CN107732116A - A kind of nickelous selenide film of graphene carbon nanotube two for lithium battery and preparation method thereof - Google Patents
A kind of nickelous selenide film of graphene carbon nanotube two for lithium battery and preparation method thereof Download PDFInfo
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- CN107732116A CN107732116A CN201711157343.9A CN201711157343A CN107732116A CN 107732116 A CN107732116 A CN 107732116A CN 201711157343 A CN201711157343 A CN 201711157343A CN 107732116 A CN107732116 A CN 107732116A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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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
Abstract
The invention discloses a kind of nickelous selenide film of graphene carbon nanotube two for lithium battery, including metallic substrate layer, graphene film layer, carbon nanotube layer and the two selenizing nickel dams set gradually from bottom to up.The invention also discloses a kind of preparation method of the nickelous selenide film of graphene carbon nanotube two for lithium battery, including ultrasonic wave cleaning is carried out to metallic substrate layer, the metallic substrate layer cleaned is put into drying in vacuum drying chamber, using chemical vapour deposition technique, direct growth is gone out graphene film layer, prepares carbon nanotube layer on graphene film layer using hot filament CVD, prepared two selenizing nickel dams on carbon nanotube layer using pulsed laser deposition in metallic substrate layer.The present invention has excellent electric property, mechanical property, while has good swell gradient, ensure that each layer film can combine closely in charge and discharge process, avoids obscission caused by caused volumetric expansion after Lithium-ion embeding.
Description
Technical field
The present invention relates to technical field of lithium batteries, more particularly to a kind of selenium of graphene-carbon nano tube-two for lithium battery
Change nickel film and preparation method thereof.
Background technology
Lithium ion battery is a kind of new and effective electrochmical power source, has that energy density is big, has extended cycle life, operating voltage
Height, memory-less effect, self discharge are small and the advantages that operating temperature range is wide, are the idealizations of current various portable type electronic products
Power supply, and the preferred electrical source of power of following electric automobile are learned, there is wide application space and economic value.
Lithium ion battery is generally made up of positive pole, negative pole and electrolyte.When being charged to lithium ion battery, battery
There is lithium ion generation on positive pole, the lithium ion of generation reaches the Lithium-ion embeding negative pole of negative pole by electrolyte movement to negative pole
In, wherein the lithium ion quantity of embedded negative pole is more, charging capacity is higher；When to lithium-ion electric tank discharge, in negative pole
Lithium ion depart from, return to positive pole by electrolyte, wherein the lithium ion for returning to positive pole is more, discharge capacity is higher.Namely
Say, the volumetric properties of negative material have important influence to the energy density of lithium ion battery in lithium ion battery.
At present, most widely used in lithium cell cathode material is graphite, and its theoretical capacity is 372mAh/g, and this is far away
Reach the high power capacity demand of the various portable products of fast development, especially new-energy automobile power battery, in addition, in charge and discharge
Graphite linings are easily gradually peeled off in electric process, so as to influence its cycle performance.In addition, silicon can also be used as lithium battery graphite
Material, but silicon its volumetric expansion after Lithium-ion embeding is very big, so as to which its capacity can be caused constantly to subtract in charge and discharge cycles
It is small, limit its further application.
To sum up, a kind of nickelous selenide film of graphene-carbon nano tube-two for lithium battery and preparation method thereof is researched and developed, is replaced
For lithium cell cathode material of the prior art, it appears increasingly important.
The content of the invention
It is an object of the invention to for above-mentioned technical problem existing for prior art, there is provided a kind of stone for lithium battery
Black alkene-nickelous selenide film of CNT-two and preparation method thereof.
In order to solve the above-mentioned technical problem, the present invention proposes a kind of selenium of graphene-carbon nano tube-two for lithium battery
Change nickel film, including metallic substrate layer, graphene film layer, carbon nanotube layer and two nickelous selenides set gradually from bottom to up
Layer.
Further, the metallic substrate layer is copper substrate, golden substrate or silver substrate.
Further, the graphene film layer is single-layer graphene or few layer graphene.
Correspondingly, present invention also offers a kind of system of the nickelous selenide film of graphene-carbon nano tube-two for lithium battery
Preparation Method, comprise the following steps：
S1, ultrasonic wave cleaning is carried out to metallic substrate layer；
S2, the metallic substrate layer cleaned is put into vacuum drying chamber and dried；
S3, using chemical vapour deposition technique in metallic substrate layer in the step S2 direct growth go out graphene film
Layer；
S4, CNT prepared on graphene film layer in the step S3 using hot filament CVD
Layer；
S5, two selenizing nickel dams are prepared on carbon nanotube layer in the step S4 using pulsed laser deposition.
Further, the step S5 further comprises：
S501, by nickel powder and selenium powder ground and mixed, mixture is pressed into disk after grinding, as used in pulsed laser deposition
Target；
S502, control the distance between the carbon nanotube layer and the target are 30-50mm, by Nd:YAG produces pulse
Laser, pulse laser are incided after lens focus on the target, by the target material deposition on the carbon nanotube layer.
Further, in the pulsed laser deposition process in the step S502, pressure 5-15Pa, argon flow amount is
30sccm, sedimentation time 45-60min.
Further, in the step S1, the metallic substrate layer is copper substrate, golden substrate or silver substrate.
Further, in the step S3, the graphene film layer is single-layer graphene or few layer graphene.
Further, in the step S1, ultrasonic wave cleaning is carried out to the metallic substrate layer using acetone soln.
Implement the present invention, have the advantages that：
(1) film of the invention has charge-discharge performance, and the electrode specific capacity of the film is maintained at 382.1-451.7Ah/
g；
(2) film in the present invention has excellent mechanical property, and boundary strength reaches 50N, and hardness is in 10GPa or so；
(3) film in the present invention also has larger specific surface area, can suitably alleviate electrode material in discharge and recharge
Caused volumetric expansion, and capacitance fade is controlled, effectively improve the cyclical stability of electrode；
(4) film in the present invention has good swell gradient, ensure that each layer film can be tight in charge and discharge process
Close combination, avoid obscission caused by caused volumetric expansion after Lithium-ion embeding.
Brief description of the drawings
, below will be to required in embodiment or description of the prior art in order to illustrate more clearly of technical scheme
The accompanying drawing used is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, right
For those of ordinary skill in the art, on the premise of not paying creative work, it can also be obtained according to these accompanying drawings
Its accompanying drawing.
Fig. 1 is the structural representation of the nickelous selenide film of graphene-carbon nano tube-two for lithium battery of the present invention.
Wherein, reference corresponds in figure：1- metallic substrate layers, 2- graphene film layers, 3- carbon nanotube layers, 4- bis-
Selenizing nickel dam.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in inventive embodiments is carried out clear, complete
Ground describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based on this
The embodiment of invention, the every other reality that those of ordinary skill in the art are obtained on the premise of creative work is not made
Example is applied, belongs to the scope of protection of the invention.
Embodiment 1
As shown in figure 1, present embodiment discloses a kind of nickelous selenide film of graphene-carbon nano tube-two for lithium battery,
The film include set gradually from bottom to up metallic substrate layer 1, graphene film layer 2, the selenizing nickel dam of carbon nanotube layer 3 and two
4。
The metallic substrate layer 1 is copper substrate, golden substrate or silver substrate, and the graphene film layer 2 is individual layer
Graphene or few layer graphene.
Sem test shows that the nickelous selenide of graphene-carbon nano tube-two film in the present embodiment is by nanoparticle subgroup
Into particle is evenly distributed.
The nickelous selenide of graphene-carbon nano tube-two film in the present embodiment uses as the negative material of lithium battery, and this is thin
Film has charge-discharge performance, and the electrode specific capacity of the film is maintained at 382.1-451.7Ah/g.Thin film system in the present embodiment
Boundary strength reaches 50N, and hardness is in 10GPa or so.Thin-film material in the present embodiment also has larger specific surface area, can be with
Appropriate electrode material of alleviating controls capacitance fade in volumetric expansion caused by discharge and recharge, effectively improves the circulation of electrode
Stability.In addition, the nickelous selenide film of graphene-carbon nano tube-two in the present embodiment has good swell gradient, ensure that
Each layer film can combine closely in charge and discharge process, avoid come off caused by caused volumetric expansion after Lithium-ion embeding it is existing
As.
Embodiment 2
Present embodiment discloses a kind of preparation for preparing the nickelous selenide film of graphene-carbon nano tube-two for lithium battery
Method, this method include step：
S1, using acetone soln to metallic substrate layer 1 carry out ultrasonic wave cleaning；
Wherein, the metallic substrate layer 1 in the step S1 is copper substrate, golden substrate or silver substrate；
S2, the metallic substrate layer 1 cleaned is put into vacuum drying chamber and dried；
S3, using chemical vapour deposition technique, to go out graphene thin for direct growth in metallic substrate layer 1 in the step S2
Film layer 2；
Wherein, the graphene film layer 2 in the step S3 is single-layer graphene or few layer graphene；
S4, CNT prepared on graphene film layer 2 in the step S3 using hot filament CVD
Layer 3；
S5, two selenizing nickel dams 4 are prepared on carbon nanotube layer 3 in the step S4 using pulsed laser deposition；
Wherein, the step S5 further comprises：
S501, by nickel powder and selenium powder ground and mixed, the amount of the material of selenium powder is 3-5 times of nickel powder, by mixture after grinding
20mm sequin is pressed into, as the target used in pulsed laser deposition；
S502, the distance between the carbon nanotube layer 3 and the target is controlled to be 30-50mm, pressure 5-15Pa, argon
Throughput is 30sccm, by Nd:YAG produces pulse laser, and pulse laser is incided after lens focus on the target, by institute
Target material deposition is stated on the carbon nanotube layer 3, sedimentation time 45-60min, the present embodiment is using pulsed laser deposition in ablation
The hybrid target of nickel powder and selenium powder directly prepares two selenizing nickel dams on carbon nanotube layer so that thin-film material integrally has theoretical hold
The advantages of amount is big, chemical stability is good.
Implement the present invention, have the advantages that：
(1) film of the invention has charge-discharge performance, and the electrode specific capacity of the film is maintained at 382.1-451.7Ah/
g；
(2) film in the present invention has excellent mechanical property, and boundary strength reaches 50N, and hardness is in 10GPa or so；
(3) film in the present invention also has larger specific surface area, can suitably alleviate electrode material in discharge and recharge
Caused volumetric expansion, and capacitance fade is controlled, effectively improve the cyclical stability of electrode；
(4) film in the present invention has good swell gradient, ensure that each layer film can be tight in charge and discharge process
Close combination, avoid obscission caused by caused volumetric expansion after Lithium-ion embeding.
Above disclosed is only several preferred embodiments of the present invention, can not limit the present invention's with this certainly
Interest field, therefore the equivalent variations made according to the claims in the present invention, still belong to the scope that the present invention is covered.
Claims (9)
- A kind of 1. nickelous selenide film of graphene-carbon nano tube-two for lithium battery, it is characterised in that including from bottom to up according to Metallic substrate layer (1), graphene film layer (2), carbon nanotube layer (3) and the two selenizing nickel dams (4) of secondary setting.
- 2. graphene-carbon nano tube-two nickelous selenide film according to claim 1 for lithium battery, it is characterised in that The metallic substrate layer (1) is copper substrate, golden substrate or silver substrate.
- 3. graphene-carbon nano tube-two nickelous selenide film according to claim 1 for lithium battery, it is characterised in that The graphene film layer (2) is single-layer graphene or few layer graphene.
- A kind of 4. preparation method of nickelous selenide film of graphene-carbon nano tube-two for lithium battery, it is characterised in that including Following steps：S1, ultrasonic wave cleaning is carried out to metallic substrate layer (1)；S2, the metallic substrate layer (1) cleaned is put into vacuum drying chamber and dried；S3, using chemical vapour deposition technique in metallic substrate layer (1) in the step S2 direct growth go out graphene film Layer (2)；S4, carbon nanotube layer prepared on graphene film layer (2) in the step S3 using hot filament CVD (3)；S5, two selenizing nickel dams (4) are prepared on carbon nanotube layer (3) in the step S4 using pulsed laser deposition.
- 5. the preparation method of graphene-carbon nano tube-two nickelous selenide film according to claim 4 for lithium battery, Characterized in that, the step S5 further comprises：S501, by nickel powder and selenium powder ground and mixed, mixture is pressed into disk after grinding, as the target used in pulsed laser deposition Material；S502, control the distance between the carbon nanotube layer (3) and the target are 30-50mm, by Nd:YAG produces pulse Laser, pulse laser are incided after lens focus on the target, by the target material deposition in the carbon nanotube layer (3) On.
- 6. the preparation method of graphene-carbon nano tube-two nickelous selenide film according to claim 5 for lithium battery, Characterized in that, in pulsed laser deposition process in the step S502, pressure 5-15Pa, argon flow amount is 30sccm, sedimentation time 45-60min.
- 7. the preparation method of graphene-carbon nano tube-two nickelous selenide film according to claim 4 for lithium battery, Characterized in that, in the step S1, the metallic substrate layer (1) is copper substrate, golden substrate or silver substrate.
- 8. the preparation method of graphene-carbon nano tube-two nickelous selenide film according to claim 4 for lithium battery, Characterized in that, in the step S3, the graphene film layer (2) is single-layer graphene or few layer graphene.
- 9. the preparation method of graphene-carbon nano tube-two nickelous selenide film according to claim 4 for lithium battery, Characterized in that, in the step S1, ultrasonic wave cleaning is carried out to the metallic substrate layer (1) using acetone soln.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112086641A (en) * | 2020-08-17 | 2020-12-15 | 深圳大学 | Three-dimensional structure carbon-based energy storage thin film, preparation method, electrode plate and application |
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| CN1913203A (en) * | 2006-08-03 | 2007-02-14 | 复旦大学 | Thin film lithium battery using diselenid nickel thin film as cathode material and its preparation method |
| CN106025244A (en) * | 2016-07-30 | 2016-10-12 | 复旦大学 | Nickel selenide/graphene/carbon nanotube composite material and preparation method thereof |
| CN106252616A (en) * | 2016-07-30 | 2016-12-21 | 复旦大学 | A kind of nickelous selenide/hollow carbon fiber composite and preparation method thereof |
| US20170062143A1 (en) * | 2015-08-24 | 2017-03-02 | Aruna Zhamu | Production process for a supercapacitor having a high volumetric energy density |
| CN106995214A (en) * | 2017-04-21 | 2017-08-01 | 北京航空航天大学 | Graphene/carbon nano-tube nano laminated composite thin film and preparation method thereof |
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- 2017-11-20 CN CN201711157343.9A patent/CN107732116A/en active Pending
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|---|---|---|---|---|
| CN1913203A (en) * | 2006-08-03 | 2007-02-14 | 复旦大学 | Thin film lithium battery using diselenid nickel thin film as cathode material and its preparation method |
| US20170062143A1 (en) * | 2015-08-24 | 2017-03-02 | Aruna Zhamu | Production process for a supercapacitor having a high volumetric energy density |
| CN106025244A (en) * | 2016-07-30 | 2016-10-12 | 复旦大学 | Nickel selenide/graphene/carbon nanotube composite material and preparation method thereof |
| CN106252616A (en) * | 2016-07-30 | 2016-12-21 | 复旦大学 | A kind of nickelous selenide/hollow carbon fiber composite and preparation method thereof |
| CN106995214A (en) * | 2017-04-21 | 2017-08-01 | 北京航空航天大学 | Graphene/carbon nano-tube nano laminated composite thin film and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112086641A (en) * | 2020-08-17 | 2020-12-15 | 深圳大学 | Three-dimensional structure carbon-based energy storage thin film, preparation method, electrode plate and application |
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