CN204156011U - Nanofiber array anode composite - Google Patents
Nanofiber array anode composite Download PDFInfo
- Publication number
- CN204156011U CN204156011U CN201420666847.9U CN201420666847U CN204156011U CN 204156011 U CN204156011 U CN 204156011U CN 201420666847 U CN201420666847 U CN 201420666847U CN 204156011 U CN204156011 U CN 204156011U
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- CN
- China
- Prior art keywords
- anode composite
- carbon
- sulphur
- metal oxide
- nanofiber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The utility model discloses a kind of nanofiber array anode composite, this anode composite-be made up of metal oxide, carbon nanofiber arrays, sulphur and conductive substrates, without the need to adding conductive agent and binding agent, described anode composite energy density is high, cycle performance is high and doubly forthright excellent.
Description
Technical field
the utility model is battery and new energy field, relates to the preparation of the excellent sulfur-based composite anode sheet of a kind of cycle performance.
Background technology
regenerative resource is grid-connected, the develop rapidly of the new energy technology such as electric automobile and intelligent grid is in the urgent need to developing the energy storage system of more high-energy-density.The volume and capacity ratio of aluminium is 8050mAh/cm
3
, be 4 times of lithium, and chemical activity being stablized, is desirable negative material; And the theoretical volume specific capacity of sulphur is 3467mAh/cm
3
, be one of positive electrode that known energy density is the highest.The aluminium-sulfur battery of the two composition is the emerging battery system of satisfying the demand.But, elemental sulfur has insulating properties, and the polysulfide produced in discharge process is soluble in electrolyte, causes the problems such as the low and electrode passivation of the utilance of active material, therefore, the solution that people commonly use is sulfur-bearing active material and the excellent carbon-based material compound of electric conductivity.
carbon nano-fiber is the excellent material of a kind of electric conductivity, and its specific area is large, and mechanical property is good and draw ratio is large.Interlaced carbon nano-fiber can form the conductive network having " confinement " and act on, and is conducive to the transmission of electronics and suppresses the dissolving of sulphur reduzate.But traditional carbon nano-fiber mostly is unordered shape, accumulation of easily reuniting, causes its effective ratio area to reduce, and has a strong impact on the load capacity of material to sulphur, and the skewness of sulphur in material with carbon element, and sulphur active material utilization is low; During discharge and recharge, carbon nano-fiber surface has a large amount of sulphur active material and becomes poly sulphide dissolves in electrolyte.
Summary of the invention
(1) utility model object
the purpose of this utility model is the defect improving existing positive plate cycle performance and poorly conductive, provides a kind of positive plate be made up of carbon nanofiber arrays, sulphur and metal oxide.This positive plate good cycle, conductivity is good and energy density is high.
(2) technical scheme
to achieve these goals, the utility model provides following technical scheme:
a kind of nanofiber array anode composite, be made up of metal oxide, carbon nanofiber arrays, elemental sulfur and conductive substrates, it is characterized in that, described carbon nanofiber arrays vertical-growth is in conductive substrates, elemental sulfur is attached on carbon nano-fiber-wall, outermost layer coated metal oxide layer, described anode composite is three-dimensional layer structure.
nanofiber array anode composite described in scheme, is characterized in that, the diameter of described carbon nanofiber arrays is 50 ~ 400nm, and length is 2 ~ 50 μm.
nanofiber array anode composite described in scheme, is characterized in that, described metal oxide comprise in TiO2, MgO, Al2O3, ZnO, SnO2, ZrO, CeO2, La2O3, V2O5 and MnO2 any one.
nanofiber array anode composite described in scheme, is characterized in that, described anode composite sheet is without the need to adding conductive agent and binding agent.
(3) beneficial effect
the anode composite sheet that the utility model provides compared with prior art, have the following advantages: carbon nanofiber arrays has the pipeline aligned, the pore structure of the pipeline of these nanoscales and material itself can a large amount of sulphur active material of load, can reduce the loss of sulphur reduzate simultaneously; The coated of metal oxide can play " confinement " effect further, suppresses to shuttle back and forth the generation of effect and the corrosion of electrode.
(4) accompanying drawing explanation
fig. 1 is anode composite chip architecture tangent plane schematic diagram.
wherein, 1-conductive substrates, 2-sulphur, 3-carbon fiber array, 4-metal oxide.
(5) embodiment
be described further below with reference to the technique effect of drawings and Examples 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, provide the anode composite bag conductive substrates 1 of a kind of excellent conductivity, good cycle in the utility model, sulphur 2, carbon fiber array 3, metal oxide 4; Wherein, carbon fiber array 3 vertical-growth is in conductive substrates 1, and added metal oxide 4 forms layer structure, and the pore structure that sulphur 2 is attached to carbon nanofiber arrays 3 is interior with on the outer wall of metal oxide 4.
embodiment 1:
1) preparation of carbon nanofiber arrays: be mixed with potassium sodium tartrate solution and each 50mL of copper-bath that concentration is 0.lmol/L, the copper-bath prepared is added drop-wise in potassium sodium tartrate solution slowly, ceaselessly stir in the process dripped, obtain cupric tartrate catalyst; Adopt chemical vapour deposition technique, cupric tartrate is that catalyst at room temperature passes into argon gas 20min with the flow of 150sccm, discharges the air in quartz ampoule; Keep the flow of argon gas constant, be raised to 400 DEG C with the speed of 50 DEG C/min, after 10min, argon gas replaced by hydrogen (70sccm) and acetylene (30sccm).To be brought into by hydrogen and acetylene gas mixture by the catalyst of heat sublimation and react, prepare the carbon nanofiber arrays of oriented growth on conductive substrates surface.
) carbon sulphur compound: by the carbon nanofiber arrays prepared and elemental sulfur in mass ratio 1:5 put into the reactor of the airtight polytetrafluoroethylene containing nitrogen, be placed in baking oven to be heated to 300 DEG C and to make sulphur fully melt and spread, be cooled to room temperature and obtain carbon sulphur composite material.
) preparation of positive pole: above-mentioned carbon sulfur materials is added in the mixed solution of 10mL glacial acetic acid, 20mL water and 40mL absolute ethyl alcohol, stir and evenly mix to obtain mixture A; Under ultrasonic agitation, 20mL butyl titanate and 40mL absolute ethyl alcohol mixed liquor are added drop-wise in said mixture A, leave standstill a period of time, 80 DEG C of dryings, calcine to obtain the carbon sulphur anode composite of coated by titanium dioxide for 300 DEG C.
embodiment 2:
1) preparation of carbon nanofiber arrays: the protective agent polyvinylpyrrolidone of 1.6g is dissolved in deionized water the solution being mixed with 40mL, 10mL solution is prepared again with soluble copper salt copper sulphate 0.037g, 10mL reducing agent 80% hydrazine hydrate is dripped after mix and blend, and keep reaction solution cumulative volume to be 50mL, heat and be stirred to 80 DEG C of insulations, become aubergine to solution colour, obtain copper colloidal sol; Adopt chemical vapour deposition technique, copper colloidal sol is that catalyst at room temperature passes into argon gas 20min with the flow of 150sccm, to discharge the air in quartz ampoule; Keep the flow of argon gas constant, be raised to 400 DEG C with the speed of 50 DEG C/min, after 10min, argon gas replaced by hydrogen (70sccm) and acetylene (30sccm); To be brought into by hydrogen and acetylene gas mixture by the catalyst of heat sublimation and carry out catalytic cracking reaction, reaction 30min, prepare the carbon nanofiber arrays of oriented growth on conductive substrates surface.
) carbon sulphur compound: preparation 0.5g/mL Na
2
s
2
o
3
solution, then dropwise adds rare HCl of 5mL mass fraction 10%, and dropping limit, limit is stirred, and obtains sulphur colloidal sol; In sulphur colloidal sol, add the carbon nanofiber arrays of 1/5 quality, stir, dipping 30min, dry carbon sulphur composite material.
) the coated same embodiment 1 of metal oxide.
embodiment 3:
1) preparation of carbon sulphur composite material is with embodiment 2.
) preparation of positive pole: compound concentration is the nitric acid solution of tin of 0.1mol/L, add carbon sulphur composite material wherein and be uniformly mixed formation mixture, subsequently gained mixture is inserted spray dryer inner drying, then gained powder heating 2 ~ 5h is obtained the coated anode composite sheet of tin oxide.
embodiment 4:
the anode composite of above-described embodiment 1,2,3 and aluminium flake, barrier film are mutually reeled and add electrolyte, be prepared into secondary aluminium cell 1#, 2#, 3# and carry out charge-discharge 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 (3)
1. a nanofiber array anode composite, be made up of metal oxide, carbon nanofiber arrays, elemental sulfur and conductive substrates, it is characterized in that, described carbon nanofiber arrays vertical-growth is in conductive substrates, elemental sulfur is attached on carbon nano-fiber-wall, outermost layer coated metal oxide layer, described anode composite is three-dimensional layer structure.
2. nanofiber array anode composite according to claim 1, is characterized in that, the diameter of described carbon nanofiber arrays is 50 ~ 400nm, and length is 2 ~ 50 μm.
3. nanofiber array anode composite according to claim 1, is characterized in that, described metal oxide comprises TiO
2, MgO, Al
2o
3, ZnO, SnO
2, ZrO, CeO
2, La
2o
3, V
2o
5and MnO
2in any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420666847.9U CN204156011U (en) | 2014-11-10 | 2014-11-10 | Nanofiber array anode composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420666847.9U CN204156011U (en) | 2014-11-10 | 2014-11-10 | Nanofiber array anode composite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN204156011U true CN204156011U (en) | 2015-02-11 |
Family
ID=52514106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201420666847.9U Expired - Fee Related CN204156011U (en) | 2014-11-10 | 2014-11-10 | Nanofiber array anode composite |
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| Country | Link |
|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110504414A (en) * | 2018-05-16 | 2019-11-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Defect metal oxide/porous nano carbonaceous composite material and preparation method and application |
-
2014
- 2014-11-10 CN CN201420666847.9U patent/CN204156011U/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110504414A (en) * | 2018-05-16 | 2019-11-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Defect metal oxide/porous nano carbonaceous composite material and preparation method and application |
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| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150211 Termination date: 20191110 |
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| CF01 | Termination of patent right due to non-payment of annual fee |