CN102983308A - Carbon nanotube array/nickel oxide nanoparticle coaxial composite cathode material and preparation method thereof - Google Patents
Carbon nanotube array/nickel oxide nanoparticle coaxial composite cathode material and preparation method thereof Download PDFInfo
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- CN102983308A CN102983308A CN201210546937XA CN201210546937A CN102983308A CN 102983308 A CN102983308 A CN 102983308A CN 201210546937X A CN201210546937X A CN 201210546937XA CN 201210546937 A CN201210546937 A CN 201210546937A CN 102983308 A CN102983308 A CN 102983308A
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Abstract
The invention relates to a carbon nanotube array/nickel oxide nanoparticle coaxial composite cathode material and a preparation method thereof. The composite cathode material comprises a carbon nanotube array growing on a metal collector substrate in situ and nickel oxide nanoparticles which are uniformly distributed on the outer surface of the carbon nanotube array and are directly combined with the outer surface of the carbon nanotube array, wherein the nickel oxide nanoparticles account for 50-85 percent by weight in the composite cathode material. According to the invention, the nickel oxide nanoparticles are uniformly dispersed and attached onto the carbon nanotube with excellent mechanical performance. The problems of poor battery cycle capability and nanoparticle aggregation caused by volume change and poor mechanical performance of the nickel oxide material in the process of embedding/taking off lithium ions are solved, and therefore the carbon nanotube array/nickel oxide nanoparticle coaxial composite cathode material is favorable in cycle performance and high specific capacity and can be applied to a lithium ion battery as a cathode material.
Description
Technical field
The present invention relates to a kind of negative electrode for lithium ion battery material, be specifically related to coaxial composite negative pole material of a kind of carbon nano pipe array/nickel oxide nanoparticle and preparation method thereof, belong to the lithium ion battery negative material field.
Background technology
Fast development along with electric automobile, portable type electronic product, people grow with each passing day to the demand of high-performance secondary cell, but lithium ion battery is because the advantage such as voltage is high, specific energy is large, have extended cycle life, security performance is good, the little fast charging and discharging of self discharge and extensively concerned.
But the theoretical specific capacity of commercial li-ion battery graphitized carbon negative material is 372mAh/g at present, is limited the specific capacity that is difficult to further improve material.In the development process of negative material of new generation, NiO is owing to its reserves are abundant, cost is low, theoretical specific capacity is high, and (718mAh/g) is subject to extensive concern.But the NiO material material fragmentation that large change in volume causes in the process of embedding/lithium ionic insertion/deinsertion lost efficacy and when hanging down electricity and having caused NiO as negative material cyclical stability poor and discharge and recharge the not good problem of charge-discharge performance under the condition at a high speed, then hindered the practical application of NiO as negative material.People attempt to dissolve certainly this difficult problem by the NiO material nano.But studies show that, NiO is prepared into the 1-dimention nano pipe is difficult to obtain good effect, only discharging and recharging afterwards through 20 times, reversible specific capacity just drops to (S.A.Needham about 170mAh/g from about 470mAh/g, Synthesis of NiO nanotubes for use as negative electrodes in lithium ion batteries, Journal of Power Sources, 159:254 – 257 (2006)); Be difficult to equally obtain good effect and NiO is prepared into the two-dimensional nano thin layer, discharging and recharging afterwards through 50 times, reversible specific capacity drops to only 145mAh/g from about 1000mAh/g.Its main cause is that NiO material low electricity in the process of embedding/lithium ionic insertion/deinsertion is led, nano material is reunited and limited (the Yun Huang of change in volume effect improving, Self-assembly of ultrathin porous NiO nanosheets/graphene hierarchical structure for high-capacity and high-rate lithium storage, J.Mater.Chem., 22:2844-2847 (2012)).
Therefore, a kind of NiO negative material that is difficult for leading because change in volume causes material fragmentation inefficacy, high electricity, being difficult for reuniting of preparation has very real meaning for obtaining high performance lithium ion battery.Chinese patent CN 102522218A discloses a kind of nano nickel oxide/graphene composite electrode material and preparation method thereof and as the application of the electrode of ultracapacitor, and Chinese patent CN102169987A discloses a kind of graphene-supported porous nickel oxide and preparation method thereof and as the application of lithium ion battery anode material.
Summary of the invention
For the problems referred to above, the object of the present invention is to provide a kind of on metal collector the method for direct in-situ carbon nano tube array grows/coaxial composite material of NiO nano particle, obtain a kind ofly to be difficult for losing efficacy because change in volume causes material fragmentation, high electricity is led, be difficult for reuniting, thereby have the electrode material of good circulation performance and height ratio capacity, and it is applied to lithium ion battery as negative material.
At this, on the one hand, the invention provides the coaxial composite negative pole material of a kind of carbon nano pipe array/nickel oxide nanoparticle, described composite negative pole material comprises growth in situ in the suprabasil carbon nano pipe array of metal afflux and the nickel oxide nanoparticle that is evenly distributed on described carbon nano pipe array outer surface and combination direct with it, and wherein said nickel oxide nanoparticle shared percentage by weight in described composite negative pole material is 50～85%.
In the present invention, described NiO nano particle Uniform Dispersion also is attached on the described carbon nano-tube of mechanical performance excellence, solved the situation of the circulating battery ability that because of change in volume and bad mechanical performance cause of NiO material in embedding/lithium ionic insertion/deinsertion process and the problem of nanoparticle agglomerates.
And, described NiO nano particle and described carbon nanotube conducting direct network access node close, eliminated because binding agent and conductive agent add extra resistance, lithium ion diffusion impedance and the active material weight that causes, thus obtained larger specific capacity and better two-forty discharge and recharge battery performance under the condition.
The average grain diameter of described nickel oxide nanoparticle is below the 50nm, mostly to be 5～20nm.Therefore, the specific area that described carbon nano pipe array/nickel oxide composite material is large and the nano-scale of described nickel oxide nanoparticle have reduced the diffusion length of lithium ion in nickel oxide in the charge and discharge process, thereby guaranteed the efficient utilization of active material, be conducive to obtain higher specific capacity and better two-forty discharge and recharge battery performance under the condition.
The height of described carbon nano pipe array is 80～300 μ m, and the height of most of carbon nano-tube surpasses 200 μ m.Its in described combination electrode material be conducting bracket also be the part of active material, high array thickness is conducive to more active material NiO and loads, improve the weight ratio of active material/inert material (comprising metal forming current collector and barrier film etc.), make in the lithium ion battery of identical weight or equal volume and contain more active material, thereby make battery that higher capacity, power and energy be arranged, significant to practical application.
Again, the diameter of each carbon nano-tube is 10nm in the described carbon nano pipe array.
On the other hand, the present invention also provides the preparation method of the coaxial composite negative pole material of a kind of described carbon nano pipe array/nickel oxide nanoparticle, comprising: adopt Ni (NO
3)
26H
2The ethanolic solution of O carries out immersion treatment to growth in situ in the suprabasil carbon nano pipe array of metal afflux; Dry carbon nano pipe array through immersion treatment; And under air atmosphere, namely made described composite negative pole material in 1～5 hour in 300～500 ℃ of lower high-temperature process.
Described Ni (NO
3)
26H
2The concentration of the ethanolic solution of O is 0.15～0.50mol/L, is preferably 0.25～0.35mol/L.
The treatment temperature of described high-temperature process is preferably 430～470 ℃, and the processing time is preferably 2 hours.
Preferably, method of the present invention also further comprises by chemical vapour deposition technique in-situ growing carbon nano tube array in the substrate of described metal afflux.
On the one hand, the present invention also provides a kind of composite negative pole again, and described composite negative pole comprises: the substrate of metal afflux; And original position is formed at the coaxial composite negative pole material of the suprabasil described carbon nano pipe array/nickel oxide nanoparticle of described metal afflux.
Every carbon nano-tube of described carbon nano-array all directly links to each other with the substrate of described metal afflux and the high electricity of carbon nano-tube itself is led with accurate one-dimentional structure and formed continuously reliable, short path, low-resistance conductive network, so has greatly improved the effective rate of utilization of charge-conduction efficient and active material NiO.
In the present invention, the described metal afflux substrate resilient coating and the catalyst layer that comprise the metal forming current collector and on described metal forming current collector, load successively.
Wherein, the thickness of described metal forming current collector can be 20 μ m, and the thickness of described resilient coating can be 30nm, and the thickness of described catalyst layer can be 5nm.
Preferably, described resilient coating can be the aluminium oxide resilient coating, and described catalyst layer can be the iron catalyst layer.
Described composite negative pole is under 50mA/g constant current charge-discharge condition, and coulombic efficiency remains on more than 90%.
Description of drawings
Fig. 1 is the SEM photo of the in-situ growing carbon nano tube array of embodiment 1 preparation;
Fig. 2 is the TEM photo of the carbon nano pipe array/nickel oxide composite negative pole material of embodiment 1 preparation;
Fig. 3 is Ni (NO among the embodiment 1
3)
26H
2The thermogravimetric analysis collection of illustrative plates of O;
Fig. 4 is the high power TEM photo of the carbon nano pipe array/nickel oxide composite negative pole material of embodiment 1 preparation;
Fig. 5 is the XRD collection of illustrative plates of the carbon nano pipe array/nickel oxide composite negative pole material of embodiment 1 preparation;
Fig. 6 is the front voltage that discharges and recharges for 10 times-specific capacity curve of the lithium ion battery of embodiment 1 preparation;
Fig. 7 is the charging and discharging curve of front 55 circulations of lithium ion battery of embodiment 1 preparation;
Fig. 8 is the enclosed pasture efficiency curve of front 55 circulations of lithium ion battery of embodiment 1 preparation.
Embodiment
Further specify the present invention below in conjunction with accompanying drawing and following execution mode, should be understood that following execution mode and/or accompanying drawing only are used for explanation the present invention, and unrestricted the present invention.
Carbon nano pipe array of the present invention/nickel oxide composite negative pole material comprises growth in situ in the suprabasil carbon nano pipe array of metal afflux and the nickel oxide nanoparticle that is evenly distributed on described carbon nano pipe array outer surface and combination direct with it, and wherein said nickel oxide nanoparticle shared percentage by weight in described composite negative pole material is 50～85%.Fig. 1 is the SEM photo that the in-situ growing carbon nano tube array in the prepared described composite negative pole material of one embodiment of the invention is shown, as shown in Figure 1, described carbon nano pipe array closely is comprised of carbon nano-tube parallel to each other, and height is many more than 200 μ m, and diameter is about 10nm.Fig. 3 and Fig. 4 are respectively high power TEM photo and the XRD collection of illustrative plates that the prepared carbon nano pipe array of one embodiment of the invention/nickel oxide composite negative pole material is shown, and as shown in Figure 3, the interplanar distance of nickel oxide nanoparticle is 0.24nm in this composite negative pole material.As shown in Figure 4, the surface particles of this composite negative pole material is nickel oxide.
The present invention adopts electron beam vapor deposition method successively deposition of aluminium oxide resilient coating and iron catalyst layer on metal forming, acquisition has the substrate of catalyst layer/resilient coating/metal forming three-decker, pass through directly in-situ growing carbon nano tube array in the three-decker substrate of chemical vapor deposition (CVD) technique under certain condition, again gained in-situ growing carbon nano tube array/metal forming is immersed Ni (NO
3)
26H
2In the ethanolic solution of O, add thermal decomposition at air drying subsequently and obtain the carbon nano pipe array that direct in-situ is grown on metal collector/coaxial composite material of NiO nano particle.And it is assembled into button cell test electric property as negative material.
More specifically, as example, method of the present invention can may further comprise the steps:
1) take the metal forming (for example tantalum paper tinsel) of 20 micron thickness purity 99.95% as substrate, by the ultra vacuum electron beam evaporation system 5.0 * 10
-8Deposit successively the thick aluminium oxide of 30nm and the thick iron of 5nm in normal temperature with the speed of 0.05nm/s under the pressure of mbar, obtain iron/aluminium oxide/tantalum three-decker.The three-decker of gained is sent into the central thermal treatment zone of hot CVD stove, be warming up to 650 ℃ under the argon shield, hydrogen pretreatment 8 minutes passes into 8sccm acetylene/60sccm hydrogen/140sccm argon gas, and pressure rises to 5 * 10
5Pa grew one hour, and rear cooling obtains the in-situ growing carbon nano tube array;
2) with step 1) in gained in-situ growing carbon nano tube array/metal forming immerse the Ni (NO of 0.15～0.50mol/L
3)
26H
2In the ethanolic solution of O.Carbon nano pipe array/metal forming after will soaking is subsequently sent in the drying box dry 5 hours, it is sent in the heat-treatment furnace that 300～500 ℃ of high-temperature process obtained in-situ growing carbon nano tube array/nickel oxide composite material in 1～5 hour under air atmosphere again;
Above-mentioned metallic substrates can be used as negative pole together with the carbon nano pipe array on it/nickel oxide composite material and is used for the assembling lithium battery, for example in vacuum glove box take metal lithium sheet as to electrode and reference electrode, Celgard2400 is barrier film, electrolyte is that LiPF6/ (EC+DMC) solution of 1M is directly with step 2) in resulting in-situ growing carbon nano tube array/nickel oxide composite material be assembled into 2025 type button half-cells (need not to add conductive agent and binding agent) as negative material, and its electric property is tested.
In step 1) in, the substrate of metal afflux is not limited to tantalum, can also be copper, aluminium etc.
In step 2) in, preferably, Ni (NO
3)
26H
2The concentration of the ethanolic solution of O is 0.25～0.35mol/L.Again, preferably, the high-temperature process temperature is 430～470 ℃, and the processing time is 2 hours.
The present invention compared with prior art has following advantage:
(1) NiO nano particle Uniform Dispersion and be attached to the carbon nano-tube of mechanical performance excellence has solved the situation of the circulating battery ability that because of change in volume and bad mechanical performance cause of NiO material in embedding/lithium ionic insertion/deinsertion process and the problem of nanoparticle agglomerates;
(2) NiO nano particle and carbon nanotube conducting direct network access node close, eliminated because binding agent and conductive agent add extra resistance, lithium ion diffusion impedance and the active material weight that causes, thus obtained larger specific capacity and better two-forty discharge and recharge battery performance under the condition;
(3) every carbon nano-tube all directly links to each other with metal collector and the high electricity of carbon nano-tube itself is led with accurate one-dimentional structure and formed continuously reliable, short path, low-resistance conductive network, so has greatly improved the effective rate of utilization of charge-conduction efficient and active material NiO;
(4) specific area that carbon nano pipe array/nickel oxide composite material is large and nickel oxide nano size reduction the diffusion length of lithium ion in nickel oxide in the charge and discharge process, thereby guaranteed the efficient utilization of active material, be conducive to obtain higher specific capacity and better two-forty discharge and recharge battery performance under the condition;
(5) carbon nano-tube in electrode material be conducting bracket also be the part of active material, high array thickness (surpassing 200 μ m) is conducive to more active material NiO and loads, improve the weight ratio of active material/inert material (comprising metal forming current collector and barrier film etc.), make in the lithium ion battery of identical weight or equal volume and contain more active material, thereby make battery that higher capacity, power and energy be arranged, significant to practical application.
The below further exemplifies embodiment to describe the present invention in detail.Should understand equally; following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The reaction temperature that following example is concrete, time, inventory, technological parameter etc. also only are examples in the OK range, namely, those skilled in the art can do in the suitable scope by the explanation of this paper and select, and not really want to be defined in the hereinafter concrete numerical value of example.
Embodiment 1
Take thickness as 20 μ m, the tantalum paper tinsel of purity as 99.95% be as substrate, by the ultra vacuum electron beam evaporation system 5.0 * 10
-8Deposit successively the thick aluminium oxide of 30nm and the thick iron of 5nm in normal temperature with the speed of 0.05nm/s under the pressure of mbar, obtain iron catalyst layer/aluminium oxide resilient coating/metal tantalum foil three-decker.The three-decker of gained is placed the central thermal treatment zone of hot CVD stove, under argon shield, be warming up to 650 ℃, then close argon gas, pass into hydrogen and preliminary treatment 8 minutes.The mist that passes into acetylene, hydrogen and argon gas with the flow velocity of 8sccm, 60sccm and 140sccm respectively again pressure to the stove rises to 5 * 10
5Pa is incubated cooling after 1 hour, obtains the in-situ growing carbon nano tube array;
Referring to Fig. 1, prepared carbon nano pipe array height is about 200 μ m, and diameter is about 10nm, and with the direct strong bonded of metallic substrates;
Gained in-situ growing carbon nano tube array/metal forming immerses the Ni (NO of 0.30mol/L
3)
26H
2In the ethanolic solution of O.Carbon nano pipe array/metal forming after will soaking is subsequently sent in the drying box dry 5 hours, it is sent in the heat-treatment furnace that 450 ℃ of high-temperature process obtained in-situ growing carbon nano tube array/nickel oxide composite negative pole material in 2 hours under air atmosphere again;
Fig. 2 is the TEM photo of the carbon nano pipe array/nickel oxide composite negative pole material of present embodiment preparation.As seen from the figure, the dispersion of nickel oxide nano-crystal particle is distributed as the change in volume of active material in charge and discharge process and has reserved cushion spaces axial along carbon nano-tube and horizontal a plurality of directions, having solved well thus active material increases the phenomenon that fails because of the specific capacity that bulk effect causes material fragmentation to cause with cycle-index, and nickel oxide and carbon nano-tube strong bonded;
Fig. 4 is the high power TEM photo of the carbon nano pipe array/nickel oxide composite negative pole material of present embodiment preparation, and as shown in the figure, the interplanar distance of nickel oxide nanoparticle is 0.24nm;
Fig. 5 is the XRD collection of illustrative plates of the carbon nano pipe array/nickel oxide composite negative pole material of present embodiment preparation, and the surface particles that can confirm thus prepared composite negative pole material is NiO;
Fig. 3 is Ni (NO in the present embodiment
3)
26H
2The thermogravimetric analysis collection of illustrative plates of O can determine that from this figure the high-temperature process temperature needs more than 300 ℃, with Ni (NO
3)
26H
2O is decomposed into NiO fully;
In vacuum glove box take metal lithium sheet as to electrode and reference electrode, Celgard2400 is barrier film, the LiPF6/ of 1M (EC+DMC) solution is electrolyte, and resulting in-situ growing carbon nano tube array group is dressed up 2025 type button half-cells, the test electric property.Test result is referring to Fig. 6,7,8.Prepared in-situ growing carbon nano tube array/nickel oxide composite negative pole material is done under the 50mA/g constant current and is discharged and recharged experiment, first discharge specific capacity is 1027.2mAh/g, the initial charge specific capacity is 664.1mAh/g, specific discharge capacity drops to the 569.3mAh/g minimum in the circulation gradually the 11st time subsequently, begin subsequently to rise and reach the peak of 744.6mAh/g with the 51st circulation, specific discharge capacity is stabilized in about 720mAh/g subsequently.The shared percentage by weight of nickel oxide is 65% in prepared in-situ growing carbon nano tube array/nickel oxide composite negative pole material, and the shared percentage by weight of carbon nano-tube is 35%.Its coulomb efficient remains on the high level about 95%.
Embodiment 2
Prepare lithium ion battery in-situ growing carbon nano tube array/nickel oxide composite negative pole material according to embodiment 1 technique, wherein the high-temperature process temperature is 400 ℃.Prepared in-situ growing carbon nano tube array/nickel oxide composite negative pole material is done under the 50mA/g constant current and is discharged and recharged experiment, first discharge specific capacity is 1036.0mAh/g, the initial charge specific capacity is 616.6mAh/g, specific discharge capacity drops to the 588.9mAh/g minimum in the circulation gradually the 7th time subsequently, begin subsequently to rise and reach the peak of 677.7mAh/g with the 35th circulation, specific discharge capacity is stabilized in about 670mAh/g subsequently.The shared percentage by weight of nickel oxide is 68% in prepared in-situ growing carbon nano tube array/nickel oxide composite negative pole material, and the shared percentage by weight of carbon nano-tube is 32%.Its coulomb efficient remains on the high level about 93%.
Embodiment 3
Prepare lithium ion battery in-situ growing carbon nano tube array/nickel oxide composite negative pole material according to embodiment 1 technique, wherein the high-temperature process temperature is 500 ℃.Prepared in-situ growing carbon nano tube array/nickel oxide composite negative pole material is done under the 50mA/g constant current and is discharged and recharged experiment, first discharge specific capacity is 980.5mAh/g, the initial charge specific capacity is 655.7mAh/g, specific discharge capacity drops to the 580.2mAh/g minimum in the circulation gradually the 13rd time subsequently, begin subsequently to rise and reach the peak of 702.3mAh/g with the 44th circulation, specific discharge capacity is stabilized in about 690mAh/g subsequently.The shared percentage by weight of nickel oxide is 74% in prepared in-situ growing carbon nano tube array/nickel oxide composite negative pole material, and the shared percentage by weight of carbon nano-tube is 26%.Its coulomb efficient remains on the high level about 95%.
Embodiment 4
Prepare lithium ion battery in-situ growing carbon nano tube array/nickel oxide composite negative pole material, wherein Ni (NO according to embodiment 1 technique
3)
26H
2The concentration of O in ethanolic solution is 0.15mol/L.Prepared in-situ growing carbon nano tube array/nickel oxide composite negative pole material is done under the 50mA/g constant current and is discharged and recharged experiment, first discharge specific capacity is 1130.5mAh/g, the initial charge specific capacity is 580.1mAh/g, specific discharge capacity drops to the 490.9mAh/g minimum in the circulation gradually the 11st time subsequently, begin subsequently to rise and reach the peak of 660.1mAh/g with the 39th circulation, specific discharge capacity is stabilized in about 650mAh/g subsequently.The shared percentage by weight of nickel oxide is 56% in prepared in-situ growing carbon nano tube array/nickel oxide composite negative pole material, and the shared percentage by weight of carbon nano-tube is 44%.Its coulomb efficient remains on the high level about 95%.
Prepare lithium ion battery in-situ growing carbon nano tube array/nickel oxide composite negative pole material, wherein Ni (NO according to embodiment 1 technique
3)
26H
2The concentration of O in ethanolic solution is 0.50mol/L.Prepared in-situ growing carbon nano tube array/nickel oxide composite negative pole material is done under the 50mA/g constant current and is discharged and recharged experiment, first discharge specific capacity is 912.0mAh/g, the initial charge specific capacity is 643.8mAh/g, and specific discharge capacity descends gradually and is stabilized in about 590mAh/g after the 20th circulation subsequently.The shared percentage by weight of nickel oxide is 85% in prepared in-situ growing carbon nano tube array/nickel oxide composite negative pole material, and the shared percentage by weight of carbon nano-tube is 15%.Its coulomb efficient remains on the high level about 92%.
Industrial applicability: the coaxial composite negative pole material of carbon nano pipe array/nickel oxide nanoparticle of the present invention is difficult for losing efficacy because change in volume causes material fragmentation, high electricity is led, be difficult for reunion, thereby have good circulation performance and height ratio capacity, can be used as negative material and be applied to lithium ion battery.
Claims (14)
1. coaxial composite negative pole material of carbon nano pipe array/nickel oxide nanoparticle, it is characterized in that, comprise growth in situ in the suprabasil carbon nano pipe array of metal afflux and the nickel oxide nanoparticle that is evenly distributed on described carbon nano pipe array outer surface and combination direct with it, wherein said nickel oxide nanoparticle shared percentage by weight in described composite negative pole material is 50～85%.
2. the coaxial composite negative pole material of carbon nano pipe array/nickel oxide nanoparticle according to claim 1 is characterized in that, the height of described carbon nano pipe array is 80～300 μ m.
3. the coaxial composite negative pole material of carbon nano pipe array/nickel oxide nanoparticle according to claim 2 is characterized in that, the height of described carbon nano pipe array is more than the 200 μ m.
4. the coaxial composite negative pole material of each described carbon nano pipe array/nickel oxide nanoparticle in 3 according to claim 1 is characterized in that the diameter of each carbon nano-tube is 10nm in the described carbon nano pipe array.
5. the coaxial composite negative pole material of each described carbon nano pipe array/nickel oxide nanoparticle in 4 according to claim 1 is characterized in that the average grain diameter of described nickel oxide nanoparticle is below the 50nm.
6. the coaxial composite negative pole material of carbon nano pipe array/nickel oxide nanoparticle according to claim 5 is characterized in that, the average grain diameter of described nickel oxide nanoparticle is 5～20nm.
7. the preparation method of the coaxial composite negative pole material of each described carbon nano pipe array/nickel oxide nanoparticle in the claim 1 to 6 is characterized in that, comprising: adopt Ni (NO
3)
26H
2The ethanolic solution of O carries out immersion treatment to growth in situ in the suprabasil carbon nano pipe array of metal afflux;
Dry carbon nano pipe array through immersion treatment; And
Under air atmosphere, namely made described composite negative pole material in 1～5 hour in 300～500 ℃ of lower high-temperature process.
8. preparation method according to claim 7 is characterized in that, described Ni (NO
3)
26H
2The concentration of the ethanolic solution of O is 0.15～0.50mol/L.
9. according to claim 7 or 8 described preparation methods, it is characterized in that, also comprise by chemical vapour deposition technique in-situ growing carbon nano tube array in the substrate of described metal afflux.
10. a composite negative pole is characterized in that, comprising:
The substrate of metal afflux; And
The coaxial composite negative pole material of each described carbon nano pipe array/nickel oxide nanoparticle in original position is formed at described metal afflux according to claim 1 suprabasil～6.
11. composite negative pole according to claim 10 is characterized in that, resilient coating and catalyst layer that the substrate of described metal afflux comprises the metal forming current collector and loads successively on described metal forming current collector.
12. composite negative pole according to claim 11 is characterized in that, the thickness of described metal forming current collector is 20 μ m, and the thickness of described resilient coating is 30nm, and the thickness of described catalyst layer is 5nm.
13. according to claim 11 or 12 described composite negative poles, it is characterized in that described resilient coating is that aluminium oxide resilient coating and described catalyst layer are the iron catalyst layer.
14. each described composite negative pole in 13 is characterized in that described composite negative pole is under 50mA/g constant current charge-discharge condition according to claim 10, coulombic efficiency remains on more than 90%.
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| CN103633304A (en) * | 2013-12-06 | 2014-03-12 | 福州大学 | Method for preparing coaxially-composite nano material by using carbon nano tube as core |
| CN103647047A (en) * | 2013-12-23 | 2014-03-19 | 中国科学院上海硅酸盐研究所 | CNT (Carbon Nano Tube)/SnO2 coaxial composite array lithium ion battery negative electrode material |
| CN103752314A (en) * | 2013-12-09 | 2014-04-30 | 中国科学院山西煤炭化学研究所 | Catalyst for preparation of long-chain alpha-olefin by olefin superposition and its preparation method and use |
| CN107369824A (en) * | 2017-07-26 | 2017-11-21 | 山东理工大学 | The preparation method of lithium ion battery NiO/MgO/C composite negative pole materials |
| US10135065B2 (en) | 2015-02-03 | 2018-11-20 | Microvast Power Systems Co., Ltd. | Composite anode material including nickel oxide and the method for preparing the same |
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| CN111261863A (en) * | 2020-02-03 | 2020-06-09 | 吉林建筑大学 | Three-dimensional nickel nanotube array, preparation method thereof, lithium ion battery and application |
| RU2758442C1 (en) * | 2020-12-08 | 2021-10-28 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской Академии наук (ФГБУН ИПХФ РАН) | Composite cathode material and method for its preparation |
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| CN111261863B (en) * | 2020-02-03 | 2022-12-23 | 吉林建筑大学 | Three-dimensional nickel nanotube array, preparation method thereof, lithium ion battery and application |
| RU2758442C1 (en) * | 2020-12-08 | 2021-10-28 | Федеральное государственное бюджетное учреждение науки Институт проблем химической физики Российской Академии наук (ФГБУН ИПХФ РАН) | Composite cathode material and method for its preparation |
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