CN104157829B - A kind of secondary aluminium cell comprising sulphur carbon composite based on polyaniline nanotube - Google Patents
A kind of secondary aluminium cell comprising sulphur carbon composite based on polyaniline nanotube Download PDFInfo
- Publication number
- CN104157829B CN104157829B CN201410418094.4A CN201410418094A CN104157829B CN 104157829 B CN104157829 B CN 104157829B CN 201410418094 A CN201410418094 A CN 201410418094A CN 104157829 B CN104157829 B CN 104157829B
- Authority
- CN
- China
- Prior art keywords
- polyaniline nanotube
- aluminium
- graphene
- polyaniline
- nanotube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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 kind of sulphur carbon composite based on polyaniline nanotube and preparation method, and the application of described composite material in secondary aluminium cell.Described composite material is composited by polyaniline nanotube, Graphene and sulfur-bearing active material, has three-dimensional network conducting matrix grain, and preparation method is simple to operate, cost is low, and the electrode prepared by above-mentioned composite material is without the need to adding conductive agent, and energy density is high.Electrode prepared by above-mentioned composite material is applied to secondary aluminium cell system as positive pole, capacity and the cycle performance of battery can be improved.
Description
Technical field
The present invention relates to a kind of anode composite material and secondary aluminium cell thereof, especially a kind of sulphur carbon composite based on polyaniline nanotube and preparation method thereof, and use this composite material as the secondary aluminium cell of positive active material, belong to new material and new forms of energy product scope.
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 aboundresources of the secondary cell formed with aluminium and sulphur, pollution-free, cheap, energy density is high, the energy storage system of use safety, be that energy is high, cost is low, the life-span is long, environmental protection, the representative of secondary cell of battery material aboundresources and reusable edible and direction.
The electrical insulating property of sulphur causes the utilance of sulphur positive active material low, and the discharge and recharge of secondary aluminium-sulfur battery to react the Small molecular sulfur-based compound intermediate product produced soluble in electrolyte, thus cause irreversible loss and the capacity attenuation of active material, cause the self-discharge rate of battery high, cycle life is short, have impact on its large-scale application.In order to overcome the defect that elemental sulfur exists, normally elemental sulfur is loaded in the carbon element class material or conducting polymer with high-specific surface area, high porosity and excellent conductive performance feature at present, form composite positive pole, to limit the various negative effects that sulfur-based compound in cyclic process dissolves in electrolyte and causes thus.
Graphene is a kind of carbon element class material of accurate Colloidal particles, and the superhigh specific surface area had, larger conductivity, make it promise to be electrode material of new generation.Polyaniline has the redox characteristic (i.e. load/reaction of unloading) of good conductivity and Rapid reversible, and cheaper starting materials is easy to get, and gets more and more people's extensive concerning in recent years in energy storage field.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, makes electrolyte be difficult to fully contact with graphenic surface.And the polyaniline of conventional chemical methods synthesis is usually in aggregated structure, structural integrity is not high, and surface area is little, and conductivity is not high; Meanwhile, in charge and discharge cycles, the embedding repeatedly of supported ionic/deviate from, makes the volume of polyaniline repeatedly change, causes the destruction of macromolecular chain, and electrode capacity decay is serious.
Summary of the invention
(1) goal of the invention
For above-mentioned existing scheme Problems existing, the invention provides a kind of sulphur carbon composite based on polyaniline nanotube.
Polyaniline nanotube, except having it as except the excellent properties of conducting polymer, also has stronger strand and is arranged with the advantages such as the large and unique hollow structure of sequence, specific area.The molecules align regularity of polyaniline nano tubular construction comparatively nano particle or fiber is enhanced, and is conducive to the transmission of charge carrier in nanotube and between pipe, makes conductivity there occurs sudden change formula and increases.Graphene has good conductivity and large specific area, for polyaniline provides huge bond area.
When polyaniline nanotube and Graphene compound tense, polyaniline is attached to graphenic surface with organized nanotube structures form, with π-pi-conjugated non-covalent bonding, form the pipe-sheet composite construction of self-supporting shape, not only efficiently avoid because Graphene folds poly-that specific area that is that cause reduces, and polyaniline molecule chain order is improved, conjugated structure is strengthened, make it have higher conductivity, the defect of elemental sulfur poorly conductive can be overcome, improve positive-active, be beneficial to battery capacity and play.In addition, superpose at pipe-sheet composite construction in the grid frame structure of the three-dimensional manometer yardstick formed, the nanometer-size of the high-ratio surface sum polyaniline nanotube of Graphene, to intermediate products such as Small molecular sulfide, there is strong superposition suction-operated, the inhibition run off to fixing, the sulphur of active material sulphur is obvious, effectively can improve the cycle performance of battery.
The present invention also aims to the preparation method that a kind of sulphur carbon composite based on polyaniline nanotube is 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 sulphur carbon composite based on polyaniline nanotube, described composite material comprises polyaniline nanotube, Graphene and elemental sulfur, wherein polyaniline nanotube is ordered structure, polyaniline nanotube and Graphene form the three-dimensional network skeleton that pipe-sheet composite construction superposes, and elemental sulfur is distributed in the three-dimensional network skeleton that polyaniline nanotube and Graphene formed with nano shape.
Based in the sulphur carbon composite of polyaniline nanotube described in scheme, polyaniline nanotube content is 10 ~ 40wt%, Graphene content is 5 ~ 10wt%, and simple substance sulfur content is 85 ~ 50wt%, and the content summation of polyaniline nanotube, elemental sulfur, Graphene is 100%.
The preparation method of the sulphur carbon composite based on polyaniline nanotube described in scheme comprises the following steps:
Step 1, polyaniline nanotube-graphene composite material preparation: polyaniline nanotube is added in graphene oxide solution in proportion, after stirring, carries out ultrasonic disperse, obtain mixture; Mixture is heated to 80 ~ 95 DEG C, adds reducing agent, and constant temperature stirs 6 ~ 24h; After reaction terminates, filter product, obtain insoluble matter, washing is dry, obtained polyaniline nanotube-graphene composite material.
Step 2; prepared by the sulphur carbon composite based on polyaniline nanotube: by polyaniline nanotube-graphene composite material of mixing and elemental sulfur mixture; under inert gas shielding, 130 ~ 180 DEG C of heating 1 ~ 12h, namely obtain the sulphur carbon composite based on polyaniline nanotube after cooling.
In step 1, by graphene oxide and polyaniline nanotube mass ratio 1 ~ 1:8, polyaniline nanotube is added in graphene oxide solution.
In step 1, the graphene oxide concentration in described graphene oxide solution is 0.01mg/ml ~ 10mg/ml.
In step 1, described reducing agent comprises hydrazine hydrate, boron alkali acid sodium.
In step 2, described polyaniline nanotube-graphene composite material and elemental sulfur mass ratio are 5:5 ~ 17.
Present invention also offers a kind of secondary aluminium cell, comprise the positive pole of sulfur-bearing active material, non-water containing aluminium electrolyte and the negative pole containing aluminium electroactive material, wherein positive pole sulfur-bearing active material is the sulphur carbon composite based on polyaniline nanotube, and described positive pole eliminates conductive agent.
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.Wherein, term " sulfur-bearing active material " here refers to comprise the positive active material containing element sulphur, and wherein, electro-chemical activity relates to fracture or the formation of sulphur-sulphur covalent bond.
Sulfur-bearing active material described in scheme is the aforementioned sulphur carbon composite based on polyaniline nanotube.
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 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.
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]
-ion.
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 comprises aluminium chloride-triethylamine hydrochloride, aluminium chloride-chlorination 1-butyl-3-methylimidazole, aluminium chloride-phenyl trimethicone ammonium chloride, aluminium bromide-1-ethyl-3-methyllimidazolium bromide ionic liquid.
Negative pole
The negative pole containing aluminium electroactive material described in scheme is metal aluminum or aluminum alloy.Metallic aluminium, the aluminium comprising 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) the sulphur carbon composite based on polyaniline nanotube provided by the invention, combine the Graphene of polyaniline nanotube and the two-dimentional conductive structure with one-dimensional electric structure, for electroactive material sulphur constructs the three-dimensional network conducting matrix grain with pipe-sheet composite construction, achieve sulphur to contact with the nanoscale of conducting matrix grain, avoid independent one dimension or two-dimentional conductive structure to the restriction in electric transmission direction, conductivity is higher, the reactivity of sulphur is larger, utilance is higher, improves battery performance.
(2) provided by the invention based in the sulphur carbon composite of polyaniline nanotube, the nanometer-size of the high-ratio surface sum polyaniline nanotube of Graphene, to intermediate products such as Small molecular sulfide, there is strong superposition suction-operated, the inhibition run off to fixing, the sulphur of active material sulphur is obvious, effectively improves the cycle performance of battery.
(3) provided by the invention based in the sulphur carbon composite of polyaniline nanotube, polyaniline nanotube 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.
(4) in the present invention based on the preparation of the sulphur carbon composite of polyaniline nanotube, equipment needed thereby is simple, condition is easy to control, simple to operate, environmental friendliness, energy consumption are low.
(5) employing provided by the invention is based on the sulphur carbon composite of polyaniline nanotube as the secondary aluminium cell of positive electrode active materials, and 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
In the sulphur carbon composite of ratio preparation based on polyaniline nanotube that polyaniline nanotube, Graphene, elemental sulfur mass ratio are 2:1:17; In prepared composite material, polyaniline nanotube content is 10wt%, and Graphene content is 5wt%, and simple substance sulfur content is 85wt%.
Step 1, polyaniline nanotube-graphene composite material preparation: be the ratio of 2:1 in polyaniline nanotube and graphene oxide mass ratio, adds in graphene oxide solution (0.3g/ml), stirring 4h by polyaniline nanotube, ultrasonic disperse 0.5h, obtains mixture; Mixture is heated to 90 DEG C, adds hydrazine hydrate in the ratio of 1ml hydrazine hydrate/100g graphene oxide, and constant temperature stirs 12h; After reaction terminates, filter product, obtain insoluble matter, washing is dry, obtained polyaniline nanotube-graphene composite material, for subsequent use.
Step 2; prepared by the sulphur carbon composite based on polyaniline nanotube: by the polyaniline nanotube-graphene composite material of above-mentioned preparation and elemental sulfur in mass ratio 3:17 mix; ball milling is even; gained mixture is 155 DEG C of heating 3h under nitrogen protection, namely obtain the sulphur carbon composite based on polyaniline nanotube after cooling.
Embodiment 2
In the sulphur carbon composite of ratio preparation based on polyaniline nanotube that polyaniline nanotube, Graphene, elemental sulfur mass ratio are 1:1:8; In prepared composite material, polyaniline nanotube content is 10wt%, and Graphene content is 10wt%, and simple substance sulfur content is 80wt%.Other are with embodiment 1.
Embodiment 3
In the sulphur carbon composite of ratio preparation based on polyaniline nanotube that polyaniline nanotube, Graphene, elemental sulfur mass ratio are 3:1:16; In prepared composite material, polyaniline nanotube content is 15wt%, and Graphene content is 5wt%, and simple substance sulfur content is 80wt%.Other are with embodiment 1.
Embodiment 4
In the sulphur carbon composite of ratio preparation based on polyaniline nanotube that polyaniline nanotube, Graphene, elemental sulfur mass ratio are 8:1:11; In prepared composite material, polyaniline nanotube content is 40wt%, and Graphene content is 5wt%, and simple substance sulfur content is 55wt%.Other are with embodiment 1.
Embodiment 5
In the sulphur carbon composite of ratio preparation based on polyaniline nanotube that polyaniline nanotube, Graphene, elemental sulfur mass ratio are 4:1:5; In prepared composite material, polyaniline nanotube content is 40wt%, and Graphene content is 10wt%, and simple substance sulfur content is 50wt%.Other are with implementing 1.
The sulphur carbon composite based on polyaniline nanotube embodiment 1,2,3,4,5 prepared, binding agent PVDF be (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 1.2V, and test result is as follows:
(1) the made battery of embodiment 1 material, open circuit voltage 1.76V, first discharge capacity 511mAh, circulate after 50 times, discharge capacity 331mAh, capacity attenuation rate is 35.2%;
(2) the made battery of embodiment 2 material, open circuit voltage 1.74V, first discharge capacity 487mAh, circulate after 50 times, discharge capacity 326mAh, capacity attenuation rate is 33.1%;
(3) the made battery of embodiment 3 material, open circuit voltage 1.74V, first discharge capacity 480mAh, circulate after 50 times, discharge capacity 324mAh, capacity attenuation rate is 32.5%;
(4) the made battery of embodiment 4 material, open circuit voltage 1.71V, first discharge capacity 337mAh, circulate after 50 times, discharge capacity 241mAh, capacity attenuation rate is 28.5%;
(5) the made battery of embodiment 5 material, open circuit voltage 1.70V, first discharge capacity 314mAh, circulate after 50 times, discharge capacity 228mAh, capacity attenuation rate is 27.4%.
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 (2)
1. a secondary aluminium cell, comprises the positive pole of sulfur-bearing active material, non-water containing aluminium electrolyte and the negative pole containing aluminium electroactive material, it is characterized in that:
Positive pole sulfur-bearing active material is the sulphur carbon composite based on polyaniline nanotube, described composite material comprises polyaniline nanotube, Graphene and elemental sulfur, wherein polyaniline nanotube is ordered structure, polyaniline nanotube and Graphene form the three-dimensional network skeleton that pipe-sheet composite construction superposes, and elemental sulfur is distributed in the three-dimensional network skeleton that polyaniline nanotube and Graphene formed with nano shape; In described composite material, polyaniline nanotube content is 10 ~ 40wt%, and Graphene content is 5 ~ 10wt%, and simple substance sulfur content is 85 ~ 50wt%, and the content summation of polyaniline nanotube, Graphene, elemental sulfur is 100%;
Non-water 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;
Negative pole containing aluminium electroactive material is metal aluminum or aluminum alloy;
Described positive pole eliminates conductive agent.
2. secondary aluminium cell as claimed in claim 1, it is characterized in that, organic salt-aluminum halide system is the one in aluminium chloride-triethylamine hydrochloride, aluminium chloride-chlorination 1-butyl-3-methylimidazole, aluminium chloride-phenyl trimethicone ammonium chloride, aluminium bromide-1-ethyl-3-methyllimidazolium bromide ionic liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410418094.4A CN104157829B (en) | 2014-08-22 | 2014-08-22 | A kind of secondary aluminium cell comprising sulphur carbon composite based on polyaniline nanotube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410418094.4A CN104157829B (en) | 2014-08-22 | 2014-08-22 | A kind of secondary aluminium cell comprising sulphur carbon composite based on polyaniline nanotube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104157829A CN104157829A (en) | 2014-11-19 |
| CN104157829B true CN104157829B (en) | 2016-01-20 |
Family
ID=51883282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410418094.4A Expired - Fee Related CN104157829B (en) | 2014-08-22 | 2014-08-22 | A kind of secondary aluminium cell comprising sulphur carbon composite based on polyaniline nanotube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104157829B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600268B (en) * | 2015-01-16 | 2017-02-22 | 中国计量学院 | Method for preparing polyaniline/sulfur/graphene composite material |
| CN105591078A (en) * | 2015-12-21 | 2016-05-18 | 昆明理工大学 | Mixed ion liquid Al/C-S secondary battery and preparation method |
| CN106450423B (en) * | 2016-09-30 | 2019-06-25 | 上海空间电源研究所 | A kind of high specific energy integrated flexible electrode and preparation method thereof |
| CN108428864B (en) * | 2018-03-02 | 2021-06-11 | 合肥国轩高科动力能源有限公司 | Sulfur-carbon composite cathode material and preparation method thereof |
| KR20200033737A (en) * | 2018-09-20 | 2020-03-30 | 주식회사 엘지화학 | Sulfur-carbon composite and lithium secondary battery including the same |
| CN112002937A (en) * | 2020-08-07 | 2020-11-27 | 山东科技大学 | Gel electrolyte for aluminum ion battery and preparation method and application thereof |
| CN112164771A (en) * | 2020-08-25 | 2021-01-01 | 合肥国轩高科动力能源有限公司 | Sulfur/polyaniline nanotube/reduced graphene oxide composite material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102315424A (en) * | 2010-07-06 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Composite anode material for lithium sulfur battery, preparation method and application thereof |
| CN102321254A (en) * | 2011-09-30 | 2012-01-18 | 西安交通大学 | Preparation method for high-concentration graphene-polyaniline nanofiber composite dispersion liquid and high-concentration graphene-polyaniline nanofiber composite film |
| CN103682274A (en) * | 2013-12-19 | 2014-03-26 | 浙江师范大学 | Graphene/polyaniline/sulfur composite material and preparation method thereof |
| CN103996830A (en) * | 2014-05-12 | 2014-08-20 | 上海大学 | A preparation method of a sulfur-supported graphene aerogel composite material |
| CN104781458A (en) * | 2012-10-01 | 2015-07-15 | 独立行政法人科学技术振兴机构 | Approval prediction device, approval prediction method, and program |
-
2014
- 2014-08-22 CN CN201410418094.4A patent/CN104157829B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102315424A (en) * | 2010-07-06 | 2012-01-11 | 中国科学院上海硅酸盐研究所 | Composite anode material for lithium sulfur battery, preparation method and application thereof |
| CN102321254A (en) * | 2011-09-30 | 2012-01-18 | 西安交通大学 | Preparation method for high-concentration graphene-polyaniline nanofiber composite dispersion liquid and high-concentration graphene-polyaniline nanofiber composite film |
| CN104781458A (en) * | 2012-10-01 | 2015-07-15 | 独立行政法人科学技术振兴机构 | Approval prediction device, approval prediction method, and program |
| CN103682274A (en) * | 2013-12-19 | 2014-03-26 | 浙江师范大学 | Graphene/polyaniline/sulfur composite material and preparation method thereof |
| CN103996830A (en) * | 2014-05-12 | 2014-08-20 | 上海大学 | A preparation method of a sulfur-supported graphene aerogel composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104157829A (en) | 2014-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104157829B (en) | A kind of secondary aluminium cell comprising sulphur carbon composite based on polyaniline nanotube | |
| CN204118182U (en) | A kind of carbon sulphur anode composite and secondary aluminium cell | |
| CN104269539A (en) | Vertical-orientated graphene-sulphur composite cathode and preparation method thereof and secondary aluminum battery | |
| CN104269543A (en) | Graphene-cladded sulfur/microporous carbon sphere composite cathode material | |
| CN104393233A (en) | Graphene array-based carbon-sulfur composite electrode and secondary cell | |
| CN104183835B (en) | A kind of aluminium carbon aerogel composite material and the secondary aluminium cell as negative pole | |
| CN104269538A (en) | Graphene-coated carbon nanofiber/sulphur composite material, preparation and application thereof | |
| CN104362290A (en) | Preparation and application of porous carbon coated orientation carbon nano tube/sulfur composite anode | |
| CN104157879A (en) | Carbon sulfur compound anode for secondary battery | |
| CN204204953U (en) | A kind of carbon sulphur combination electrode based on graphene array and secondary cell | |
| CN104201350A (en) | Secondary battery based on graphene aerogel/sulphur composite material | |
| CN104201358B (en) | Based on the sulphur anode composite and preparation method thereof of nano polyaniline coated graphite alkene | |
| CN104300127A (en) | Sulfur-based composite material coated with carbon, preparation and application thereof | |
| CN104078654B (en) | Sulfhydryl compound carbon nanotube composite positive electrode and secondary aluminium battery | |
| CN104157878A (en) | Carbon nanotube array-nano polyaniline-sulfur composite positive electrode, and preparation method and application thereof | |
| CN104201352A (en) | Preparation and application of carbon-sulfur composite positive electrode based on CNT (carbon nano tube) sponge | |
| CN104183850A (en) | Carbon-sulphur composite electrode based on carbon nano tube arrays as well as preparation method and application of carbon-sulphur composite electrode | |
| CN104241616A (en) | Carbon-sulphur composite material based on nano polyaniline array as well as preparation and application of composite material | |
| CN104078678A (en) | Sulfur-carbon conductive polymer positive electrode and secondary aluminium battery using same | |
| CN204088457U (en) | The carbon sulphur anode composite that a kind of nano polyaniline is coated and secondary cell | |
| CN204156009U (en) | A kind of secondary aluminium cell | |
| CN204156012U (en) | A kind of aluminum matrix composite materials negative pole and secondary aluminium cell | |
| CN104218230A (en) | Carbon nano tube sponge conducting polymer composite cathode for secondary battery | |
| CN104078700A (en) | Secondary aluminum cell with positive electrode made of double-cladding carbon-sulfur composite material | |
| CN104269544B (en) | Graphene array anode composite and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20190822 |