CN103474630A - Silicon/oriented carbon nanotube yarn as well as preparation method and application thereof - Google Patents
Silicon/oriented carbon nanotube yarn as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of electrochemistry and particularly relates to silicon/oriented carbon nanotube yarn as well as a preparation method and application thereof. The silicon/oriented carbon nanotube yarn provided by the invention is formed by twisting a silicon/oriented carbon nanotube film. The silicon/oriented carbon nanotube film is formed by arranging silicon-carbon nanotube skin-core structures and pure carbon nanotubes in the same orientation according to certain distribution, and the axial direction of the silicon/oriented carbon nanotube film is consistent with the length direction of the film. In the silicon/oriented carbon nanotube yarn, oriented carbon nanotubes provide a rapid electron transmission channel, and in addition, a framework constructed by using the oriented carbon nanotubes has high strength and favorable flexibility, so that the silicon/oriented carbon nanotube yarn can be used as a lithium ion battery cathode material, and the stability of an electrode material in a circulation process can be ensured; moreover, silicon is wrapped in the yarn, so that a silicon material can be prevented from falling off in the circulation process; meanwhile, the periphery of the silicon material is uniformly filled with the oriented carbon nanotubes, so that good electric contact can be ensured.
Description
Technical field
The invention belongs to technical field of electrochemistry, be specifically related to a kind of silicon/aligned carbon nanotube yarn and its preparation method and application.
Background technology
Lithium ion battery have high voltage, high specific energy, self discharge little, have extended cycle life and the plurality of advantages such as memory-less effect, be widely used in such as in the consumption electronic products such as mobile phone, camera, super, and also obtained increasing research and application and development in recent years in electric automobile and electric energy storage device.Improving power density, energy density and useful life, is the main direction of lithium ion battery present stage research and development and the main demand that meets its more application scenarios.The performance of energy storage device depends on the performance of used material to a great extent.With regard to negative material, traditional graphite cathode, due to its lower theoretical specific capacity (372 mAh/g), is difficult to meet the application requirements improved constantly.And silicon materials have known maximum embedding lithium capacity (4212 mAh/g), there is the advantages such as reserves are large, nontoxic, cheap simultaneously, therefore be considered to the negative material of the alternative graphite of following the best.But the silicium cathode material, in the embedding lithium of circulating battery/de-lithium process, can experience violent change in volume (> 300%).Can cause the pulverizing of electrode material thus, the problems such as poor electric contact between electrode material and collector, finally make the capacity of electrode material decay fast, and battery has the cycle performance of non-constant.Therefore, the quick attenuation problem of the capacity while effectively solving silicon for lithium ion battery negative, become one of hot issue of current lithium ion battery negative research.
Carbon nano-tube can be regarded the curling quasi-one-dimensional nanometer material formed of graphene sheet layer as, has good conductivity, an advantage such as chemical stability is high, intensity is high and pliability is good.Recent research shows, the composite material that silicon and carbon nano-tube form can improve the silicon materials capacity that the volume acute variation causes in the circulating battery process problem of decay fast to a certain extent.Document (Juchen Guo, Ann Sun, Xilin Chen, Chunsheng Wang, Ayyakkannu Manivannan, Electrochim. Acta 56:3981-3987 (2011)) adopt the method for ball milling that silicon nanoparticle and carbon nano-tube are mixed, result is presented under the current density of 0.2 A/g, through 50 circulations, the capacity of composite material drops to 1300 mAh/g from 2300 mAh/g.Document (Lifeng Cui, Liangbing Hu, Jang Wook Choi, Yi Cui, ACS Nano 4:3671-3678 (2010)) prepared the random carbon nano-tube film that covers nano-silicon, under the current density of 0.36 A/g, after 50 circulations, the retention rate of capacity is 80%.Patent CN 102983311 A disclose a kind of random carbon nano-tube film that covers silicon, but there is no performance data.Make a general survey of existing report, the composite material of silicon and carbon nano-tube is compared simple silicon materials, aspect cycle performance, be greatly improved, but cycle-index and capacity retention rate and practical application also has very large distance.
In the composite material of silicon and carbon nano-tube, silicon materials provide high power capacity, and carbon nano-tube provides conductive carrier on the one hand, and structural framework is provided on the other hand.As conductive carrier, need to guarantee the fast transport of electronics, improve thus high rate performance and the capacity of material; And, as skeleton, should there is certain intensity and flexibility can tolerate the violent change in volume of silicon materials in cyclic process, keep integrally-built integrality, and will prevent coming off of silicon materials, finally realize good cycle performance.Therefore, how to design the structure of silicon and carbon nano tube compound material, the effect that makes carbon nano-tube can effectively give play to conductive carrier and structural framework is to realize high performance key.From existing patent and bibliographical information, it is all to be built into the random network structure that the carbon nano-tube in composite material goes up substantially, silicon materials or be present in that it is inner or be present in its surface.But random carbon nano-tube can not give full play of the mechanical property of single-root carbon nano-tube excellence, and random easily causes the reunion of carbon nano-tube and the contact resistance between the rising carbon nano-tube, simultaneously single, the easy-regulating not of the structure of silicon/random carbon nano tube compound material, limited the further raising of silicon/random carbon nano tube compound material electrode performance.
Summary of the invention
The object of the invention is to the weak point for existing Silicon Based Anode Materials for Lithium-Ion Batteries, a kind of silicon-based composite anode material for Li-ion battery with high power capacity and good circulation performance and its preparation method and application is provided.
The silicon-based composite anode material for Li-ion battery that the present invention proposes, it is the composite material of a kind of silicon and aligned carbon nanotube, be specially a kind of silicon/aligned carbon nanotube yarn, this silicon/aligned carbon nanotube yarn is formed by silicon/orientation carbon nanotube film twisting, angle of twist is 5o～35o, and diameter is 100 nm～200 μ m.
In the present invention, described silicon/orientation carbon nanotube film, the single-stage oriented film that can be formed by silico-carbo nanotube skin-core structure, the two-stage oriented film that also can be formed by carbon nano-tube and silico-carbo nanotube skin-core structure, three grades of oriented films that also can be formed by carbon nano-tube, silico-carbo nanotube skin-core structure and carbon nano-tube.
Described silico-carbo nanotube skin-core structure refers to the single-root carbon nano-tube of coated with uniform one deck nano-silicon.The thickness of nanometer silicon layer is 5 nm～100 nm.
The described single-stage oriented film be comprised of silico-carbo nanotube skin-core structure, refer to that film only consists of silico-carbo nanotube skin-core structure, and all have same orientation, and it is axially consistent with the film length direction.Film thickness is 20 nm～20 μ m.
The described two-stage oriented film formed by carbon nano-tube and silico-carbo nanotube skin-core structure, refer to that film is divided into upper and lower two parts, a part consists of pure nano-carbon tube, another part consists of silico-carbo nanotube skin-core structure, and all carbon nano-tube and silico-carbo nanotube skin-core structure all have same orientation, and it is axially consistent with the film length direction.The thickness of film each several part is 20 nm～20 μ m.
Described three grades of oriented films that formed by carbon nano-tube, silico-carbo nanotube skin-core structure and carbon nano-tube, refer to that film is divided into upper, middle, and lower part, upper and lower part consists of pure nano-carbon tube, mid portion consists of silico-carbo nanotube skin-core structure, and all carbon nano-tube and silico-carbo nanotube skin-core structure all have same orientation, and it is axially consistent with the film length direction.The thickness of film each several part is 20 nm～20 μ m.
In the present invention, the percentage by weight of described silicon in composite negative pole material is 10%～90%.
The preparation method of the silicon that the present invention proposes/aligned carbon nanotube yarn, its concrete steps are:
(1) prepare the aligned carbon nanotube monofilm.By chemical vapor deposition method carbon nano tube array grows on silicon substrate, directly membrane obtains single-orientated carbon nano-tube monofilm thus.
(2) prepare silico-carbo nanotube skin-core structure.Adopt electron beam evaporation process or chemical vapor deposition method depositing nano silicon on the aligned carbon nanotube monofilm.
(3) prepare silicon/orientation carbon nanotube film.Choose the aligned carbon nanotube monofilm of certain number of plies and the aligned carbon nanotube monofilm of depositing nano silicon, stack with same orientation, obtain single-stage oriented film or two-stage oriented film or the three grades of oriented films of setting thickness.
(4) twisting silicon/orientation carbon nanotube film.Silicon/orientation carbon nanotube film one end is fixed, thereby the other end is twisted and is obtained silicon/aligned carbon nanotube yarn by spinning-drawing machine.
Described chemical vapor deposition method carbon nano tube array grows on silicon substrate specifically describes as follows: at first, on silicon substrate, by electron beam evaporation process deposited catalyst layer, this catalyst layer structure is Al
2o
3/ Fe.Wherein, Al
2o
3thickness is 3～20 nm, and Fe thickness is 0.5～2 nm, Al
2o
3be positioned at the centre of silicon chip and Fe, as resilient coating, Fe is as catalyst; Then, adopt chemical vapour deposition technique, do carbon source with ethene, take hydrogen as reducing gases, take argon gas as carrier gas, synthetic aligned carbon nanotube array on the silicon substrate of catalyst is being arranged, the therein ethylene flow is 80～200 sccm, and argon flow amount is 300～600 sccm, and hydrogen flowing quantity is 20～50 sccm, growth temperature is 720～800 ℃, and growth time is 5～20 min.
Described electron-beam evaporation nano-silicon technique specifically describes as follows: control electron gun current and regulate deposition rate, deposition rate is set as 0.5～2/s, by controlling sedimentation time, obtains the nanometer silicon layer of setting thickness.
Described chemical vapour deposition (CVD) nano-silicon technique specifically describes as follows: take silane as the silicon source, take argon gas as carrier gas, the flow of silane is 15～30 sccm, the flow of argon gas is 200～600 sccm, and growth temperature is 500～700 ℃, and growth time is 10～90 min.
The silicon that the present invention proposes/aligned carbon nanotube yarn, can be used as lithium ion battery negative material.This silicon/aligned carbon nanotube yarn can be prepared into non-woven film, also can be prepared into weaved film, without any conductive agent, binding agent and collector.
The preparation method of the non-woven film of lithium ion battery negative that the present invention proposes, the steps include: that a silicon/aligned carbon nanotube yarn immerses in ethanolic solution, stirs, and the polytetrafluoroethylene that aperture is 1 μ m of then take is filter membrane, and suction filtration forms non-woven film.
Compared with prior art, the present invention adopt silicon and aligned carbon nanotube compound, and due to the controllable design of aligned carbon nanotube structure a kind of novel silicon/carbon nano-tube composite negative pole material---silicon/aligned carbon nanotube yarn.In silicon/aligned carbon nanotube yarn, the use of aligned carbon nanotube has overcome that the carbon nano-tube that exists in random carbon nano tube network is reunited and the drawback of large contact resistance, makes electronics to transmit rapidly; And the carbon nano-tube of orientation can give full play of the excellent mechanical property of single-root carbon nano-tube, guaranteed that the skeleton constructed by aligned carbon nanotube has high intensity and good flexibility, make electrode material keep integrality in the circulating battery process; And because the mode that adopts twisting makes silicon be wrapped in yarn, prevented silicon materials coming off in cyclic process, the while silicon materials are oriented carbon nano-tube filled on every side equably, have guaranteed good electrically contacting.Therefore, the silicon that the present invention proposes/aligned carbon nanotube composite material has high capacity and good cycle performance.And can be prepared into easily lithium ion battery negative by silicon/aligned carbon nanotube yarn.Both can obtain by the mode of suction filtration non-woven film, textile technology that also can applicable industry circle is prepared into weaved film.And this negative material is without any need for conductive agent, binding agent and collector.
The accompanying drawing explanation
Fig. 1 is the schematic diagram that is formed silicon/aligned carbon nanotube yarn by the twisting of two-stage oriented film of the present invention.
Embodiment
Below embodiments of the invention are elaborated: the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
On silicon substrate, by electron beam evaporation process deposited catalyst layer, structure is Al
2o
3/ Fe.Wherein, Al
2o
3thickness is 5 nm, and Fe thickness is 1.2 nm.Adopt chemical vapour deposition technique, with ethene, do carbon source, take hydrogen as reducing gases, take argon gas as carrier gas, synthetic aligned carbon nanotube array on the silicon substrate of catalyst is being arranged.The therein ethylene flow is 90 sccm, and argon flow amount is 400 sccm, and hydrogen flowing quantity is 30 sccm, and growth temperature is 740 ℃, and growth time is 10 min.Obtain single-orientated carbon nano-tube monofilm from the direct membrane of aligned carbon nanotube array.Adopt electron beam evaporation process, depositing nano silicon on the carbon nano-tube monofilm, speed is 0.8/s, silicon layer is thick is 16 nm, forms silico-carbo nanotube skin-core structure monofilm.Form the single-stage oriented films with 4 layers of silico-carbo nanotube skin-core structure monofilm so, twisting forms silicon/aligned carbon nanotube yarn, and angle of twist is 5o, and diameter is 5 μ m, and the percentage by weight of silicon is 65%.
Embodiment 2
On silicon substrate, by electron beam evaporation process deposited catalyst layer, structure is Al
2o
3/ Fe.Wherein, Al
2o
3thickness is 5 nm, and Fe thickness is 1.2 nm.Adopt chemical vapour deposition technique, with ethene, do carbon source, take hydrogen as reducing gases, take argon gas as carrier gas, synthetic aligned carbon nanotube array on the silicon substrate of catalyst is being arranged.The therein ethylene flow is 90 sccm, and argon flow amount is 400 sccm, and hydrogen flowing quantity is 30 sccm, and growth temperature is 740 ℃, and growth time is 10 min.Obtain single-orientated carbon nano-tube monofilm from the direct membrane of aligned carbon nanotube array.Adopt electron beam evaporation process, depositing nano silicon on the carbon nano-tube monofilm, speed is 0.8/s, silicon layer is thick is 16 nm, forms silico-carbo nanotube skin-core structure monofilm.So 4 layers of silico-carbo nanotube skin-core structure monofilm of take are upper part, the 2 layers of pure nano-carbon tube monofilm of take are grouped into the two-stage oriented film as bottom, twisting forms silicon/aligned carbon nanotube yarn, and angle of twist is 6o, diameter is 6 μ m, and the percentage by weight of silicon is 55%.
Embodiment 3
On silicon substrate, by electron beam evaporation process deposited catalyst layer, structure is Al
2o
3/ Fe.Wherein, Al
2o
3thickness is 5 nm, and Fe thickness is 1.2 nm.Adopt chemical vapour deposition technique, with ethene, do carbon source, take hydrogen as reducing gases, take argon gas as carrier gas, synthetic aligned carbon nanotube array on the silicon substrate of catalyst is being arranged.The therein ethylene flow is 90 sccm, and argon flow amount is 400 sccm, and hydrogen flowing quantity is 30 sccm, and growth temperature is 740 ℃, and growth time is 10 min.Obtain single-orientated carbon nano-tube monofilm from the direct membrane of aligned carbon nanotube array.Adopt electron beam evaporation process, depositing nano silicon on the carbon nano-tube monofilm, speed is 0.8/s, silicon layer is thick is 16 nm, forms silico-carbo nanotube skin-core structure monofilm.So 4 layers of silico-carbo nanotube skin-core structure monofilm of take are mid portion, take 2 layers of pure nano-carbon tube monofilm as upper part, the 2 layers of pure nano-carbon tube monofilm of take are grouped into three grades of oriented films as bottom, twisting forms silicon/aligned carbon nanotube yarn, angle of twist is 6o, diameter is 7 μ m, and the percentage by weight of silicon is 48%.
Embodiment 4
On silicon substrate, by electron beam evaporation process deposited catalyst layer, structure is Al
2o
3/ Fe.Wherein, Al
2o
3thickness is 5 nm, and Fe thickness is 1.2 nm.Adopt chemical vapour deposition technique, with ethene, do carbon source, take hydrogen as reducing gases, take argon gas as carrier gas, synthetic aligned carbon nanotube array on the silicon substrate of catalyst is being arranged.The therein ethylene flow is 90 sccm, and argon flow amount is 400 sccm, and hydrogen flowing quantity is 30 sccm, and growth temperature is 740 ℃, and growth time is 10 min.Obtain single-orientated carbon nano-tube monofilm from the direct membrane of aligned carbon nanotube array.Adopt electron beam evaporation process, depositing nano silicon on the carbon nano-tube monofilm, speed is 0.8/s, silicon layer is thick is 16 nm, forms silico-carbo nanotube skin-core structure monofilm.So 4 layers of silico-carbo nanotube skin-core structure monofilm of take are mid portion, take 4 layers of pure nano-carbon tube monofilm as upper part, the 4 layers of pure nano-carbon tube monofilm of take are grouped into three grades of oriented films as bottom, twisting forms silicon/aligned carbon nanotube yarn, angle of twist is 6o, diameter is 8 μ m, and the percentage by weight of silicon is 38%.
Embodiment 5
On silicon substrate, by electron beam evaporation process deposited catalyst layer, structure is Al
2o
3/ Fe.Wherein, Al
2o
3thickness is 5 nm, and Fe thickness is 1.2 nm.Adopt chemical vapour deposition technique, with ethene, do carbon source, take hydrogen as reducing gases, take argon gas as carrier gas, synthetic aligned carbon nanotube array on the silicon substrate of catalyst is being arranged.The therein ethylene flow is 90 sccm, and argon flow amount is 400 sccm, and hydrogen flowing quantity is 30 sccm, and growth temperature is 740 ℃, and growth time is 10 min.Obtain single-orientated carbon nano-tube monofilm from the direct membrane of aligned carbon nanotube array.Adopt chemical vapor deposition method to cover nano-silicon, take silane as the silicon source, take argon gas as carrier gas, the flow of silane is 30 sccm, the flow of argon gas is 500 sccm, and growth temperature is 500 ℃, and growth time is 60 min, the silicon layer formed is thick is 40 nm, is prepared into silico-carbo nanotube skin-core structure monofilm.Form the single-stage oriented films with 4 layers of silico-carbo nanotube skin-core structure monofilm so, twisting forms silicon/aligned carbon nanotube yarn, and angle of twist is 5o, and diameter is 8 μ m, and the percentage by weight of silicon is 82%.
Embodiment 6
On silicon substrate, by electron beam evaporation process deposited catalyst layer, structure is Al
2o
3/ Fe.Wherein, Al
2o
3thickness is 5 nm, and Fe thickness is 1.2 nm.Adopt chemical vapour deposition technique, with ethene, do carbon source, take hydrogen as reducing gases, take argon gas as carrier gas, synthetic aligned carbon nanotube array on the silicon substrate of catalyst is being arranged.The therein ethylene flow is 90 sccm, and argon flow amount is 400 sccm, and hydrogen flowing quantity is 30 sccm, and growth temperature is 740 ℃, and growth time is 10 min.Obtain single-orientated carbon nano-tube monofilm from the direct membrane of aligned carbon nanotube array.Adopt chemical vapor deposition method to cover nano-silicon, take silane as the silicon source, take argon gas as carrier gas, the flow of silane is 30 sccm, the flow of argon gas is 500 sccm, and growth temperature is 500 ℃, and growth time is 60 min, the silicon layer formed is thick is 40 nm, is prepared into silico-carbo nanotube skin-core structure monofilm.So 4 layers of silico-carbo nanotube skin-core structure monofilm of take are upper part, the 6 layers of pure nano-carbon tube monofilm of take are grouped into the two-stage oriented film as bottom, twisting forms silicon/aligned carbon nanotube yarn, and angle of twist is 5o, diameter is 12 μ m, and the percentage by weight of silicon is 65%.
Embodiment 7
On silicon substrate, by electron beam evaporation process deposited catalyst layer, structure is Al
2o
3/ Fe.Wherein, Al
2o
3thickness is 5 nm, and Fe thickness is 1.2 nm.Adopt chemical vapour deposition technique, with ethene, do carbon source, take hydrogen as reducing gases, take argon gas as carrier gas, synthetic aligned carbon nanotube array on the silicon substrate of catalyst is being arranged.The therein ethylene flow is 90 sccm, and argon flow amount is 400 sccm, and hydrogen flowing quantity is 30 sccm, and growth temperature is 740 ℃, and growth time is 10 min.Obtain single-orientated carbon nano-tube monofilm from the direct membrane of aligned carbon nanotube array.Adopt chemical vapor deposition method to cover nano-silicon, take silane as the silicon source, take argon gas as carrier gas, the flow of silane is 30 sccm, the flow of argon gas is 500 sccm, and growth temperature is 500 ℃, and growth time is 60 min, the silicon layer formed is thick is 40 nm, is prepared into silico-carbo nanotube skin-core structure monofilm.So 4 layers of silico-carbo nanotube skin-core structure monofilm of take are mid portion, take 8 layers of pure nano-carbon tube monofilm as upper part, the 8 layers of pure nano-carbon tube monofilm of take are grouped into three grades of oriented films as bottom, twisting forms silicon/aligned carbon nanotube yarn, angle of twist is 5o, diameter is 18 μ m, and the percentage by weight of silicon is 48%.
Embodiment 8
The silicon of gained in embodiment 1/aligned carbon nanotube yarn is immersed in ethanolic solution, stir, the polytetrafluoroethylene that aperture is 1 μ m of then take is filter membrane, and suction filtration forms non-woven film, as the negative pole of lithium ion battery.Take lithium metal as to electrode, and electrolyte is 1mol/L LiPF
6solution, the mixed liquor that solvent is ethylene carbonate and diethyl carbonate (volume ratio is 1:1), barrier film is microporous polypropylene membrane, in being full of the glove box of argon gas, is assembled into experimental cell.
By Arbin(BT2000) battery test system carries out the charge and discharge cycles test, and discharge cut-off voltage is 0.05 V, and charge cutoff voltage is 2.0 V.Described silicon/aligned carbon nanotube composite negative pole, the capacity under the current density of 100 mA/g is 1500 mAh/g, after 50 circulations, capacity is 1000 mAh/g.
Embodiment 9
The silicon of gained in embodiment 2/aligned carbon nanotube yarn is immersed in ethanolic solution, stir, the polytetrafluoroethylene that aperture is 1 μ m of then take is filter membrane, and suction filtration forms non-woven film, as the negative pole of lithium ion battery.The preparation process of battery and method of testing are with embodiment 8.Described silicon/aligned carbon nanotube composite negative pole, the capacity under the current density of 100 mA/g is 1400 mAh/g, after 50 circulations, capacity is 1100 mAh/g.
Embodiment 10
The silicon of gained in embodiment 3/aligned carbon nanotube yarn is immersed in ethanolic solution, stir, the polytetrafluoroethylene that aperture is 1 μ m of then take is filter membrane, and suction filtration forms non-woven film, as the negative pole of lithium ion battery.The preparation process of battery and method of testing are with embodiment 8.Described silicon/aligned carbon nanotube composite negative pole, the capacity under the current density of 100 mA/g is 1200 mAh/g, and after 50 circulations, capacity is 1100 mAh/g, and after 500 circulations, capacity is 1000 mAh/g.
Embodiment 11
The silicon of gained in embodiment 7/aligned carbon nanotube yarn is made to weaved film, as the negative pole of lithium ion battery.The preparation process of battery and method of testing are with embodiment 8.Described silicon/aligned carbon nanotube composite negative pole, the capacity under the current density of 100 mA/g is 800 mAh/g, after 500 circulations, capacity is 600 mAh/g.
Claims (7)
1. silicon/aligned carbon nanotube yarn is characterized in that: by silicon/orientation carbon nanotube film twisting, formed, angle of twist is 5o～35o, and diameter is 100 nm～200 μ m; Wherein,
The single-stage oriented film that described silicon/orientation carbon nanotube film is comprised of silico-carbo nanotube skin-core structure, or the two-stage oriented film formed by carbon nano-tube and silico-carbo nanotube skin-core structure, or three grades of oriented films that formed by carbon nano-tube, silico-carbo nanotube skin-core structure and carbon nano-tube;
Described silico-carbo nanotube skin-core structure refers to the single-root carbon nano-tube of coated with uniform one deck nano-silicon; The thickness of nano-silicon is 5 nm～100 nm;
The described single-stage oriented film be comprised of silico-carbo nanotube skin-core structure, refer to that film only consists of silico-carbo nanotube skin-core structure, and all have same orientation, and it is axially consistent with the film length direction; Film thickness is 20 nm～20 μ m;
The described two-stage oriented film formed by carbon nano-tube and silico-carbo nanotube skin-core structure, refer to that film is divided into upper and lower two parts, a part consists of pure nano-carbon tube, another part consists of silico-carbo nanotube skin-core structure, and all carbon nano-tube and silico-carbo nanotube skin-core structure all have same orientation, and it is axially consistent with the film length direction; The thickness of film each several part is 20 nm～20 μ m;
Described three grades of oriented films that formed by carbon nano-tube, silico-carbo nanotube skin-core structure and carbon nano-tube, refer to that film is divided into upper, middle, and lower part, upper and lower part consists of pure nano-carbon tube, mid portion consists of silico-carbo nanotube skin-core structure, and all carbon nano-tube and silico-carbo nanotube skin-core structure all have same orientation, and it is axially consistent with the film length direction; The thickness of film each several part is 20 nm～20 μ m.
2. silicon according to claim 1/aligned carbon nanotube yarn, it is characterized in that: the percentage by weight of described silicon in yarn is 10%～90%.
3. the preparation method of silicon as claimed in claim 1/aligned carbon nanotube yarn, it is characterized in that: concrete steps are:
(1) prepare the aligned carbon nanotube monofilm
By chemical vapor deposition method carbon nano tube array grows on silicon substrate, directly membrane obtains single-orientated carbon nano-tube monofilm thus;
(2) prepare silico-carbo nanotube skin-core structure
Adopt electron beam evaporation process or chemical vapor deposition method depositing nano silicon on the aligned carbon nanotube monofilm;
(3) prepare silicon/orientation carbon nanotube film
Choose the aligned carbon nanotube monofilm of certain number of plies and the aligned carbon nanotube monofilm of depositing nano silicon, stack with same orientation, obtain single-stage oriented film or two-stage oriented film or the three grades of oriented films of setting thickness;
(4) twisting silicon/orientation carbon nanotube film
Silicon/orientation carbon nanotube film one end is fixed, and the other end is twisted by spinning-drawing machine, thereby obtains silicon/aligned carbon nanotube yarn.
4. preparation method according to claim 3, it is characterized in that: described chemical vapor deposition method carbon nano tube array grows on silicon substrate, concrete steps are as follows: at first, on silicon substrate, by electron beam evaporation process deposited catalyst layer, this catalyst layer structure is Al
2o
3/ Fe; Wherein, Al
2o
3thickness is 3～20 nm, and Fe thickness is 0.5～2 nm, Al
2o
3be positioned at the centre of silicon chip and Fe, as resilient coating, Fe is as catalyst; Then, adopt chemical vapour deposition technique, do carbon source with ethene, take hydrogen as reducing gases, take argon gas as carrier gas, synthetic aligned carbon nanotube array on the silicon substrate of catalyst is being arranged, the therein ethylene flow is 80～200 sccm, and argon flow amount is 300～600 sccm, and hydrogen flowing quantity is 20～50 sccm, growth temperature is 720～800 ℃, and growth time is 5～20 min.
5. preparation method according to claim 3, it is characterized in that: described electron-beam evaporation nano-silicon technique, concrete steps are as follows: control electron gun current and regulate deposition rate, deposition rate is set as 0.5～2/s, by controlling sedimentation time, obtains the nanometer silicon layer of setting thickness.
6. preparation method according to claim 3, it is characterized in that: described chemical vapour deposition (CVD) nano-silicon technique, concrete steps are as follows: take silane as the silicon source, take argon gas as carrier gas, the flow of silane is 15～30 sccm, the flow of argon gas is 200～600 sccm, and growth temperature is 500～700 ℃, and growth time is 10～90 min.
7. silicon as claimed in claim 1/aligned carbon nanotube yarn is as the application of lithium ion battery negative material.
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Cited By (5)
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|---|---|---|---|---|
| CN105780242A (en) * | 2016-05-04 | 2016-07-20 | 东华大学 | Carbon nanotube fabric with multi-scale pore structure and preparation method thereof |
| CN107799778A (en) * | 2017-10-30 | 2018-03-13 | 上海泰坦科技股份有限公司 | A kind of carbon fiber loaded noble metal catalyst and its preparation method and application |
| CN110010860A (en) * | 2019-03-01 | 2019-07-12 | 深圳鸿鹏新能源科技有限公司 | Composite negative pole material and lithium ion battery for lithium ion battery |
| CN110028789A (en) * | 2019-04-11 | 2019-07-19 | 东华大学 | A kind of preparation method of high-strength wearable strain sensing fiber |
| CN114023924A (en) * | 2021-11-01 | 2022-02-08 | 湖南立方新能源科技有限责任公司 | Preparation method of current collector-free silicon-based negative electrode and fiber lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105780242A (en) * | 2016-05-04 | 2016-07-20 | 东华大学 | Carbon nanotube fabric with multi-scale pore structure and preparation method thereof |
| CN107799778A (en) * | 2017-10-30 | 2018-03-13 | 上海泰坦科技股份有限公司 | A kind of carbon fiber loaded noble metal catalyst and its preparation method and application |
| CN110010860A (en) * | 2019-03-01 | 2019-07-12 | 深圳鸿鹏新能源科技有限公司 | Composite negative pole material and lithium ion battery for lithium ion battery |
| CN110028789A (en) * | 2019-04-11 | 2019-07-19 | 东华大学 | A kind of preparation method of high-strength wearable strain sensing fiber |
| CN114023924A (en) * | 2021-11-01 | 2022-02-08 | 湖南立方新能源科技有限责任公司 | Preparation method of current collector-free silicon-based negative electrode and fiber lithium ion battery |
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| CN103474630B (en) | 2015-12-09 |
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