
The object of the invention is to improve existing carbon sulphur anode composite Problems existing and deficiency, a kind of vertical orientated graphene-sulfur anode composite is provided, in this positive pole, Graphene is three-dimensional network conducting matrix grain, is vertically grown in conductive substrates, therebetween the sulfur-bearing active material of composite nanostructure.Described orientation graphene-sulfur anode composite can give full play to the excellent specific property of Graphene itself, compare unordered stacking Graphene, the orderly laminated structure of vertical orientated Graphene and open bore structure, have the advantages such as specific surface is huge, absorption affinity strong, good stability, electro transfer and charge transfer are fast; The network configuration of its nano-scale not only can provide more active material load byte simultaneously, 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, and then promote cell integrated efficiency for charge-discharge and cycle performance; In addition, owing to eliminating the interpolation of binding agent and conductive agent in electrode production process, the specific capacity of electrode is further increased.
The object of the present invention is to provide a kind of vertical orientated graphene-sulfur anode composite and preparation method thereof.
The present invention also aims to provide a kind of secondary aluminium cell comprising vertical orientated graphene-sulfur anode composite.
(2) technical scheme
For achieving the above object, the present invention takes following technical scheme:
A kind of vertical orientated graphene-sulfur anode composite, is characterized in that, comprising:
(a) vertical orientated Graphene;
(b) conductive substrates; With
(c) sulfur-bearing active material.
Vertical orientated graphene-sulfur anode composite described in scheme, is characterized in that, Graphene vertically grows on conductive substrates surface.
Vertical orientated graphene-sulfur anode composite described in scheme, it is characterized in that, described conductive substrates includes but not limited to the metals or nonmetal such as carbon fiber, 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.
Vertical orientated graphene-sulfur anode composite described in scheme, is characterized in that, described sulfur-bearing active material comprises elemental sulfur or the organic compound containing S-S key.
Vertical orientated graphene-sulfur anode composite described in scheme, is characterized in that, described sulfur-bearing active material is distributed in orientation Graphene with nanoscale.
The preparation method of the vertical orientated graphene-sulfur anode composite described in scheme, is characterized in that, comprise the following steps:
Step 1, prepares vertical orientated Graphene: by plasma enhanced chemical vapor deposition at the vertical orientated Graphene of conductive substrates superficial growth;
Step 2, composite sulfur: adopt heat treated mode to be infiltrated by sulphur in the orientation graphene-structured prepared, preparation orientation graphene-sulfur anode composite; Or adopt the mode of electrochemical deposition to be carried on by elemental sulfur in the vertical orientated graphene-structured prepared.
Present invention also offers a kind of secondary aluminium cell, it is characterized in that:
(a) vertical orientated graphene-sulfur anode composite according to claim 1;
B () is containing aluminum honeycomb;
C () non-water is containing aluminium electrolyte.
Secondary aluminium cell described in scheme also can comprise the barrier film between positive pole and negative pole.Suitable solid porous separator material includes but not limited to: polyolefin is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.
Described in scheme containing aluminum honeycomb active material, include but not limited to: aluminum metal, such as aluminium foil and the aluminium that is deposited on base material; 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.
Non-water described in scheme is organic salt-aluminum halide system ionic liquid containing aluminium electrolyte, and wherein, the mol ratio of organic salt and aluminum halide is 1:1.1 ~ 3.0.
In organic salt described in scheme-aluminum halide system, the cation of 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
-, PF
6 -, BF
4 -, CN
-, SCN
-, [N (CF
3sO
2)
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: positive electrode is cut into 40mm wide × pole piece that 15mm length × 0.33mm 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 vertical orientated graphene-sulfur anode composite and comprise the secondary aluminium cell of this positive pole.Described positive pole is vertically to grow orientation Graphene in conductive substrates for three-dimensional network conducting matrix grain, and the sulfur-bearing active material of composite Nano size, compares with traditional electrode therebetween, this electrode preparation section is easy, with low cost, and without additional conductive agent and binding agent, doubly forthright good, energy density is high; Simultaneously due to its huge specific area, substantially increase the load capacity of sulphur, and the strong suction-operated of nano pore can realize fixing sulphur, suppress the loss of positive active material; In addition, 3-D nano, structure can provide effective conductive network and unobstructed ion channels, effectively can improve the specific capacity of secondary aluminium cell, stability and cyclicity.
(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:
(1) vertical orientated Graphene is prepared: 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, take out for subsequent use.
(2) prepare vertical orientated graphene-sulfur composite material: by the orientation Graphene prepared and elemental sulfur in mass ratio 1:10 put into tube furnace, be heated to 155 DEG C under nitrogen atmosphere and form vertical orientated graphene-sulfur composite materials.
(3) secondary aluminium cell preparation method: orientation graphene-sulfur composite positive pole is cut into 40mm wide × pole piece that 15mm length × 0.33mm is thick, the glass fibre thick with 0.16mm is non-to be knitted barrier film and is wound into battery core loading nickel plating box hat with aluminium flake as the negative pole that negative active core-shell material is made, reinject aluminium chloride-triethylamine hydrochloride ionic liquid, and AA type cylinder secondary aluminium cell is made in sealing.
During battery charging and discharging loop test, carry out charging to 2.5V with 1C, 0.1C discharges, and discharge cut-off voltage is 1.2V.Battery open circuit voltage is 1.77V, and discharge capacity is 586mAh first, and after 50 charge and discharge cycles, capability retention is 68.4%.
Embodiment 2:
Prepare vertical orientated Graphene method with embodiment 1.
Prepare vertical orientated graphene-sulfur composite material: first configure the 0.05mol/L Na2S2O3 aqueous solution, below hydrochloric acid to pH value to 4 is dripped in this solution, then with orientation Graphene be work electrode, saturated calomel electrode is reference electrode, platinum electrode is to electrode, adopt cyclic voltammetry composite sulfur, deposition voltage is 0.6V, reaction time 1h; Finally take out product, through distilled water flushing, dry obtained orientation graphene-sulfur composite material.
Secondary aluminium cell preparation method and method of testing are with embodiment 1.
Battery open circuit voltage is 1.75V, and discharge capacity is 565mAh first, and after 50 charge and discharge cycles, capability retention is 67.2%.
Embodiment 3:
(1) prepare vertical orientated Graphene: adopt the stainless steel-based end, 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 for standby;
Prepare vertical orientated graphene-sulfur composite process with embodiment 2.
Secondary aluminium cell preparation method and method of testing are with embodiment 1.
Battery open circuit voltage is 1.76V, and discharge capacity is 560mAh first, and after 50 charge and discharge cycles, capability retention is 66.1%.
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. a vertical orientated graphene-sulfur anode composite, is characterized in that, comprising:
(a) vertical orientated Graphene;
(b) conductive substrates; With
(c) sulfur-bearing active material.
2. vertical orientated graphene-sulfur anode composite as claimed in claim 1, is characterized in that, Graphene vertically grows on conductive substrates surface.
3. vertical orientated graphene-sulfur anode composite as claimed in claim 1, it is characterized in that, described conductive substrates includes but not limited to the metals or nonmetal such as carbon fiber, 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.
4. vertical orientated graphene-sulfur anode composite as claimed in claim 1, is characterized in that, described sulfur-bearing active material comprises elemental sulfur or the organic compound containing S-S key.
5. vertical orientated graphene-sulfur anode composite as claimed in claim 1, is characterized in that, described sulfur-bearing active material is distributed in orientation Graphene with nanoscale.
6. the preparation method of vertical orientated graphene-sulfur anode composite according to claim 1, is characterized in that, comprise the following steps:
Step 1, prepares vertical orientated Graphene: by plasma enhanced chemical vapor deposition at the vertical orientated Graphene of conductive substrates superficial growth;
Step 2, composite sulfur: adopt heat treated mode to be infiltrated by sulphur in the orientation graphene-structured prepared, preparation orientation graphene-sulfur anode composite; Or adopt the mode of electrochemical deposition to be carried on by elemental sulfur in the vertical orientated graphene-structured prepared.
7. a secondary aluminium cell, comprises positive pole, negative pole and electrolyte, it is characterized in that:
(a) vertical orientated graphene-sulfur anode composite according to claim 1;
B () is containing aluminum honeycomb;
C () non-water is containing aluminium electrolyte.
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| CN201410519437.6A CN104269539A (en) | 2014-09-30 | 2014-09-30 | Vertical-orientated graphene-sulphur composite cathode and preparation method thereof and secondary aluminum battery |
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| CN201410519437.6A CN104269539A (en) | 2014-09-30 | 2014-09-30 | Vertical-orientated graphene-sulphur composite cathode and preparation method thereof and secondary aluminum battery |
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Cited By (14)
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|---|---|---|---|---|
| CN105428594A (en) * | 2015-12-09 | 2016-03-23 | 江苏科技大学 | High-performance battery and preparation method |
| CN105529492A (en) * | 2015-12-09 | 2016-04-27 | 江苏科技大学 | Secondary ion battery adopting pure aluminium as negative electrode, and preparation method |
| CN105826081A (en) * | 2016-06-13 | 2016-08-03 | 东南大学 | Titanium-dioxide-based nanorod array counter electrode and preparation method and application thereof |
| US20160240841A1 (en) * | 2015-02-18 | 2016-08-18 | Hui He | Pre-sulfurized cathode for alkali metal-sulfur secondary battery and production process |
| CN106159316A (en) * | 2016-09-08 | 2016-11-23 | 海悦高科电池技术（大连）有限公司 | A kind of lithium ion cell positive collector and comprise the battery of this collector |
| CN108666531A (en) * | 2018-04-27 | 2018-10-16 | 西安理工大学 | A kind of electrochemical preparation method of graphene/sulphur positive plate |
| CN109950479A (en) * | 2017-12-21 | 2019-06-28 | 中国科学院上海硅酸盐研究所 | A kind of three-dimensional porous structure graphene/sulfur composite positive electrode material and preparation method thereof |
| CN109950544A (en) * | 2017-12-21 | 2019-06-28 | 中国科学院上海硅酸盐研究所 | It is a kind of to prepare graphene modified collector and preparation method thereof using plasma auxiliary chemical vapor deposition |
| CN110459732A (en) * | 2019-08-14 | 2019-11-15 | 上海昱瓴新能源科技有限公司 | A kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece and preparation method thereof and lithium ion battery |
| CN111969186A (en) * | 2020-07-22 | 2020-11-20 | 自贡兴川储能技术有限公司 | Silicon-carbon film cathode with graphene as framework and preparation method thereof |
| US11038164B2 (en) | 2015-02-18 | 2021-06-15 | Global Graphene Group, Inc. | Alkali metal-sulfur secondary battery containing a pre-sulfurized cathode and production process |
| CN113178555A (en) * | 2021-04-20 | 2021-07-27 | 中国航发北京航空材料研究院 | Preparation method of iron disulfide cathode composite material |
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| CN116154098A (en) * | 2023-04-18 | 2023-05-23 | 南昌航空大学 | High-conductivity electrode structure and preparation method thereof |
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| US11038164B2 (en) | 2015-02-18 | 2021-06-15 | Global Graphene Group, Inc. | Alkali metal-sulfur secondary battery containing a pre-sulfurized cathode and production process |
| US20160240841A1 (en) * | 2015-02-18 | 2016-08-18 | Hui He | Pre-sulfurized cathode for alkali metal-sulfur secondary battery and production process |
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| CN105529492A (en) * | 2015-12-09 | 2016-04-27 | 江苏科技大学 | Secondary ion battery adopting pure aluminium as negative electrode, and preparation method |
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| CN105826081A (en) * | 2016-06-13 | 2016-08-03 | 东南大学 | Titanium-dioxide-based nanorod array counter electrode and preparation method and application thereof |
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| CN109950479A (en) * | 2017-12-21 | 2019-06-28 | 中国科学院上海硅酸盐研究所 | A kind of three-dimensional porous structure graphene/sulfur composite positive electrode material and preparation method thereof |
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| CN108666531A (en) * | 2018-04-27 | 2018-10-16 | 西安理工大学 | A kind of electrochemical preparation method of graphene/sulphur positive plate |
| CN110459732A (en) * | 2019-08-14 | 2019-11-15 | 上海昱瓴新能源科技有限公司 | A kind of silicon/graphene/carbon composite cellulosic membrane cathode pole piece and preparation method thereof and lithium ion battery |
| CN110459732B (en) * | 2019-08-14 | 2021-04-09 | 上海昱瓴新能源科技有限公司 | Silicon/graphene/carbon composite fiber membrane negative electrode plate, preparation method thereof and lithium ion battery |
| CN111969186A (en) * | 2020-07-22 | 2020-11-20 | 自贡兴川储能技术有限公司 | Silicon-carbon film cathode with graphene as framework and preparation method thereof |
| CN111969186B (en) * | 2020-07-22 | 2021-09-28 | 自贡兴川储能技术有限公司 | Silicon-carbon film cathode with graphene as framework and preparation method thereof |
| CN113178555A (en) * | 2021-04-20 | 2021-07-27 | 中国航发北京航空材料研究院 | Preparation method of iron disulfide cathode composite material |
| CN114975979A (en) * | 2022-07-06 | 2022-08-30 | 广东墨睿科技有限公司 | C/G/CNT-S negative electrode material, preparation method and application |
| CN114975979B (en) * | 2022-07-06 | 2024-01-26 | 广东墨睿科技有限公司 | C/G/CNT-S negative electrode material, preparation method and application |
| CN116154098A (en) * | 2023-04-18 | 2023-05-23 | 南昌航空大学 | High-conductivity electrode structure and preparation method thereof |
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Application publication date: 20150107 |