CN104773762B - A kind of NiCo being grown on carbon cloth2O4Meso-porous nano tube material and preparation method thereof - Google Patents
A kind of NiCo being grown on carbon cloth2O4Meso-porous nano tube material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of NiCo being grown on carbon cloth2O4Meso-porous nano tube material, NiCo2O4Meso-porous nano tube material is grown in carbon cloth substrate, described NiCo2O4Meso-porous nano tube material is the NiCo of 5～10nm by particle diameter2O4Nanocrystalline assembling, internal diameter is 20～50nm, and wall thickness is 10～20nm, and pipe range is 0.5～2.0 μm, and draw ratio is 250～1000；Described mesoporous for NiCo2O4Hole between nanocrystalline, mesopore size is 2～5nm。Present invention also offers its preparation method, by the accurate control to hydrothermal reaction condition, carbon cloth grown the NiCo with special construction2O4Meso-porous nano tube material, when using as electrode material for super capacitor, possesses high ratio electric capacity, high rate performance under high current density and long-term cycle performance。
Description
Technical field
The present invention relates to the preparation field of nano material, particularly relate to a kind of NiCo being grown on carbon cloth2O4Meso-porous nano tube material and preparation method thereof。
Background technology
Transition metal oxide is NiO, Co such as3O4、MnO2、NiCo2O4Deng aboundresources, cheap, theoretical higher than electric capacity, electrochemical reversibility is good, it is believed that be a kind of electrode material for super capacitor having a extensive future。Wherein, the transiton metal binary oxides NiCo of spinel structure2O4Because of advantages such as its theoretical specific capacity height, Stability Analysis of Structures, good cycle, receive extensive concern。Owing to fake capacitance reaction occurs mainly in material surface, the material with high specific surface area will have higher actual ratio electric capacity, and high rate during charging-discharging also can be better, therefore by NiCo2O4Making nano material, the bigger serface characteristic utilizing nano material is an effective strategy to improve its chemical property, NiCo2O4The multiple nanostructureds such as nano wire, nanometer rods and nanometer sheet all have been reported that in recent years, all show higher electrochemical capacitance performance。
NiCo2O4Primary synthetic methods have: high temperature solid-state method, mechanochemical synthesis, sol-gal process, liquid phase chemical coprecipitation, co-precipitation thermal decomposition and hydro-thermal method etc., high temperature solid-state method is traditional synthetic method, although technique is simple, but due to NiCo2O4The character of poor heat stability, decomposed between 400-600 DEG C so that it is some activity such as the reduction of catalysis activity。Mechanical activation synthetic method, introduces a large amount of strain and defect, products therefrom bad dispersibility in preparation process。The product grain particle diameter that sol-gal process obtains by adding surfactant is less and is evenly distributed, but is readily incorporated impurity。And the product structure of liquid chemical precipitation method synthesis is imperfect, can generating portion metastable phase。
At present, many employing co-precipitation thermal decompositions and hydro-thermal method prepare NiCo2O4。The preparation method that Chinese patent literature if publication number is CN103318978A discloses a kind of mesoporous nickel cobalt, with soluble nickel salt, cobalt salt for raw material, oxalates is precipitant, at Ni2+—Co2+—NH3—NH4 +—SGn-—Co2O4 2—H2O—C2H5OH system is prepared threadiness presoma, is subsequently placed in 250-400 DEG C of temperature, air atmosphere and thermally decomposes to yield mesoporous NiCo2O4Fiber。And for example publication number is method and the application thereof that the Chinese patent literature of CN102745752A discloses a kind of water heat transfer mesoporous nickel cobalt nano wire, by CoCl2.6H2O、NiCl2.6H2O and CO (NH2) be dissolved in appropriate amount of deionized water, wherein CoCl2.6H2O and NiCl2.6H2The mol ratio of O is 1:2, utilizes magnetic stirring apparatus stirred by mixed solution and be transferred in autoclave, heats to 100 DEG C, constant temperature 10h。After being cooled to room temperature, reactant filtered, wash, after drying 250 DEG C of annealing 2h in air atmosphere。But the product that said method prepares respectively is fibre structure。
Currently for NiCo2O4Nano-tube material also have research, but mainly adopt method of electrostatic spinning to prepare, the nanotube caliber prepared by this method is thick, and residual organic matter can reduce NiCo2O4Electrical conductivity, it is made electrode of super capacitor and is generally adopted the slurry-scraping method of mixed chemical glue and conductive agent, and the electrode interior material dense packing made, internal resistance are relatively big, and these factors reduce Ni nanoparticle Co2O4Nanometer size effect, be unfavorable for the further improvement of electrochemical capacitance performance。Although additionally, NiCo2O4Electrical conductivity is higher, but with material with carbon element and metal oxide containing precious metals phase specific conductivity or not high enough, more very fast than capacitance fade under high current density, high rate performance is poor, existing research or with high conductive material compound, as with the compound such as CNT, Graphene, or by NiCo2O4It is grown directly upon in the metallic substrates such as nickel foam, but is limited to NiCo2O4The restriction of material structure and base material, electrochemical capacitance performance is improved limited。
Summary of the invention
The invention provides a kind of NiCo being grown on carbon cloth2O4The preparation method of meso-porous nano tube material, by the accurate control to hydrothermal reaction condition, grown the NiCo with special construction on carbon cloth2O4Meso-porous nano tube material, when using as electrode material for super capacitor, possesses high ratio electric capacity, high rate performance under high current density and long-term cycle performance。
A kind of NiCo being grown on carbon cloth2O4Meso-porous nano tube material, NiCo2O4Meso-porous nano tube material is grown in carbon cloth substrate, described NiCo2O4Meso-porous nano tube material is the NiCo of 5～10nm by particle diameter2O4Nanocrystalline assembling, internal diameter is 20～50nm, and wall thickness is 10～20nm, and pipe range is 0.5～2.0 μm, and draw ratio is 250～1000；Described mesoporous for NiCo2O4Hole between nanocrystalline, mesopore size is 2～5nm。
A kind of described NiCo being grown on carbon cloth2O4The preparation method of meso-porous nano tube material, specifically comprises the following steps that
It is stoichiometrically that 42～48:1:2:6～8 mix with deionized water by carbamide, nickel nitrate, cobaltous chloride and hexamethylenetetramine, dissolve after completely and obtain precursor solution, carbon cloth is placed in precursor solution, through hydro-thermal reaction 6～8h at 90～110 DEG C, then through washing, dry and be thermally treated resulting in the described NiCo being grown on carbon cloth2O4Meso-porous nano tube material。
Add after substrate, at substrate surface fabricated in situ by NiCo2O4The nanocrystalline NiCo assembled2O4Meso-porous nano tube material。
As preferably, Ni in described precursor solution2+Concentration is 2.6～3.2g/L。
Described nickel nitrate can also be Nickelous nitrate hexahydrate, and cobaltous chloride is cobalt chloride hexahydrate。
As preferably, described hydro-thermal reaction carries out in politef reactor, and the compactedness of described reactor is 60～80%。It is preferred that, described hydrothermal temperature is 95～105 DEG C。
As preferably, described carbon cloth is of a size of 2 × 2cm2。
As preferably, described baking temperature is 70 DEG C。
As preferably, described heat treatment carries out under inert gas shielding, and heat treatment temperature is 300～400 DEG C, and temperature retention time is 2～6h。
Prepared by the present invention is grown in the NiCo on carbon cloth2O4Meso-porous nano tube material is a kind of excellent electrode material for super capacitor, particle diameter be that the nanocrystalline of 5～10nm assembles, and little size particle materials can be substantially reduced electronics, ion in the transmission range of material internal, improves large current density power；Material specific surface area is big, and skin-material accounting is high, can significantly improve NiCo2O4Discharge and recharge utilization ratio；NiCo2O4Having the hole being of a size of 2～5nm between nanocrystalline, make tube wall present meso-hole structure, material center also has a bigger hollow pipeline simultaneously, and the characteristic in these structures makes to construct NiCo2O4The inside and outside crystal grain of meso-porous nano pipe all facilitates and is adequately exposed to electrolyte, and the bigger serface of material efficiently and is effectively utilized, thus significantly improving NiCo2O4Ratio electric capacity, high rate performance under high current density and long-term cycle performance。The carbon cloth of Choice of substrate materials high connductivity。The carbon cloth being made up of neat carbon fiber, it is ensured that be grown in suprabasil NiCo2O4Nano-tube material and electrolyte are fully contacted, and increase effective contact area, are conducive to the quick transmission in electrode of electronics, ion, it is possible to strengthen NiCo simultaneously2O4Electric conductivity。The NiCo of growth2O4Electrode material maintains suitable space each other, reduces the resistance that electrolyte ion interts between electrode material, also can promote NiCo2O4Utilization rate, improve high current charge-discharge when NiCo2O4Multiplying power property。
Compared with prior art, present invention have the advantage that
The present invention, by the accurate control to hydrothermal reaction condition, is prepared for a kind of NiCo being grown on carbon cloth2O4Meso-porous nano tube material, this NiCo2O4Meso-porous nano tube material possesses special pattern, when using as electrode material for super capacitor, possesses high ratio electric capacity, high rate performance under high current density and long-term cycle performance。
Accompanying drawing explanation
The NiCo being grown on carbon cloth of Fig. 1 and Fig. 2 respectively embodiment 1 preparation2O4Meso-porous nano tube material SEM figure under different amplification, the illustration of Fig. 1 is NiCo2O4The partial enlargement SEM figure of meso-porous nano pipe。
Fig. 3 is the NiCo of embodiment 1 preparation2O4The XRD spectra of meso-porous nano tube material。
Detailed description of the invention
Embodiment 1
Take 0.32gNi (NO3)2·6H2O、0.53gCoCl2·6H2O、2.97gCO(NH2)2And 1.1gN4(CH2)6It is dissolved in 100mL deionized water, to being completely dissolved the pink colour solution forming clarification；Then 60mL solution is transferred in the autoclave of 100mL, then by 2 × 2cm that one piece cleans up2Carbon cloth be positioned over solution, put into baking oven after reactor is airtight, heating is to 95 DEG C; temperature retention time 8h; clean with deionized water after carbon cloth after hydro-thermal reaction is taken out, 70 DEG C of drying, then be placed in the quartz tube furnace under inert gas shielding and make annealing treatment; heating-up temperature is 350 DEG C; temperature retention time is 3h, is cooled to room temperature and takes out sample, its SEM atlas analysis is found; as illustrated in fig. 1 and 2, the NiCo on carbon cloth it is grown in2O4Presenting nanotube morphologies, bore is about 40nm, and thickness of pipe wall is about 20nm, pipe range about 1.2 μm, draw ratio about 300。To a nanometer mouth of pipe amplifying observation, as shown in Fig. 1 illustration, NiCo2O4Nanotube is assembled by nanocrystalline, nanocrystalline particle diameter about 5～10nm, there is the mesoporous of size about 2～5nm between nanocrystalline。Sample is placed in aqueous solution and uses vibration of ultrasonic wave, shake off powder and regather and carry out XRD material phase analysis, shown in Fig. 3, the diffraction maximum of sample and NiCo2O4(JCPDS20-0781) fit like a glove, there is no other impurity peaks and exist, it was shown that product is high-purity NiCo2O4Material。
Embodiment 2
Take 0.29gNi (NO3)2·6H2O、0.48gCoCl2·6H2O、2.50gCO(NH2)2And 1gN4(CH2)6It is dissolved in 100mL deionized water, to being completely dissolved the pink colour solution forming clarification；Then 80mL solution is transferred in the autoclave of 100mL, then by 2 × 2cm that one piece cleans up2Carbon cloth be positioned over solution; put into baking oven after reactor is airtight, heat to 100 DEG C, insulation reaction 8h; clean with deionized water after carbon cloth after hydro-thermal reaction is taken out; 70 DEG C of drying, then be placed in the quartz tube furnace under inert gas shielding and make annealing treatment, heating-up temperature is 380 DEG C; temperature retention time is 2h; it is cooled to room temperature and takes out sample, it is carried out SEM atlas analysis discovery, is grown in the NiCo on carbon cloth2O4The nanocrystalline particle diameter about 5～10nm of meso-porous nano tube material, mesopore size is 2～5nm about, and bore is about 30nm, and thickness of pipe wall is about 16nm, pipe range about 0.9 μm, draw ratio about 300。
Embodiment 3
Take 0.26gNi (NO3)2·6H2O、0.43gCoCl2·6H2O、2.43gCO(NH2)2And 0.9gN4(CH2)6It is dissolved in 100mL deionized water, to being completely dissolved the pink colour solution forming clarification；Then 80mL solution is transferred in the autoclave of 100mL, then by 2 × 2cm that one piece cleans up2Carbon cloth be positioned over solution, put into baking oven after reactor is airtight, heating to 105 DEG C, temperature retention time 6h, 70 DEG C of drying；Being placed in the quartz tube furnace under inert gas shielding again and make annealing treatment, heating-up temperature is 300 DEG C, and temperature retention time is 6h, is cooled to room temperature and takes out sample, its SEM atlas analysis is found, is grown in the NiCo on carbon cloth2O4The nanocrystalline particle diameter about 5～10nm of meso-porous nano tube material, mesopore size is 2～5nm about, and bore is about 20nm, and thickness of pipe wall is about 12nm, pipe range 0.6 μm, draw ratio about 300。
Claims (8)
1. the NiCo being grown on carbon cloth2O4Meso-porous nano tube material, it is characterised in that NiCo2O4Meso-porous nano tube material is grown in carbon cloth substrate, described NiCo2O4Meso-porous nano tube material is the NiCo of 5～10nm by particle diameter2O4Nano-crystalline granule assembles, and internal diameter is 20～50nm, and wall thickness is 10～20nm, and pipe range is 0.5～2.0 μm, and draw ratio is 250～1000；Described mesoporous for NiCo2O4Hole between nanocrystalline, mesopore size is 2～5nm。
2. the NiCo being grown on carbon cloth according to claim 12O4The preparation method of meso-porous nano tube material, it is characterised in that step is as follows:
It is stoichiometrically that 42～48:1:2:6～8 mix with deionized water by carbamide, nickel nitrate, cobaltous chloride and hexamethylenetetramine, dissolve after completely and obtain precursor solution, carbon cloth is placed in precursor solution, through hydro-thermal reaction 6～8h at 90～110 DEG C, then through washing, dry and be thermally treated resulting in the described NiCo being grown on carbon cloth2O4Meso-porous nano tube material。
3. the NiCo being grown on carbon cloth according to claim 22O4The preparation method of meso-porous nano tube material, it is characterised in that Ni in described precursor solution2+Concentration is 2.6～3.2g/L。
4. the NiCo being grown on carbon cloth according to claim 22O4The preparation method of meso-porous nano tube material, it is characterised in that described hydro-thermal reaction carries out in politef reactor, the compactedness of described reactor is 60～80%。
5. the NiCo being grown on carbon cloth according to claim 42O4The preparation method of meso-porous nano tube material, it is characterised in that described hydrothermal temperature is 95～105 DEG C。
6. the NiCo being grown on carbon cloth according to claim 22O4The preparation method of meso-porous nano tube material, it is characterised in that described carbon cloth is of a size of 2 × 2cm2。
7. the NiCo being grown on carbon cloth according to claim 22O4The preparation method of meso-porous nano tube material, it is characterised in that described baking temperature is 70 DEG C。
8. the NiCo being grown on carbon cloth according to claim 22O4The preparation method of meso-porous nano tube material, it is characterised in that described heat treatment carries out under inert gas shielding, heat treatment temperature is 300～400 DEG C, and temperature retention time is 2～6h。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105070515A (en) * | 2015-08-19 | 2015-11-18 | 华东理工大学 | Foamed nickel composite material, and preparation method and application thereof |
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| CN105417590B (en) * | 2015-11-24 | 2016-10-05 | 青岛能迅新能源科技有限公司 | A kind of method synthesizing cobalt acid nickel spinelle |
| CN106299271A (en) * | 2016-08-23 | 2017-01-04 | 南京理工大学 | A kind of nano nickel cobalt oxide/graphene composite material and preparation method thereof |
| CN107195470B (en) * | 2017-05-27 | 2019-05-10 | 中国海洋大学 | The nanotube-shaped composite material and preparation method of nickel cobalt iron ternary metal oxide |
| CN109148163B (en) * | 2017-06-16 | 2020-10-30 | 南京理工大学 | Carbon cloth/nickel cobaltate/nickel oxide flexible electrode material and preparation method thereof |
| CN109216663A (en) * | 2017-06-30 | 2019-01-15 | 南京理工大学 | A kind of nano particle/carbon cloth combination electrode material and preparation method thereof |
| CN107774264A (en) * | 2017-09-19 | 2018-03-09 | 浙江工商大学 | Load composite oxides magnetic nanometer and the electrode of CNT and its preparation and application |
| CN107740136A (en) * | 2017-10-16 | 2018-02-27 | 太原理工大学 | A kind of preparation method of the order mesoporous cathode composite of MEC |
| CN107993849B (en) * | 2017-11-27 | 2019-12-17 | 陕西科技大学 | Flexible electrode material of carbon fiber loaded nickel cobaltate nano array and preparation method thereof |
| CN108010733A (en) * | 2017-12-25 | 2018-05-08 | 电子科技大学 | A kind of flower-shaped Cu2SnS3The preparation method of flexible super capacitor electrode material |
| CN114632536B (en) * | 2022-04-01 | 2023-10-20 | 吉林化工学院 | NiCo with photocatalytic properties 2 O 4 /NiO/g-C 3 N 4 Nanotube preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003455A (en) * | 2014-06-18 | 2014-08-27 | 中国环境科学研究院 | Method for preparing multi-shape controllable nano nikel-cobalt spinel oxide |
| CN104291385A (en) * | 2014-08-26 | 2015-01-21 | 江苏合志锂硫电池技术有限公司 | Nickel cobalt oxide mesoporous microsphere and preparation method thereof |
-
2015
- 2015-03-16 CN CN201510114920.0A patent/CN104773762B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003455A (en) * | 2014-06-18 | 2014-08-27 | 中国环境科学研究院 | Method for preparing multi-shape controllable nano nikel-cobalt spinel oxide |
| CN104291385A (en) * | 2014-08-26 | 2015-01-21 | 江苏合志锂硫电池技术有限公司 | Nickel cobalt oxide mesoporous microsphere and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| "High Electrochemical Performance of Monodisperse NiCo2O4 Mesoporous Microspheres as an Anode Material for Li-Ion Batteries";Jingfa Li et al.;《ACS Applied Materials & Interfaces》;20130116;第5卷;第981-988页 * |
| "Mesoporous NiCo2O4 Nanowire Arrays Grown on Carbon Textiles as Binder-Free Flexible Electrodes for Energy Storage";Laifa Shen et al.;《Adv. Funct. Mater.》;20131216;第24卷;第2631页第3段、第2633页第1段、第2636页第2段实验部分 * |
| "Rapid Microwave-Assisted Green Synthesis of 3D Hierarchical Flower-Shaped NiCo2O4 Microsphere for High-Performance Supercapacitor";Ying Lei et al.;《ACS Applied Materials & Interfaces》;20140120;第6卷;第1773-1780页 * |
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