CN104157878A - Carbon nanotube array-nano polyaniline-sulfur composite positive electrode, and preparation method and application thereof - Google Patents
Carbon nanotube array-nano polyaniline-sulfur composite positive electrode, and preparation method and application thereof Download PDFInfo
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- CN104157878A CN104157878A CN201410418161.2A CN201410418161A CN104157878A CN 104157878 A CN104157878 A CN 104157878A CN 201410418161 A CN201410418161 A CN 201410418161A CN 104157878 A CN104157878 A CN 104157878A
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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Abstract
The invention discloses a composite positive electrode for a secondary aluminum battery, wherein the composite positive electrode is prepared by compounding a carbon nanotube array, nano polyaniline and a sulfur-containing active material and has a three-dimensional network conductive skeleton. The electrode has the advantages of simple preparation method, low cost, no superaddition of conductive agents and binders, and high energy density. The secondary aluminum battery applying the composite positive electrode is high in capacity and good in cycle performance.
Description
Technical field
The invention belongs to battery material scientific domain, relate to a kind of carbon nano pipe array-nano polyaniline-sulphur 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 mankind are more and more higher to the battery performance demand of supporting power supply, 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 is stable, 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 forming with aluminium and sulphur is a kind of aboundresources, pollution-free, cheap, energy density is high, use safe energy storage system, is representative and the direction of secondary cell.
The electrical insulating property of sulphur causes the utilance of sulphur positive active material low, and secondary aluminium-sulfur battery to discharge and recharge the little molecular sulfur based compound intermediate product that reaction produces soluble in electrolyte, thereby cause irreversible loss and the capacity attenuation of active material, cause the self-discharge rate of battery high, cycle life is short, has affected its large-scale application.The defect existing in order to overcome elemental sulfur, normally elemental sulfur is loaded at present there is high-specific surface area, in the carbon element class material and conducting polymer of high porosity and excellent conductive performance, form composite positive pole, to limit the various negative effects that in cyclic process, sulfur-based compound dissolves in electrolyte and causes thus.
Wherein, polyaniline have the ability of electric charge of storage high, to oxygen and the advantage such as water stability is good, chemical property is good, density is little, and there is reversible oxidation/reduction characteristic, in composite electrode, not only can be used as conductive matrices but also can be used as active material, be used to the electrode material of high-polymer lithium battery and solar cell etc., and the polyaniline structure of nanostructure is regular, specific area is large, has more excellent physical and chemical performance.Carbon nano-tube has the advantages such as good conductivity, draw ratio are large, between them, can be barricaded as natural conductive network by bridge, is conducive to electrical conductivity and ion diffusion.But the carbon nano-tube of unordered accumulated growth presents certain aggregate structure, be wound around seriously, charge transfer efficiency is very low.And it is mainly by the absorption sulfur loaded of carbon nano tube surface, sulfur content in composite material is low, skewness, can enter sulphur in carbon pipe little, easily dissolves in electrolyte, cause the loss of active material, fail to give full play to carbon nano-tube tubular material advantage.In addition, inert matter conductive agent in electrode, adding of binding agent, also makes the energy density of electrode significantly be cut down.
Summary of the invention
(1) goal of the invention
The object of the invention is to improve the problem and shortage that existing carbon sulphur composite material exists, a kind of carbon nano pipe array-nano polyaniline-sulphur composite material is provided, it classifies skeleton as with carbon nano-pipe array, is compounded with sulphur and polyaniline therebetween, and polyaniline and sulphur are nanostructure.
Compare unordered carbon nano-tube, favorable orientation, arrange in order, purity is high, be vertically attached to the suprabasil carbon nano pipe array of solid conduction, with the three-dimensional network skeleton structure of its orderly pore structure and the nanotubes height of formation ordered nano yardstick that aligns, have that specific surface is huge, absorption affinity strong, good stability, electronics shifts and the advantage such as charge transfer is fast efficiently.With polyaniline compound tense, polyaniline is uniformly distributed in order with nano shape in three-dimensional network skeleton, closely compound with carbon back skeleton, further strengthens its conductivity.
In the time that heat treated temperature exceedes the fusing point of active material sulphur and polyaniline, polyaniline is closely bonded in the sulphur of melting on conducting matrix grain.And the network configuration of nano-scale not only can further be adsorbed fixing sulphur, sulphur is joined 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 little molecular sulfur compound, thereby slow down the loss of sulphur.Meanwhile, polyaniline supplements as active material, also can promote the capacity of electrode material, and then promote cell integrated efficiency for charge-discharge and cycle performance.
In addition, have the conducting matrix grain and the polyaniline that has cementation of high conductivity in anode composite, can avoid using traditional binding agent and conductive agent, can significantly improve the specific capacity of electrode, the energy density of electrode is also higher.
The object of the present invention is to provide a kind of carbon nano pipe array-nano polyaniline-sulphur anode composite and preparation method thereof.
The present invention also aims to provide a kind of secondary aluminium cell that comprises carbon nano pipe array-nano polyaniline-sulphur anode composite.
(2) technical scheme
For achieving the above object, the present invention takes following technical scheme.
A kind of carbon nano pipe array-nano polyaniline-sulphur anode composite, comprising:
A) carbon nano pipe array;
B) conductive substrates;
C) nano polyaniline; With
D) sulfur-bearing active material.
Carbon nano pipe array-nano polyaniline-sulphur composite material described in scheme, is characterized in that, carbon nano pipe array and conductive substrates vertical connection form three-dimensional conductive network skeleton.
Carbon nano pipe array-nano polyaniline-sulphur composite material described in scheme, it is characterized in that, described conductive substrates 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.
Carbon nano pipe array-nano polyaniline-sulphur composite material described in scheme, is characterized in that, described polyaniline is to form carbon nano pipe array-nano polyaniline composite construction with nanoscale enveloped carbon nanometer tube array.
Carbon nano pipe array-nano polyaniline-sulphur composite material described in scheme, is characterized in that, described sulfur-bearing active material is to be distributed in polyaniline-carbon nano pipe array composite construction with nanoscale.
Carbon nano pipe array-nano polyaniline-sulphur composite material described in scheme, is characterized in that, described sulfur-bearing active material is elemental sulfur or the organic compound that contains S-S key.
Carbon nano pipe array-nano polyaniline-sulphur composite material described in scheme, is characterized in that, comprises 70 ~ 80% sulphur, 10 ~ 30% polyaniline and 10 ~ 15% carbon nano pipe array, and described is mass percentage content.
The preparation method of the carbon nano pipe array-nano polyaniline-sulphur composite material described in scheme, is characterized in that, comprises the following steps:
Step 1, adopts physics or chemical vapour deposition technique in conductive substrates, to prepare carbon nano pipe array;
Step 2, composite polyphenylene amine: configuration 0.5mol/L sulfuric acid solution, to the aniline monomer that adds 0.2mol/L in this solution, passes into nitrogen and stir stand-by; Then classify work electrode, saturated calomel electrode as reference electrode, platinum electrode are as to electrode taking the carbon nano-pipe array preparing, adopt cyclic voltammetry to prepare polyaniline, its potential range is 0.6V-0.8V, reaction time 1h; Finally take out product, through distilled water flushing, dry, obtain carbon nano pipe array-polyaniline composite material;
Step 3, composite sulfur: by the carbon nano pipe array-polyaniline composite material preparing and sulfur-bearing active material in mass ratio 1:5 ~ 1:20 mix, under inert gas shielding, be heated to 155 ~ 300 DEG C and form carbon nano pipe array-nano polyaniline-sulphur composite materials; Or sulfur-bearing active material is heated to molten state; under inert gas shielding, the carbon nano pipe array-polyaniline composite material preparing is put into wherein; keep taking out after 5 ~ 10h that to put into baking oven dry, form carbon nano pipe array-nano polyaniline-sulphur composite material.
The present invention also provides a kind of secondary aluminium cell, comprising:
(a) carbon nano pipe array-nano polyaniline claimed in claim 1-sulphur anode composite;
(b) containing aluminium negative pole;
(c) non-water is containing aluminium electrolyte.
Described secondary aluminium cell also comprises the barrier film between positive pole and negative pole.Suitable solid porous diaphragm material includes but not limited to: polyolefin is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.Other example that is applicable to diaphragm material of the present invention is to comprise micropore pseudobochmite layer, and it can be the form of free-standing film or be coated directly onto on an electrode.
Described in scheme containing aluminium negative active core-shell material, include but not limited to: aluminum metal, for example aluminium foil and be deposited on the aluminium on base material; Aluminium alloy, comprises and contains at least one element of being selected from Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Mn, Sn, Pb, Ma, Ga, In, Cr, Ge and the alloy of 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-aluminum halide system described in scheme, the cation of organic salt comprises imidazol ion, pyridinium ion, pyrroles's ion, piperidines ion, morpholine 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-aluminum halide system described in scheme, 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: by positive electrode be cut into 40mm wide × pole piece that 15mm length × 0.33mm is thick, be wound into battery core with the thick barrier film of 0.16mm and the negative pole made as negative active core-shell material with aluminium flake and pack nickel plating box hat into, the electrolyte that reinjects, secondary aluminium cell is made in sealing.
(3) beneficial effect
The invention provides a kind of carbon nano pipe array-nano polyaniline-sulphur anode composite, classify skeleton with vertical-growth as at the lip-deep carbon nano-pipe array of conducting base, the polyaniline of composite Nano size and sulfur-bearing active material therebetween, has following beneficial effect:
A) electrode preparation method is simple to operate, cost is low, and prepared electrode is without additional conductive agent and binding agent, and electrode active material contacts with electric conductor on nanoscale, and contact resistance is little, and doubly forthright good, energy density is high.
B) preparation process green safety, does not use poisonous reducing agent and oxidant, has avoided the pollution to composite material and environment.
C) prepared anodal good conductivity, the specific area of this composite material is large, and sulphur load capacity improves greatly, and due to nano pore suction-operated, also can realize fixing to sulphur; 3-D nano, structure can provide effective conductive network and unobstructed ion channel simultaneously; Can effectively improve specific capacity, stability and the cyclicity of secondary aluminium cell.
(4) embodiment
Below with reference to embodiment, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object of the present invention, feature and effect.The following examples have been described several execution mode of the present invention, and they are only illustrative, and nonrestrictive.
Embodiment 1
(1) prepare carbon nano pipe array: taking conductive paper of carbon fiber as substrate, Fe (NO
3)
3for catalyst, be coated in advance carbon paper surface, taking methane as carbon source, nitrogen is protection gas, adopts chemical vapour deposition technique (CVD) to prepare carbon nano pipe array.
(2) composite polyphenylene amine: configuration 0.5mol/L sulfuric acid solution, to the aniline monomer that adds 0.2mol/L in this solution, passes into nitrogen and stir; Carbon nano pipe array is placed in to aniline-sulfuric acid solution and soaks 20min, then classify work electrode, saturated calomel electrode as reference electrode, platinum electrode are as to electrode taking carbon nano-pipe array, adopt cyclic voltammetry to prepare polyaniline, electro-deposition voltage is 0.7V, reaction time 1h; Finally take out carbon nano pipe array, through distilled water flushing, drying for standby.
(3) composite sulfur: by be compounded with the carbon nano pipe array of polyaniline and elemental sulfur in mass ratio 1:10 put into tube furnace, under nitrogen atmosphere, be heated to 155 DEG C and form carbon nano pipe array-nano polyaniline-sulphur composite materials.
(4) secondary aluminium cell preparation method: taking carbon nano pipe array-nano polyaniline-sulphur composite material as anodal, by positive electrode be cut into 40mm wide × pole piece that 15mm length × 0.33mm is thick, be wound into battery core with the thick non-negative pole of knitting barrier film and make as negative active core-shell material with aluminium flake of glass fibre of 0.16mm and pack nickel plating box hat into, aluminium chloride-triethylamine hydrochloride ionic liquid that reinjects, AA type cylinder secondary aluminium cell is made in sealing.
When battery charging and discharging loop test, charge to 2.5V with 1C, 0.1C electric discharge, discharge cut-off voltage is 1.2V.Battery open circuit voltage is 1.77V, and discharge capacity is 865mAh first, and after 50 charge and discharge cycles, capability retention is 81.2%.
Embodiment 2
The preparation of carbon nano-tube array composite material: taking stainless steel as substrate, Fe is catalyst, taking ethene as carbon source, hydrogen and nitrogen are carrier gas, adopt chemical vapour deposition technique (CVD) to prepare carbon nano pipe array.
Compound and the battery preparation method of polyaniline and sulphur and method of testing are with embodiment 1.
Battery open circuit voltage is 1.75V, and discharge capacity is 860mAh first, and after 50 charge and discharge cycles, capability retention is 80.6%.
Embodiment 3
The compound same embodiment 1 of the preparation of carbon nano pipe array and polyaniline.
Composite sulfur: sulfur-bearing active material is heated to molten state; under nitrogen protection, the carbon nano pipe array-polyaniline composite material preparing is put into wherein; keep taking out after 10h that to put into baking oven dry, form carbon nano pipe array-nano polyaniline-sulphur composite material.
The preparation of battery and method of testing are with embodiment 1.
Battery open circuit voltage is 1.80V, and discharge capacity is 880mAh first, and after 50 charge and discharge cycles, capability retention is 82.4%.
Although the present invention is described in detail with reference to embodiment, but those skilled in the art is to be understood that, in the case of the spirit and scope of the present invention described in not departing from appended claims and equivalent thereof, can make various amendments and replacement to it.
Claims (9)
1. carbon nano pipe array-nano polyaniline-sulphur anode composite, comprising:
A) carbon nano pipe array;
B) conductive substrates;
C) nano polyaniline; With
D) sulfur-bearing active material.
2. carbon nano pipe array-nano polyaniline as claimed in claim 1-sulphur composite material, is characterized in that, carbon nano pipe array and conductive substrates vertical connection form three-dimensional conductive network skeleton.
3. carbon nano pipe array-nano polyaniline as claimed in claim 1-sulphur composite material, it is characterized in that, described conductive substrates 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.
4. carbon nano pipe array-nano polyaniline as claimed in claim 1-sulphur composite material, is characterized in that, described polyaniline is to form carbon nano pipe array-nano polyaniline composite construction with nanoscale enveloped carbon nanometer tube array.
5. carbon nano pipe array-nano polyaniline as claimed in claim 1-sulphur composite material, is characterized in that, described sulfur-bearing active material is to be distributed in polyaniline-carbon nano pipe array composite construction with nanoscale.
6. carbon nano pipe array-nano polyaniline as claimed in claim 1-sulphur composite material, is characterized in that, described sulfur-bearing active material is elemental sulfur or the organic compound that contains S-S key.
7. carbon nano pipe array-nano polyaniline as claimed in claim 1-sulphur composite material, is characterized in that, comprises 60 ~ 80% sulphur, 10 ~ 30% polyaniline and 10 ~ 15% carbon nano pipe array, and described is mass percentage content.
8. the preparation method of carbon nano pipe array-nano polyaniline claimed in claim 1-sulphur composite material, is characterized in that, comprises the following steps:
Step 1, adopts physics or chemical vapour deposition technique in conductive substrates, to prepare carbon nano pipe array;
Step 2, composite polyphenylene amine: configuration 0.5mol/L sulfuric acid solution, to the aniline monomer that adds 0.2mol/L in this solution, passes into nitrogen and stir stand-by; Then classify work electrode, saturated calomel electrode as reference electrode, platinum electrode are as to electrode taking the carbon nano-pipe array preparing, adopt cyclic voltammetry to prepare polyaniline, its potential range is 0.6V ~ 0.8V, reaction time 1h; Finally take out product, through distilled water flushing, dry, obtain carbon nano pipe array-polyaniline composite material;
Step 3, composite sulfur: by the carbon nano pipe array-polyaniline composite material preparing and sulfur-bearing active material in mass ratio 1:5 ~ 1:20 mix, under inert gas shielding, be heated to 155 ~ 300 DEG C and form carbon nano pipe array-nano polyaniline-sulphur composite materials; Or sulfur-bearing active material is heated to molten state; under inert gas shielding, the carbon nano pipe array-polyaniline composite material preparing is put into wherein; keep taking out after 5 ~ 10h that to put into baking oven dry, form carbon nano pipe array-nano polyaniline-sulphur composite material.
9. a secondary aluminium cell, comprising:
A) carbon nano pipe array-nano polyaniline claimed in claim 1-sulphur anode composite;
B) containing aluminium negative pole;
C) non-water is containing aluminium electrolyte.
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Cited By (5)
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| CN106058151A (en) * | 2016-08-12 | 2016-10-26 | 深圳博磊达新能源科技有限公司 | Carbon nanotube/nano sulfur/polyaniline composite electrode, and preparation method and application thereof |
| CN106356555A (en) * | 2016-11-02 | 2017-01-25 | 武汉理工大学 | Preparation method of carbon nanotube/conductive polymer double-modified sulfur composite cathode material |
| CN109802105A (en) * | 2018-12-24 | 2019-05-24 | 肇庆市华师大光电产业研究院 | A kind of polyaniline nano tube packaging metal nanometer line array/sulphur composite material, controllable method for preparing and application |
| CN111261863A (en) * | 2020-02-03 | 2020-06-09 | 吉林建筑大学 | Three-dimensional nickel nanotube array, preparation method thereof, lithium ion battery and application |
| CN113823802A (en) * | 2020-12-02 | 2021-12-21 | 湖南聚锂能源科技有限公司 | Flexible battery and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058151A (en) * | 2016-08-12 | 2016-10-26 | 深圳博磊达新能源科技有限公司 | Carbon nanotube/nano sulfur/polyaniline composite electrode, and preparation method and application thereof |
| CN106356555A (en) * | 2016-11-02 | 2017-01-25 | 武汉理工大学 | Preparation method of carbon nanotube/conductive polymer double-modified sulfur composite cathode material |
| CN106356555B (en) * | 2016-11-02 | 2019-09-10 | 武汉理工大学 | The preparation method of the sulphur composite positive pole of the dual modification of carbon nano tube/conducting polymer |
| CN109802105A (en) * | 2018-12-24 | 2019-05-24 | 肇庆市华师大光电产业研究院 | A kind of polyaniline nano tube packaging metal nanometer line array/sulphur composite material, controllable method for preparing and application |
| CN111261863A (en) * | 2020-02-03 | 2020-06-09 | 吉林建筑大学 | Three-dimensional nickel nanotube array, preparation method thereof, lithium ion battery and application |
| CN113823802A (en) * | 2020-12-02 | 2021-12-21 | 湖南聚锂能源科技有限公司 | Flexible battery and preparation method and application thereof |
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Application publication date: 20141119 |