CN104332590A - Sulfur-base composite positive electrode based on carbon nanotube arrays, preparation method and application thereof - Google Patents

Sulfur-base composite positive electrode based on carbon nanotube arrays, preparation method and application thereof Download PDF

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Publication number
CN104332590A
CN104332590A CN201410435975.7A CN201410435975A CN104332590A CN 104332590 A CN104332590 A CN 104332590A CN 201410435975 A CN201410435975 A CN 201410435975A CN 104332590 A CN104332590 A CN 104332590A
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carbon nano
pipe array
sulfur
nano pipe
polyacrylonitrile
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CN201410435975.7A
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赵宇光
钟毓娟
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NANJING ZHONGCHU NEW ENERGY Co Ltd
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NANJING ZHONGCHU NEW ENERGY Co Ltd
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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
    • 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
    • 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
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 sulfur-base composite positive electrode based on carbon nanotube arrays, a preparation method thereof, and an application of the positive electrode in secondary aluminum battery. The positive electrode is prepared by compounding carbon nanotube arrays and sulfur-containing active substances and is characterized in that the carbon nanotube arrays vertically grow on a electro-conductive substrate as an electro-conductive skeleton, and sulfur(simple substance)-containing substances and polyacrylonitrile composite material are all loaded on the electro-conductive skeleton. The composite positive electrode does not need any conductive agent or binding agent, the procedure is simple, the cost is low, the material morphology is controllable, the contact resistance is small, and the energy density is high. Moreover the secondary aluminum battery using the composite positive electrode has the advantages of large capacity and good circulation performance.

Description

Based on the sulfur-based composite anode of carbon nano pipe array, preparation method and application
Technical field
The invention belongs to battery material scientific domain, relate to a kind of sulfur-based composite anode based on carbon nano pipe array and preparation method thereof, the invention still further relates to a kind of secondary aluminium cell comprising this anode composite.
Background technology
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 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 produces self discharge reaction and be deposited on negative pole and make the problems such as its passivation, finally causes that sulphur active material utilization is low, capacity attenuation is rapid, cycle performance of battery is poor.
In order to reduce these unfavorable factors, modal strategy is exactly by being distributed to by elemental sulfur in porous carbon sill, stronger affinity interaction is produced among the active porosity that element sulphur fully embeds carbon matrix with carbon matrix, form sulphur-carbon composite electrode material, to obtain higher capacitance and excellent cycle characteristics.Wherein, carbon nano-tube has the advantages such as good conductivity, draw ratio be large, can be barricaded as natural conductive network by bridge, be conducive to electrical conductivity and ion diffuse between them.But traditional carbon nano-tube is unordered reunion shape, mainly through the absorption carriage sulphur of carbon nano tube surface, the sulfur content in composite material is low, skewness.During discharge and recharge, a large amount of sulphur directly can dissolve in electrolyte from the surface of carbon nano-tube, causes the loss of active material, and battery energy density is difficult to improve.And inert matter conductive agent in electrode, adding of binding agent, also make the energy density of electrode significantly be cut down.But be subject to 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, these materials shortcoming such as still existence and stability is poor, sulfur content is low and in practical application processing characteristics is limited.Therefore, 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.
Because the mutual absorption affinity of the crosslinked action in sulphur-carbon chemical bond than sulphur and carbon matrix surface is eager to excel, organic sulfur compound is used to prepare sulfur-bearing char-forming material to obtain the sulphur positive electrode of high stability as carbon matrix precursor.In the secondary aluminium-sulfur battery that patent CN200910234924.7 provides, polyacrylonitrile mixes with sulphur and heats cyclization occurs, and the sulfurized polyacrylonitrile of formation is that one has long-range π key conjugated system polymer, and this polymer has higher specific capacity.But because the above-mentioned cyclisation degree preparing sulfurized polyacrylonitrile is not high, the conjugatedπbond playing electric action formed is less, thus makes the conductivity of sulfurized polyacrylonitrile lower, causes the utilance of sulphur positive active material low.
Summary of the invention
(1) goal of the invention
For the problems referred to above and deficiency, the object of the present invention is to provide a kind of sulfur-based composite anode based on carbon nano pipe array, described positive pole arranges as conducting matrix grain with the carbon nano-pipe array of vertical-growth in conductive substrates, adopt the mode of in-situ polymerization at its Surface coating polyacrylonitrile, again in the mode of hot melt infiltration by the load of active material sulphur wherein, advantages such as having that conductivity is good, capacity is high, have extended cycle life, the excellent and cost of comprehensive electrochemical is low.
In order, draw ratio is high, favorable orientation, purity are high in carbon nano pipe array arrangement, avoids the inferior positions such as the sulphur load that the carbon nano-tube of applying unordered accumulation produces is uneven, contact resistance is high, can give full play to carbon nano-tube tubular material advantage.With polyacrylonitrile compound tense, polyacrylonitrile is uniformly distributed in order with nano shape in its three-dimensional network skeleton, and the cooperative effect of the two can strengthen positive conductive further, promotes electrode capacity.
When adopting hot melt osmotic load active material sulphur, more load byte can be provided because carbon nano pipe array has huge specific area on the one hand, greatly can improve the load capacity of sulphur; And due between its orderly pore structure and pipe space form three-dimensional conductive network channel be nanoscale, sulphur can be made dispersed with nano shape, with the tight compound of conducting matrix grain, effectively improve the reactivity of sulphur, simultaneously, to being filled in nanotube and the sulphur in space between pipe, the major diameter of the orderly hole of these nanoscales and network channel and nanotube can produce the constraint than common carbon-based material more " long-range ", the stripping of sulphur in battery charge and discharge process can be suppressed further, thus slow down the loss of sulphur.On the other hand, polyacrylonitrile can strengthen its conductivity in conjunction with the nano-sulfur based composites of formation on a molecular scale further with sulphur, and the formation of part sulphur participation binding reaction has long-range π key conjugated system polymer, greatly improves its specific capacity.
In addition, due to without additional conductive agent and binding agent, can significantly improve the specific capacity of electrode, the energy density of electrode is also higher.
The present invention also aims to provide a kind of sulfur-based composite anode based on carbon nano pipe array and preparation method thereof.
The present invention also aims to provide a kind of secondary aluminium cell comprising this sulfur-based composite anode.
(2) technical scheme
For achieving the above object, the invention provides following technical scheme:
Based on a sulfur-based composite anode for carbon nano pipe array, comprising:
A () carbon nano pipe array, is characterized in that, described carbon nano pipe array vertical-growth is in conductive substrates;
(b) polyacrylonitrile; With
C () sulphur, is characterized in that, described sulphur is elemental sulfur.
The sulfur-based composite anode based on carbon nano pipe 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.
The sulfur-based composite anode based on carbon nano pipe array described in scheme, is characterized in that, in described carbon nano pipe array, the caliber of carbon nano-tube is 1 ~ 50nm, pipe range 1 ~ 2000nm, tube pitch 2 ~ 100nm.
The sulfur-based composite anode based on carbon nano pipe array described in scheme, is characterized in that, described polyacrylonitrile is coated on carbon nano pipe array surface with nano-scale.
The sulfenyl combination electrode based on carbon nano pipe array described in scheme, is characterized in that, described sulphur by heat treated mode with nano-scale uniform load at carbon nano pipe array-polyacrylonitrile material.
The sulfur-based composite anode based on carbon nano pipe array described in scheme, is characterized in that, comprises 1 ~ 20wt% carbon nano pipe array, 30 ~ 50wt % polyacrylonitrile, 30-60 wt% sulphur.
The preparation method of the sulfur-based composite anode based on carbon nano pipe array described in scheme, is characterized in that, comprise the following steps:
Step 1, the preparation of carbon nano pipe array: adopt physics or chemical vapour deposition technique at conductive substrates surface vertical-growth carbon nano pipe array;
Step 2, composite polypropylene nitrile: the mixed solution of configuration dimethyl sulfoxide (DMSO) and water (mass ratio is 1:1), add 20wt% acrylonitrile, initiator ammonium persulfate, the carbon nano pipe array prepared is placed in one, Keep agitation be warming up to 50 DEG C under nitrogen protection, take out product after insulation a period of time, washing and drying makes carbon nano pipe array-polyacrylonitrile composite material;
Step 3: composite sulfur: by the carbon nano pipe array prepared-polyacrylonitrile composite material and elemental sulfur in mass ratio 1:5 ~ 1:20 put into tube furnace, under inert gas shielding, be heated to 155 ~ 400 DEG C obtain anode composite; Or elemental sulfur is heated to molten state, under inert gas shielding, the carbon nano pipe array prepared-polyacrylonitrile composite material is put into wherein, take out after keeping 5 ~ 10h and put into baking oven drying, form the sulfur-based composite anode of carbon nano pipe array.
A kind of secondary aluminium cell, comprising:
A () positive pole, is characterized in that, described just very based on the sulfenyl combination electrode of carbon nano pipe array;
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 -, 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: above-mentioned sulfur-based composite anode 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 sulfur-based composite anode based on carbon nano pipe array, preparation method and the application in secondary aluminium cell thereof, have the following advantages:
(1) described anode composite has three-dimensional network conducting matrix grain, huge specific area, load capacity, the conductivity of active material sulphur significantly improve, positive active material sulphur is dispersed with the form of nano particle, compound tight with conducting matrix grain, contact resistance is little, effectively improves the reactivity of sulphur.
(2) part sulphur has long-range π key conjugated system polymer with polyacrylonitrile reaction formation, further increases specific capacity.
(3) nano pore of described anode composite has strong suction-operated to intermediate products such as Small molecular sulfide, fixing, the suppression to positive electrode active materials sulphur can be realized, slow down the loss of sulphur, its three-dimensional structure can provide effective conductive network and unobstructed ion channel simultaneously, improves the overall chemical property of electrode material.
(4) simple, with low cost with the preparation section of this electrode secondary aluminium cell that is positive pole, without the need to additional conductive agent and binding agent, electrode active material on nanoscale with conductive body contact, doubly forthright good, energy density is high.
(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) preparation of carbon nano pipe array: take stainless steel as substrate, Fe is catalyst take ethene as carbon source, and hydrogen and nitrogen are carrier gas, adopts chemical vapour deposition technique (CVD) to prepare carbon nano pipe array.
(2) composite polypropylene nitrile: the mixed solution of configuration dimethyl sulfoxide (DMSO) and water (mass ratio is 1:1), add 20wt% acrylonitrile, initiator ammonium persulfate, 1 wt% carbon nano pipe array is placed in one, Keep agitation be warming up to 50 DEG C under nitrogen protection, insulation 5h, take out product, washing and drying makes carbon nano pipe array-polyacrylonitrile composite material;
(3) composite sulfur: by the carbon nano pipe array prepared-polyacrylonitrile composite material and elemental sulfur in mass ratio 1:10 put into tube furnace, be heated to 350 DEG C, passing under condition of nitrogen gas, keep 10h, form the sulfur-based composite anode based on carbon nano pipe array.
(4) preparation of secondary aluminium cell: above-mentioned sulfur-based composite anode is dried be cut into 40mm wide × pole piece that the long 0.33mm of 15mm is thick, 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 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 1.78V, and discharge capacity is 1068mAh first, and after 50 charge and discharge cycles, capability retention is 87.5%.
Embodiment 2
The preparation of carbon nano pipe array: take conductive paper of carbon fiber as substrate, Fe (NO3) 3 is catalyst, is coated in carbon paper surface in advance, take methane as carbon source, nitrogen is protection gas, adopts chemical vapour deposition technique (CVD) to prepare carbon nano pipe array.
All the other preparation methods are with embodiment 1.Recording battery open circuit voltage is 1.80V, and discharge capacity is 1060mAh first, and after 50 charge and discharge cycles, capability retention is 88.4%.
Embodiment 3
The preparation of carbon nano pipe array is with embodiment 2, and composite polypropylene nitrile is with embodiment 1.
Composite sulfur: elemental sulfur is heated to 155 DEG C, puts into wherein by the carbon nano pipe array prepared under inert gas shielding, keeps 15h, puts into 40 DEG C of baking ovens dry, keeps 24 hours, form the sulfur-based composite anode based on carbon nano pipe array.
The preparation of secondary aluminium cell and method of testing are with embodiment 1.Battery open circuit voltage is 1.80V, and discharge capacity is 1072mAh first, and after 50 charge and discharge cycles, capability retention is 88.7%.
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 (8)

1., based on a sulfur-based composite anode for carbon nano pipe array, comprising:
A () conducting matrix grain, is characterized in that, described conducting matrix grain is the carbon nano pipe array of vertical-growth in conductive substrates;
B () sulfur-bearing active material, is characterized in that, described sulfur-bearing active material is elemental sulfur/polyacrylonitrile composite material.
2. as claimed in claim 1 based on the sulfur-based composite anode of carbon nano pipe 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.
3., as claimed in claim 1 based on the sulfur-based composite anode of carbon nano pipe array, it is characterized in that, in described carbon nano pipe array, the caliber of carbon nano-tube is 1 ~ 50nm, pipe range 1 ~ 2000nm, tube pitch 2 ~ 100nm.
4., as claimed in claim 1 based on the sulfur-based composite anode of carbon nano pipe array, it is characterized in that, described polyacrylonitrile is coated on carbon nano pipe array surface with nano-scale.
5., as claimed in claim 1 based on the sulfenyl combination electrode of carbon nano pipe array, it is characterized in that, described sulphur is by heat treated mode with polyacrylonitrile compound, and uniform load is in conducting matrix grain.
6., as claimed in claim 1 based on the sulfur-based composite anode of carbon nano pipe array, it is characterized in that, comprise 1 ~ 20wt% carbon nano pipe array, 30 ~ 50wt % polyacrylonitrile, 30 ~ 60 wt% sulphur.
7. the preparation method of the sulfur-based composite anode based on carbon nano pipe array according to claim 1, is characterized in that, comprise the following steps:
Step 1, the preparation of carbon nano pipe array: adopt physics or chemical vapour deposition technique at conductive substrates surface vertical-growth carbon nano pipe array;
Step 2, composite polypropylene nitrile: the mixed solution of configuration dimethyl sulfoxide (DMSO) and water (mass ratio is 1:1), add 20wt% acrylonitrile, initiator ammonium persulfate, the carbon nano pipe array prepared is placed in one, Keep agitation be warming up to 50 DEG C under nitrogen protection, take out product after insulation a period of time, washing and drying makes carbon nano pipe array-polyacrylonitrile composite material;
Step 3: composite sulfur: by the carbon nano pipe array prepared-polyacrylonitrile composite material and elemental sulfur in mass ratio 1:5 ~ 1:20 put into tube furnace, under inert gas shielding, be heated to 155 ~ 400 DEG C obtain anode composite; Or elemental sulfur is heated to molten state, under inert gas shielding, the carbon nano pipe array prepared-polyacrylonitrile composite material is put into wherein, take out after keeping 5 ~ 10h and put into baking oven drying, form the sulfur-based composite anode of carbon nano pipe array.
8. a secondary aluminium cell, comprising:
A () positive pole, is characterized in that, described just very based on the sulfenyl combination electrode of carbon nano pipe array;
B () is containing aluminum honeycomb active material;
C () non-water is containing aluminium electrolyte.
CN201410435975.7A 2014-08-29 2014-08-29 Sulfur-base composite positive electrode based on carbon nanotube arrays, preparation method and application thereof Pending CN104332590A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016211036A1 (en) * 2016-06-21 2017-12-21 Robert Bosch Gmbh Method for producing a cathode and battery cell
CN113328061A (en) * 2021-07-12 2021-08-31 浙江王点科技有限公司 Preparation method of positive pole piece of lithium-sulfur battery
CN113764829A (en) * 2021-08-30 2021-12-07 珠海冠宇电池股份有限公司 Composite electrode sheet body and lithium battery
CN117239074A (en) * 2023-09-04 2023-12-15 中能鑫储(北京)科技有限公司 Sulfur-coated high-conductivity nano composite material, preparation method and aluminum ion battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016211036A1 (en) * 2016-06-21 2017-12-21 Robert Bosch Gmbh Method for producing a cathode and battery cell
CN107528045A (en) * 2016-06-21 2017-12-29 罗伯特·博世有限公司 For manufacturing the method and battery cell of negative electrode
CN113328061A (en) * 2021-07-12 2021-08-31 浙江王点科技有限公司 Preparation method of positive pole piece of lithium-sulfur battery
CN113764829A (en) * 2021-08-30 2021-12-07 珠海冠宇电池股份有限公司 Composite electrode sheet body and lithium battery
CN117239074A (en) * 2023-09-04 2023-12-15 中能鑫储(北京)科技有限公司 Sulfur-coated high-conductivity nano composite material, preparation method and aluminum ion battery

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Application publication date: 20150204