CN104241616A - Carbon-sulphur composite material based on nano polyaniline array as well as preparation and application of composite material - Google Patents
Carbon-sulphur composite material based on nano polyaniline array as well as preparation and application of composite material Download PDFInfo
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Abstract
The invention discloses a carbon-sulphur composite material based on a nano polyaniline array as well as preparation and application of the composite material, and also discloses a secondary aluminium cell taking the composite material as a positive electrode active material. A preparation method of the carbon-sulphur composite material is simple, and the composite material has high electric conductivity, high capacity of adsorbing sulphur and obvious effect of inhibiting sulphur; a positive electrode prepared from the composite material is high in electric conductivity and sulphur utilization ratio; the secondary aluminium cell adopting the positive electrode prepared from the composite material is simple in preparing process, high in capacity and excellent in circulating performance.
Description
Technical field
The invention belongs to battery material and new forms of energy product scope, relate to a kind of anode composite material, especially a kind of carbon sulphur composite material based on nano polyaniline array and preparation method thereof, and use this composite material as the secondary aluminium cell of positive active material.
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.Secondary aluminium-sulfur battery is one of ideal battery system meeting these demands.
Compared with existing electrode material, the advantages such as the metallic element aluminium that earth's crust reserves are maximum has that solid density is large, aboundresources, cheap, environmentally friendly, use safety.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.A kind of energy of the secondary cell formed with aluminium and sulphur is high, cost is low, the life-span is long, environmental protection, use safety and reusable edible energy storage system, represent the developing 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.
Graphene is a kind of carbon element class material of accurate Colloidal particles, the great specific area had, the conductivity of superelevation and outstanding heat conductivility.Polyaniline has good conductivity and the redox characteristic of Rapid reversible, and cheaper starting materials is easy to get.The two is subject to extensive concern in energy storage field.The cooperative effect that Graphene and polyaniline compound produce, can be reduced the internal resistance of composite material, the various negative effects that in restriction cyclic process, sulfur-based compound dissolves in electrolyte and causes thus.The Chinese patent application that publication number is CN103682274A provides a kind of Graphene/polyanilinecomposite composite material, preparation method is simple, controlled, the good Graphene of conductivity provides conductive network, the coated sulphur nano particle of conductive polymer polyanaline, not only improve the conductivity of sulphur, and the dissolving of discharging product polysulfide can be stoped and alleviate volumetric expansion.
But, because Graphene has the common shortcoming of nano material---easily reunite, this greatly reduces its surface area as electrode material, not only makes electrolyte be difficult to fully contact with graphenic surface, and the adsorbance of active material is few, utilance is low.And the polyaniline of conventional chemical methods synthesis is usually in disordered gathering state structure, structural integrity is not high, and surface area is little, and conductivity is not high.The two combines the composite material being difficult to obtain even structure.
Summary of the invention
(1) goal of the invention
The invention reside in and solve prior art Problems existing, provide a kind of even structure, the carbon sulphur composite material based on nano polyaniline array of function admirable.
This programme provide based in the carbon sulphur composite material of nano polyaniline array, as the sulfonated graphene of matrix, the sulfonic acid group-SO containing sterically hindered structure
3h, can overcome the defect of the easy stacking reunion of Graphene, forms the stacked in layers that the degree of order is high.Aniline oligomer is attached to sulfonated graphene π-pi-conjugated bonding action of producing of surface and sulfonic group to the chanza of aniline oligomer, can form with sulfonated graphene the nano polyaniline array structure of the self-supporting shape being core growth in situ.This special 3 D stereo network skeleton, can avoid Graphene to reunite effectively, and polyaniline molecule chain order is improved, and conjugated structure is strengthened, and makes skeleton structure have larger specific area and the conductivity of Geng Gao.With active material sulphur compound tense, the high-specific surface area of the ordered nano hole in three-dimensional net structure and the collaborative generation of Graphene has strong superposition suction-operated, effectively can fix active material sulphur, suppress the dissolving of polysulfide intermediate product, improve the cycle performance of battery.In addition, the high conductivity of this composite material also can overcome the defect of elemental sulfur poorly conductive, improves positive-active, is beneficial to positive electrode capacity and plays.
The present invention also aims to the preparation method of the carbon sulphur composite material based on polyaniline array that a kind of specific capacity height and cycle performance excellence are provided.
The present invention also aims to provide a kind of and use that this composite material is large as the capacity of positive electrode active materials, the secondary aluminium cell of price economy, Environmental Safety.
Term " secondary aluminium cell " in the present invention comprises such as " aluminum secondary battery ", " secondary aluminium-sulfur battery ", " rechargeable aluminium battery ", " aluminium storage battery ", " aluminium energy-storage battery " and similar concept.
(2) technical scheme
For achieving the above object, the invention provides a kind of carbon sulphur composite material based on nano polyaniline array, described composite material comprises:
(a) sulfonated graphene;
(b) nano polyaniline array;
(c) elemental sulfur.
Described in scheme based in the carbon sulphur composite material of nano polyaniline array, sulfonated graphene and nano polyaniline array are compounded to form the sulfonated graphene loaded with nano polyaniline array with three-dimensional network skeleton.
Described in scheme based in the carbon sulphur composite material of nano polyaniline array, elemental sulfur is distributed in the three-dimensional network skeleton of sulfonated graphene loaded with nano polyaniline array with nano shape.
Described in scheme based in the carbon sulphur composite material of nano polyaniline array, sulfonated graphene loaded with nano polyaniline array content is 15 ~ 50wt%, and simple substance sulfur content is 85 ~ 50wt%.
Based on a preparation method for the carbon sulphur composite material of nano polyaniline array, comprise the following steps:
Step 1, the preparation of sulfonated graphene loaded with nano polyaniline array
(1) preparation of aqueous phase, oil phase reactant liquor
It is in the protonic acid aqueous solution of 0.1 ~ 5mol/L that sulfonated graphene is joined concentration in the ratio of 0.1 ~ 10g/L protonic acid aqueous solution, ultrasonic disperse; Add ammonium persulfate, fully stir and make it dissolve; Then adding ethanol in proper amount, mix, is aqueous phase reactions liquid; Aniline being dissolved in organic solvent, fully stirring, make the aniline organic solvent solution that concentration of aniline is 0.01 ~ 0.5mol/L, is oil phase reactant liquor.
(2) preparation of sulfonated graphene loaded with nano polyaniline array
In above-mentioned aqueous phase, oil phase reactant liquor one is poured in another phase mutually, mix ,-10 ~ 10 DEG C of standing reactions 6 ~ 48 hours, filter, solid insoluble ethanol and deionized water washes clean, dry obtained sulfonated graphene loaded with nano polyaniline array material.
Step 2, based on the preparation of the carbon sulphur composite material of nano polyaniline array
By the sulfonated graphene loaded with nano polyaniline array that mixes and elemental sulfur mixture, 130 ~ 180 DEG C of heating 1 ~ 12h under inert gas shielding, the obtained carbon sulphur composite material based on nano polyaniline array after cooling.
In step 1, described Bronsted acid is the one in hydrochloric acid, sulfuric acid, perchloric acid; Described organic solvent is one or more mixing in chloroform, carbon tetrachloride, carrene, carbon disulfide, toluene, dimethylbenzene.
In step 1, described ammonium persulfate and the mol ratio of aniline are ammonium persulfate: aniline=1:1 ~ 6; The volume ratio of described ethanol and protonic acid aqueous solution is ethanol: protonic acid aqueous solution=1:5 ~ 20.
In step 2, in the mixture of described sulfonated graphene loaded with nano polyaniline array and elemental sulfur, sulfonated graphene loaded with nano polyaniline array content is 15 ~ 50wt%, and simple substance sulfur content is 85 ~ 50wt%.。
Present invention also offers a kind of secondary aluminium cell, comprising:
(a) positive pole, wherein said positive pole contains the carbon sulphur composite material based on nano polyaniline array;
B () non-water is containing aluminium electrolyte;
C () is containing the negative pole of aluminium electroactive material.
Here is the preferred positive pole of electrochemical cell of the present invention, negative pole, electrolytical description.
Positive pole
The positive pole of battery of the present invention comprises positive active material, binding agent and collector containing sulfur-bearing active material.
Described sulfur-bearing active material is the aforementioned carbon sulphur composite material based on nano polyaniline array.
Adhesive described in scheme is polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), Kynoar (PVDF), polystyrenebutadienes copolymer (SBR), Viton and polyurethane, PVP, polyethyl acrylate, polyvinyl chloride, polyacrylonitrile, polycaprolactam, polybutadiene, polyisoprene, polyacrylic acid, and derivative, mixture or copolymer.
Collector includes but not limited to stainless steel, copper, nickel, titanium, aluminium.More preferably the aluminium collector of carbon coating, more easily covers the coating comprising positive active material, has lower contact resistance, and can suppress the corrosion of sulfide.
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.
Electrolyte
Non-water described in scheme is organic salt-aluminum halide system containing aluminium electrolyte, and 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.
In organic salt described in scheme-aluminum halide system, aluminum halide is the one in aluminium chloride, aluminium bromide, silver iodide.
Organic salt described in scheme-aluminum halide system includes but not limited to aluminium chloride-triethylamine hydrochloride, aluminium chloride-chlorination 1-butyl-3-methylimidazole, aluminium chloride-phenyl trimethicone ammonium chloride, aluminium bromide-1-ethyl-3-methyllimidazolium bromide plasma liquid.
Negative pole
The negative pole containing aluminium electroactive material described in scheme is metal aluminum or aluminum alloy.Metallic aluminium, the aluminium including but not limited to aluminium foil, aluminium wire, aluminium flake and be 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.
The manufacture method of the secondary aluminium cell described in scheme is as follows: positive electrode active materials, binding agent are made active material slurry in proportion, be applied on nickel foam substrate, oven dry rolls makes anode pole piece, battery core loading nickel plating box hat is wound into the negative pole that barrier film and use negative active core-shell material are made, the non-water that reinjects is containing aluminium electrolyte, and secondary aluminium cell is made in sealing.
(3) beneficial effect
Compared with prior art, it has following beneficial effect in the present invention:
(1) provided by the invention based in the carbon sulphur composite material of nano polyaniline array, the nano level three-dimensional net structure that sulfonated graphene and nano polyaniline array are formed, not only specific area is larger, there is strong superposition suction-operated, fixing, obvious to the inhibition of the intermediate products such as Small molecular sulfide to active material sulphur, and conductivity is higher, and the reactivity of sulphur is larger, utilance is higher, effectively improves capacity and the cycle performance of positive pole.
(2) polyaniline in composite material has electroactive, both can be used as supplementing positive active material, can apply as conductive agent together with Graphene again, when making electrode slice, can avoid using traditional conductive agent, thus significantly improve the specific capacity of electrode slice, further increase battery capacity.
(3) composite material prepare that equipment needed thereby is simple, condition is easy to control, simple to operate, environmental friendliness, energy consumption are low.
(4) adopt carbon sulphur composite material based on nano polyaniline array as the secondary aluminium cell of positive electrode active materials, manufacturing process is simple, and energy density is high, good cycle.
(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
Step 1, the preparation of sulfonated graphene
Will in the ratio of 0.01g graphene oxide/ml aqueous solution, graphene oxide being joined PH is in the aqueous solution of 9 ~ 10, and ultrasonic disperse is even, and low-speed centrifugal place to go is precipitated, obtained graphene oxide colloidal solution; In sodium borohydride: graphene oxide mass ratio is that the ratio of 3:1 adds sodium borohydride in graphene oxide colloidal solution, stirring reaction 2h under 80 DEG C of conditions, remove most of oxy radical in graphene oxide, the graphene oxide of obtained partial reduction; The graphene oxide of above-mentioned partial reduction and Diazosalt of sulfanilic acid are blended in ice-water bath and react 2.5h, the graphene oxide of control section reduction: the mass ratio of Diazosalt of sulfanilic acid is 1:1.5, and sulfonic acid group is incorporated into surface of graphene oxide; Above-mentioned sulfonated products and hydrazine hydrate are reacted 12h at 98 DEG C, removes remaining oxy radical, through deionized water washing to neutral, obtained sulfonated graphene after dry.
Step 2, the preparation of sulfonated graphene loaded with nano polyaniline array
1. aqueous phase, oil phase reactant liquor is prepared.0.25g sulfonated graphene being joined 500ml concentration is in the hydrochloric acid of 1mol/L, ultrasonic disperse 20min, then adds 2.28g ammonium persulfate and 50ml ethanol, is fully uniformly mixed, and is aqueous phase reactions liquid.2.79g aniline being dissolved in 300ml chloroform, fully stirring, make the aniline chloroform soln that concentration of aniline is 0.1mol/L, is oil phase reactant liquor.
2. sulfonated graphene loaded with nano polyaniline array is prepared.0 DEG C is cooled to by putting into mixture of ice and water respectively in above-mentioned aqueous phase, oil phase reactant liquor, again aqueous phase reactions liquid is slowly joined in oil phase reactant liquor, mix, reaction 48 hours are left standstill in ice-water bath, filter product, solid insoluble ethanol and deionized water washes clean, dry obtained sulfonated graphene loaded with nano polyaniline array material.
Step 3, based on the preparation of the carbon sulphur composite material of nano polyaniline array
By the sulfonated graphene loaded with nano polyaniline array of above-mentioned preparation and elemental sulfur in mass ratio 3:17 mix, ball milling is even, and gained mixture is 155 DEG C of heating 3h under nitrogen protection, namely obtain the carbon sulphur composite material based on nano polyaniline array after cooling.
Prepared based in the carbon sulphur composite material of nano polyaniline array, sulfonated graphene loaded with nano polyaniline array content is 15wt%, and simple substance sulfur content is 85wt%.
Embodiment 2
In step 3, the 3:7 mixing in mass ratio of sulfonated graphene loaded with nano polyaniline array, elemental sulfur, other are with embodiment 1.
Prepared based in the carbon sulphur composite material of nano polyaniline array, sulfonated graphene loaded with nano polyaniline array content is 30wt%, and simple substance sulfur content is 70wt%.
Embodiment 3
In step 3, the 1:1 mixing in mass ratio of sulfonated graphene loaded with nano polyaniline array, elemental sulfur, other are with embodiment 1.
Prepared based in the carbon sulphur composite material of nano polyaniline array, sulfonated graphene loaded with nano polyaniline array content is 50wt%, and simple substance sulfur content is 50wt%.Other are with embodiment 1.
By embodiment 1,2,3, the carbon sulphur composite material based on nano polyaniline array of preparation, binding agent PVDF (7:1) mixing in proportion, making active material slurry is applied on the thick nickel foam substrate of 0.6mm, oven dry roll to 0.33 millimeter be cut into 40mm wide × the long pole piece of 15mm, 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 electrolyte, and AA type secondary aluminium cell is made in sealing.
Carry out charge and discharge cycles test to made battery, charge to 2.2V with 1C, 0.5C discharges, and discharge cut-off voltage is 1.2 V, and test result is as follows:
(1) the made battery of embodiment 1 material, open circuit voltage 1.76V, first discharge capacity 521mAh, circulate after 50 times, discharge capacity 331mAh, capacity attenuation rate is 36.5%;
(2) the made battery of embodiment 2 material, open circuit voltage 1.74V, first discharge capacity 493mAh, circulate after 50 times, discharge capacity 322mAh, capacity attenuation rate is 34.7%;
(3) the made battery of embodiment 3 material, open circuit voltage 1.73V, first discharge capacity 461mAh, circulate after 50 times, discharge capacity 315mAh, capacity attenuation rate is 31.7%.
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 (10)
1., based on a carbon sulphur composite material for nano polyaniline array, comprising:
(a) sulfonated graphene;
(b) nano polyaniline array;
(c) elemental sulfur.
2., as claimed in claim 1 based on the carbon sulphur composite material of nano polyaniline array, it is characterized in that, described sulfonated graphene and nano polyaniline array are compounded to form the sulfonated graphene loaded with nano polyaniline array with three-dimensional network skeleton.
3., as claimed in claim 1 or 2 based on the carbon sulphur composite material of nano polyaniline array, it is characterized in that, described elemental sulfur is distributed in the three-dimensional network skeleton of sulfonated graphene loaded with nano polyaniline array with nano shape.
4. the carbon sulphur composite material based on nano polyaniline array as described in claim 1 or 3, is characterized in that, in described composite material, sulfonated graphene loaded with nano polyaniline array content is 15 ~ 50wt%, and simple substance sulfur content is 85 ~ 50wt%.
5. described in a claim 1 based on the preparation method of the carbon sulphur composite material of nano polyaniline array:
By the sulfonated graphene loaded with nano polyaniline array that mixes and elemental sulfur mixture, 130 ~ 180 DEG C of heating 1 ~ 12h under inert gas shielding, the obtained carbon sulphur composite material based on nano polyaniline array after cooling.
6. as claimed in claim 5 based on the carbon sulphur composite material and preparation method thereof of nano polyaniline array, it is characterized in that, in the mixture of described sulfonated graphene loaded with nano polyaniline array and elemental sulfur, sulfonated graphene loaded with nano polyaniline array content is 15 ~ 50wt%, and simple substance sulfur content is 85 ~ 50wt%.
7., as claimed in claim 5 based on the carbon sulphur composite material and preparation method thereof of nano polyaniline array, it is characterized in that, the preparation of described sulfonated graphene loaded with nano polyaniline array comprises the following steps:
(1) aqueous phase, oil phase reactant liquor is prepared
It is in the protonic acid aqueous solution of 0.1 ~ 5mol/L that sulfonated graphene is joined concentration in the ratio of 0.1 ~ 10g/L protonic acid aqueous solution, ultrasonic disperse; Add ammonium persulfate, fully stir and make it dissolve; Then adding ethanol in proper amount, mix, is aqueous phase reactions liquid; Aniline being dissolved in organic solvent, fully stirring, make the aniline organic solvent solution that concentration of aniline is 0.01 ~ 0.5mol/L, is oil phase reactant liquor;
(2) sulfonated graphene loaded with nano polyaniline array is prepared
By above-mentioned aqueous phase, the mixing of oil phase reactant liquor ,-10 ~ 10 DEG C of standing reactions 6 ~ 48 hours, filter, solid insoluble ethanol and deionized water washes clean, dry obtained sulfonated graphene loaded with nano polyaniline array material.
8., as claimed in claim 7 based on the carbon sulphur composite material and preparation method thereof of nano polyaniline array, it is characterized in that: described Bronsted acid is the one in hydrochloric acid, sulfuric acid, perchloric acid; Described organic solvent is one or more mixing in chloroform, carbon tetrachloride, carrene, carbon disulfide, toluene, dimethylbenzene.
9., as claimed in claim 7 based on the carbon sulphur composite material and preparation method thereof of nano polyaniline array, it is characterized in that, described ammonium persulfate and the mol ratio of aniline are ammonium persulfate: aniline=1:1 ~ 6; Described ethanol and the volume ratio of protonic acid aqueous solution are ethanol: protonic acid aqueous solution=1:5 ~ 20.
10. a secondary aluminium cell, comprising:
(a) positive pole, wherein said positive pole contains the carbon sulphur composite material based on nano polyaniline array according to claim 1;
B () non-water is containing aluminium electrolyte;
C () is containing the negative pole of aluminium electroactive material.
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| CN106473261A (en) * | 2016-11-17 | 2017-03-08 | 无锡市长安曙光手套厂 | A kind of detachable plate exposure suit |
| CN107034569A (en) * | 2016-11-17 | 2017-08-11 | 无锡市长安曙光手套厂 | A kind of radiation resistant fiber fabric |
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| CN106473260A (en) * | 2016-11-17 | 2017-03-08 | 无锡市长安曙光手套厂 | A kind of detachable plate exposure suit |
| CN106473261A (en) * | 2016-11-17 | 2017-03-08 | 无锡市长安曙光手套厂 | A kind of detachable plate exposure suit |
| CN107034569A (en) * | 2016-11-17 | 2017-08-11 | 无锡市长安曙光手套厂 | A kind of radiation resistant fiber fabric |
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