CN204179148U - A kind of carbon nano-fiber/sulphur composite material of graphene coated and secondary cell - Google Patents
A kind of carbon nano-fiber/sulphur composite material of graphene coated and secondary cell Download PDFInfo
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- CN204179148U CN204179148U CN201420565904.4U CN201420565904U CN204179148U CN 204179148 U CN204179148 U CN 204179148U CN 201420565904 U CN201420565904 U CN 201420565904U CN 204179148 U CN204179148 U CN 204179148U
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The utility model discloses a kind of carbon nano-fiber/sulphur composite material of graphene coated and comprise the secondary cell of this composite material.Described carbon nano-fiber/sulphur composite material is by after carbon nano-fiber and nano-sulfur compound, adds graphene coated and obtains.The positive pole adopting this composite material to prepare, conducts electricity very well, and sulphur number of dropouts is low; Apply the preparation of this composite positive pole and the high and Environmental Safety of the secondary cell good cycle, the energy that obtain.
Description
Technical field
The utility model belongs to battery material and new forms of energy product scope, carbon nano-fiber/sulphur composite material relating to a kind of graphene coated and preparation method thereof.It is the secondary aluminium cell of positive pole that the utility model also relates to a kind of this composite material that adopts.
Background technology
Along with developing rapidly of the new forms of energy such as mobile communication equipment, electric automobile, wind power generation and thermal power generation, more and more higher to the requirement of high-energy-density, cheap and eco-friendly battery.With metal aluminum or aluminum alloy for positive pole, sulfenyl material is that the battery system of negative pole then can meet these demands.
The energy density of aluminium is 2980mAh/g, is a kind of high-energy carrier, is often used as the negative pole of battery; And the energy density of sulphur is 1675mAh/g, it is the positive electrode that known energy density is the highest.But, elemental sulfur is at room temperature insulator, and the Small molecular organic sulfur compound produced during sulphur-sulfur bonds is dissolved in the unordered sulphur that electrolyte generates irreversible reaction, and active material is run off, the cycle performance of battery is caused to be deteriorated, the development of restriction aluminium sulfur rechargeable battery.
In order to overcome the defect of sulphur simple substance, the carbon-based material with conductivity and bigger serface can be added in elemental sulfur, forming composite positive pole, thus the electric conductivity improving elemental sulfur reduces the loss of active material in cyclic process simultaneously.Carbon nano-fiber, as a kind of novel high performance material, has high intensity, excellent electric conductivity and strong absorption property, can adsorb nano-sulfur in a large number, reduces the loss of sulphur active material.But the sulphur being distributed in carbon nano-fiber surface increases the contact resistance of carbon nano-fiber/sulphur composite material surface on the one hand, causes battery high rate performance to reduce; On the other hand, the absorption property of carbon nano-fiber is only leaned on to be difficult to the loss of the reduzate produced when suppressing sulphur active material and sulphur electric discharge completely.
Summary of the invention
(1) goal of the invention
For the problems referred to above and defect, the purpose of this utility model is the carbon nano-fiber/sulphur composite material providing a kind of graphene coated.Described graphene coated, after carbon nano-fiber/sulphur composite material surface, adds the specific area of material, improves the load capacity of sulphur.The coated one side of Graphene can suppress the effect of shuttling back and forth of material, improves the chemical property of positive electrode; The dissolving of sulphur reduzate can be suppressed on the other hand further, improve the cycle performance of positive electrode.
The purpose of this utility model is also to provide a kind of secondary aluminium cell being positive pole with this composite material.
(2) technical scheme
For achieving the above object, the utility model provides following technical scheme,
A kind of carbon nano-fiber/sulphur composite material of graphene coated, comprise carbon nano-fiber, elemental sulfur and Graphene, it is characterized in that, the nucleocapsid structure of carbon nano-fiber/be interconnected to form between elemental sulfur composite material kernel and graphene coated shell three-dimensional conductive network.
The scope of the diameter of the carbon nano-fiber described in scheme is 300 ~ 800nm.
Elemental sulfur described in scheme is distributed in aperture and the surface of carbon nano-fiber with Nano grade.
In the carbon nano-fiber/sulphur composite material of the graphene coated described in scheme, the mass ratio of carbon nano-fiber, sulphur and Graphene is 1:2 ~ 9:0.1 ~ 0.5.
A preparation method for the carbon nano-fiber/sulphur composite material of graphene coated, is characterized in that:
Step 1, the preparation of carbon nano-fiber: prepare cellulose acetate spinning fibre by method of electrostatic spinning, is put in obtained cellulose acetate nanofiber in alkali lye after 24h, obtains cellulose nano-fibrous, takes out drying for standby; The ZnCl that mass fraction is 1% ~ 6% is placed in by cellulose nano-fibrous
2in the aqueous solution, be put in the water-bath of 60 ~ 100 DEG C about the 6 ~ 12h that vibrates, then take out be put in 55 ~ 85 DEG C can dry 18 ~ 36h in the air dry oven of temperature programming, apply pulling force simultaneously in tunica fibrosa lower end and make it obtain stretching; Dried tunica fibrosa is placed in carbide furnace, obtains carbon nano-fiber at about 350 ~ 550 DEG C high-temperature heating 20 ~ 50min; With the hydrochloric acid cleaning carbon nano-fiber 3 ~ 8 times of 0.1mol/L ~ 0.5mol/L, removing zinc oxide, finally by washed with de-ionized water to the aqueous solution in neutral;
Step 2, the preparation of carbon nano-fiber/sulphur composite material: preparation 25g mass fraction is the sodium sulfide solution of 2% ~ 4%, and add the sublimed sulfur powder of 0.6 ~ 0.9g, stirred at ambient temperature 1.5 ~ 3h makes sulphur powder all dissolve, and obtains sodium polysulfide solution, filters; Preparation mass fraction is the surfactant 100mL of 1% ~ 5%, and add 0.15 ~ 0.40g carbon nano-fiber ultrasonic 8 ~ 15h formation Homogeneous phase mixing liquid under 50 DEG C of conditions, add the sodium polysulfide solution after above-mentioned filtration, ultrasonic agitation 2 ~ 5h obtains uniform mixed solution A; The formic acid solution 100mL of preparation 2mol/L, add proper amount of surfactant, stirring obtains uniform mixed solution, slowly solution A is dripped in this mixed solution, stirring reaction 2 ~ 8h, filters, respectively washs 3 times respectively with deionized water and acetone, under 45 ~ 65 DEG C of conditions, dry 48 ~ 80h, obtains carbon nano-fiber/sulphur composite material;
Step 3, the preparation of the carbon nano-fiber/sulphur composite material of graphene coated: by carbon nano-fiber/sulphur composite material of preparing and graphene oxide water solution 2:1 ~ 8:1 mixing in mass ratio, ultrasonic 5 ~ 16h, add reducing agent, 60 ~ 80 DEG C of isothermal reaction 2 ~ 12h, filter, obtain the carbon nano-fiber/sulphur composite material of graphene coated.
In the preparation method of the carbon nano-fiber/sulphur composite material of graphene coated described in scheme, the surfactant in step 2 includes but not limited to the one in softex kw (CTAB), sodium cetanesulfonate (SDS), neopelex (SDBS) or PEG-4000 (PEG-400).
In the preparation method of the carbon nano-fiber/sulphur composite material of graphene coated described in scheme, in step 3, reducing agent includes but not limited to one or more in hydrazine hydrate, sodium borohydride, natrium citricum and thiourea dioxide.
Scheme additionally provides a kind of secondary cell, comprises positive pole, negative pole and electrolyte, and described positive pole contains the carbon nano-fiber/sulphur composite material of graphene coated, and negative pole is for containing aluminum honeycomb, and electrolyte is that non-water is containing aluminium electrolyte.
In the utility model, the positive pole of battery comprises the carbon nano-fiber of graphene coated/sulphur composite material, conductive agent, binding agent and collector.
Conductive agent described in scheme comprises graphite-based material, carbon-based material and conducting polymer.Graphite-based material comprises electrically conductive graphite KS6, and carbon-based material comprises that Super P, Ketjen are black, acetylene black or carbon black.Conducting polymer comprises polyaniline, polypyrrole, polythiophene, polyacetylene, or their mixture.
Binding agent 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 described in scheme comprises 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 comprises: polyolefin is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.
Described in scheme containing aluminum honeycomb active material, comprising: 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: by the carbon nano-fiber of graphene coated/sulphur composite material, conductive agent, binding agent (ratio is 7:2:1), 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 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
Carbon nano-fiber/sulphur the composite positive pole of a kind of graphene coated that the utility model provides, preparation method and the application in secondary aluminium cell have the following advantages:
1) the utility model adopts a kind of carbon nano-fiber with higher-strength, excellent conductive capability and specific area as carbon-based material, its large specific area and strong absorption property can adsorb sulphur active material effectively, the sulphur of nano shape can combine more closely with carbon-based material, improves the electro-chemical activity of sulphur.
2) graphene coated is on the surface of carbon nano-fiber/sulphur composite material, forms a kind of conductive network of nucleocapsid structure.On the one hand, this conductive network structure better for the migration of ion, electronics provides passage, can improve the electric conductivity of positive electrode; On the other hand, Graphene, in the coated dissolving that can suppress sulphur reduzate further of composite material surface, improves the cycle performance of positive electrode.
3) adopt secondary aluminium cell prepared by this composite positive pole, energy density be high, capacity is large, good cycle, price economy, Environmental Safety and application prospect is extensive.
(4) accompanying drawing explanation
Below in conjunction with accompanying drawing, utility model is further illustrated.
Fig. 1 is combined electrode structure schematic diagram described in the utility model.Fig. 2 is the structural representation of secondary aluminium cell described in the utility model.
Wherein, 1-Graphene, 2-carbon nano-fiber, 3-sulphur, 4-upper cover, 5-negative current collector, 6-negative lug, 7-negative pole, 8-barrier film, 9-positive electrode, 10-Ni substrate, 11-battery container, 12-positive pole ear, 13-plus plate current-collecting body.
(5) embodiment
Be described further below with reference to the technique effect of embodiment to design of the present utility model, concrete structure and generation, to understand the purpose of this utility model, characteristic sum effect fully.The following examples describe several execution mode of the present utility model, and they are only illustrative, and nonrestrictive.
See accompanying drawing 1, the utility model provides a kind of anode composite with high-energy-density and good circulation performance and comprises Graphene 1, carbon nano-fiber 2 and sulphur 3.After carbon nano-fiber 2 and sulphur 3 compound, add the coated and conductive network structure obtained of Graphene 1.
See accompanying drawing 2, the utility model also provides a kind of secondary aluminium cell applying this anode composite.Comprise battery container 11, cell cover 4, the positive electrode 9 being positioned over inside battery, Ni substrate 10, positive pole ear 12, plus plate current-collecting body 13, barrier film 8, negative pole 7, negative lug 6 and negative current collector 5.Positive electrode 9 be coated in Ni substrate 10 formed anode pole piece, then anode pole piece, barrier film 8 and negative pole 7 mutually winding form.
embodiment 1:
1) preparation of carbon nano-fiber: prepare cellulose acetate spinning fibre by method of electrostatic spinning, is put in obtained cellulose acetate nanofiber in alkali lye after 24h, obtains cellulose nano-fibrous, takes out drying for standby; The ZnCl that mass fraction is 3% is placed in by cellulose nano-fibrous
2in the aqueous solution, be put in the water-bath of 80 DEG C about the 8h that vibrates, then take out be put in 70 DEG C can dry 18h in the air dry oven of temperature programming, apply pulling force simultaneously in tunica fibrosa lower end and make it obtain stretching; Dried tunica fibrosa is placed in carbide furnace, obtains carbon nano-fiber at about 400 DEG C high-temperature heating 30min; With the hydrochloric acid cleaning carbon nano-fiber 6 times of 0.3mol/L, removing zinc oxide, finally by washed with de-ionized water to the aqueous solution in neutral.
2) preparation of carbon nano-fiber/sulphur composite material: preparation 25g mass fraction is the sodium sulfide solution of 2%, and add the sublimed sulfur powder of 0.75g, stirred at ambient temperature 2h makes sulphur powder all dissolve, and obtains sodium polysulfide solution, filters; Preparation mass fraction is the surfactant 100mL of 1%, and adds 0.30g carbon nano-fiber ultrasonic 10h formation Homogeneous phase mixing liquid under 50 DEG C of conditions, and add the sodium polysulfide solution after above-mentioned filtration, ultrasonic agitation 3h obtains uniform mixed solution A; The formic acid solution 100mL of preparation 2mol/L, add proper amount of surfactant, stirring obtains uniform mixed solution, above-mentioned solution A is slowly dripped in this mixed solution, stirring reaction 5h, filters, respectively washs 3 times respectively with deionized water and acetone, dry 60h under 55 DEG C of conditions, obtains carbon nano-fiber/sulphur composite material.
3) preparation of the carbon nano-fiber/sulphur composite material of graphene coated: by carbon nano-fiber/sulphur composite material of preparing and graphene oxide water solution 6:1 mixing in mass ratio, ultrasonic 10h, add sodium borohydride, 60 DEG C of isothermal reaction 8h, filter, obtain the carbon nano-fiber/sulphur composite material of graphene coated.
4) preparation of secondary aluminium cell: by positive electrode active materials, conductive agent, binding agent (ratio is 7:2:1), 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 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.
embodiment 2:
1) preparation of carbon nano-fiber: prepare cellulose acetate spinning fibre by method of electrostatic spinning, is put in obtained cellulose acetate nanofiber in alkali lye after 24h, obtains cellulose nano-fibrous, takes out drying for standby; The ZnCl that mass fraction is 1% is placed in by cellulose nano-fibrous
2in the aqueous solution, be put in the water-bath of 60 DEG C about the 8h that vibrates, then take out be put in 70 DEG C can dry 18h in the air dry oven of temperature programming, apply pulling force simultaneously in tunica fibrosa lower end and make it obtain stretching; Dried tunica fibrosa is placed in carbide furnace, obtains carbon nano-fiber at about 400 DEG C high-temperature heating 30min; With the hydrochloric acid cleaning carbon nano-fiber 6 times of 0.3mol/L, removing zinc oxide, finally by washed with de-ionized water to the aqueous solution in neutral.
2) preparation of the carbon nano-fiber/sulphur composite material of graphene coated: by carbon nano-fiber/sulphur composite material of preparing and graphene oxide water solution 8:1 mixing in mass ratio, ultrasonic 10h, add sodium borohydride, 60 DEG C of isothermal reaction 8h, filter, obtain the carbon nano-fiber/sulphur composite material of graphene coated.
3) other are with embodiment 1.
embodiment 3:
1) preparation of the carbon nano-fiber/sulphur composite material of graphene coated: by carbon nano-fiber/sulphur composite material of preparing and graphene oxide water solution 4:1 mixing in mass ratio, ultrasonic 10h, add sodium borohydride, 60 DEG C of isothermal reaction 8h, filter, obtain the carbon nano-fiber/sulphur composite material of graphene coated.
2) other are with embodiment 1.
embodiment 4:
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 shown in the table:
Although be described in detail the utility model with reference to embodiment, but those skilled in the art is to be understood that, when the design of the present utility model do not departed from described in appended claims and equivalent thereof and scope, various amendment and replacement can be made to it.
Claims (4)
1. carbon nano-fiber/sulphur the composite material of a graphene coated, comprise carbon nano-fiber, elemental sulfur and Graphene, it is characterized in that, the nucleocapsid structure of carbon nano-fiber/be interconnected to form between elemental sulfur composite material kernel and Graphene shell three-dimensional conductive network.
2. carbon nano-fiber/sulphur the composite material of graphene coated as claimed in claim 1, it is characterized in that, the scope of the diameter of described carbon nano-fiber is 300 ~ 800nm.
3. carbon nano-fiber/sulphur the composite material of graphene coated as claimed in claim 1, it is characterized in that, described elemental sulfur is distributed in aperture and the surface of carbon nano-fiber with nano shape.
4. a secondary cell, comprises positive pole, negative pole and electrolyte, it is characterized in that, described positive pole contains the carbon nano-fiber/sulphur composite material of graphene coated according to claim 1, and negative pole is for containing aluminum honeycomb, and electrolyte is that non-water is containing aluminium electrolyte.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269538A (en) * | 2014-09-29 | 2015-01-07 | 南京中储新能源有限公司 | Graphene-coated carbon nanofiber/sulphur composite material, preparation and application thereof |
| CN107192485A (en) * | 2017-05-11 | 2017-09-22 | 中原工学院 | A kind of multifunctional nano fiber sensor of flexible extensible and preparation method thereof |
| CN108292740A (en) * | 2015-11-10 | 2018-07-17 | 格兰巴特能源有限公司 | Carbon composite |
-
2014
- 2014-09-29 CN CN201420565904.4U patent/CN204179148U/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104269538A (en) * | 2014-09-29 | 2015-01-07 | 南京中储新能源有限公司 | Graphene-coated carbon nanofiber/sulphur composite material, preparation and application thereof |
| CN108292740A (en) * | 2015-11-10 | 2018-07-17 | 格兰巴特能源有限公司 | Carbon composite |
| CN108292740B (en) * | 2015-11-10 | 2022-07-19 | 格兰巴特能源有限公司 | Carbon composite material |
| CN107192485A (en) * | 2017-05-11 | 2017-09-22 | 中原工学院 | A kind of multifunctional nano fiber sensor of flexible extensible and preparation method thereof |
| CN107192485B (en) * | 2017-05-11 | 2019-04-26 | 中原工学院 | A kind of multifunctional nano fiber sensor of flexible extensible and preparation method thereof |
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