CN110212168A - A kind of preparation method of the nanocomposite of simple hydrothermal synthesis beta phase nickel hydroxide/graphene - Google Patents
A kind of preparation method of the nanocomposite of simple hydrothermal synthesis beta phase nickel hydroxide/graphene Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of the nanocomposite of simple hydrothermal synthesis beta phase nickel hydroxide/graphene, the preparation method includes using graphene oxide colloid, soluble nickel salt, highly basic as raw material, by hydrothermal synthesis, then it is freeze-dried, to obtain beta phase nickel hydroxide/graphene nano complex coacervation.Nickel hydroxide particle is compounded in graphene film layer surface in nano-level by the present invention, constructs the three-dimensional conductive skeleton formed with graphene film, and nano-sized nickel hydroxide particle is dispersed in the Ni (OH) on graphene film surface2/ rGO composite material plays dispersion and support Ni nanoparticle (OH)2The effect of particle improves the electric conductivity of composite material, prevents Ni nanoparticle (OH)2The reunion of particle；And nano-sized nickel hydroxide particle plays active material, graphene film is also prevented from simultaneously to stack again, with meso-hole structure, big specific surface area, improve the utilization rate and solid liquid phase contact area of active material, to improve the electrochemical reaction speed of active material, the final chemical property for improving composite material.
Description
Technical field
The present invention relates to a kind of preparation methods of simple hydrothermal synthesis beta phase nickel hydroxide/graphene nanocomposite material, belong to
In electrode material for nickel-hydrogen cell technical field.
Background technique
Currently as the nickel-metal hydride battery of main secondary cell, there are the distinguishing features such as environmentally friendly, safe.Has conduct
The potentiality of power battery, but nickel-metal hydride battery performance especially high rate performance is not met by the needs of power battery.Therefore, compel
Be essential the performance of nickel-metal hydride battery to be improved, restricted electrode of the positive electrode as nickel-metal hydride battery, and chemical property is determined substantially
Determine the performance of nickel-metal hydride battery.Beta phase nickel hydroxide is anode of nickel-metal hydride battery active material, improves the electrochemistry of beta phase nickel hydroxide
It can be most important for improving the performance of nickel-metal hydride battery.Studies have shown that there are intrinsic conductivities is poor for beta phase nickel hydroxide, in charge and discharge
Proton is shown as in battery use process the problems such as the diffusion rate of solid phase is slow in electric process, high rate performance and cycle performance
The problems such as poor and big there are the internal resistance of cell.
Currently, business is micron-size spherical pattern with beta phase nickel hydroxide, tap density is high.In charge and discharge process, research
Show that nano beta beta-phase nickel hydroxide can reduce the transmission path of proton in solid phase, its diffusion rate is improved, so as to improve battery
Chemical property.But nano beta beta-phase nickel hydroxide is easy to reunite, and chemical property is caused to deteriorate rapidly.Graphene has
Two-dimensional structure, electric conductivity is excellent, large specific surface area, excellent chemical and thermal stability energy.These properties make it be applied to energy
The carrier field of amount conversion and memory device, it is considered to be big most potential one of the new material of future ten.However, graphene film
Layer is easy to stack, and the excellent properties of graphene is made to be not fully utilized.
Summary of the invention
The present invention is realized by following approach, using graphene oxide colloid, soluble nickel salt, highly basic as raw material, by water
Then thermal synthesis is freeze-dried, to obtain beta phase nickel hydroxide/graphene nano complex coacervation.The present invention provides a kind of simple
1) hydrothermal synthesis beta phase nickel hydroxide/graphene nanocomposite material preparation method, the preparation method include the following steps:
Graphene oxide (GO) is add to deionized water ultrasound to obtain ultrasonic solution, then by NiSO4·6H2It is super that O is added to this
In sound solution, after stirring to all dissolutions, NaOH solution is added dropwise, and is persistently stirred to react, it is molten to obtain a mixing
Liquid；2) after the mixed solution forms uniform clear solution, which is transferred to the height of the stainless steel with Teflon lining
It is reacted in means of press seals reaction kettle, it places into dry in baking oven；3) it after reaction, is cooled to room temperature, collects to reaction kettle
In reaction kettle then gained sample for several times with deionized water centrifuge washing is freeze-dried, to obtain beta phase nickel hydroxide/graphene
Nano combined cohesion；4) beta phase nickel hydroxide for preparing step 3)/graphene nano complex coacervation, conductive agent acetylene black and
Binder 60wt% polytetrafluoroethylene (PTFE) concentrate is mixed according to the mass ratio of 8:1:1, then adds appropriate ethanol solution,
It is ultrasonic after mixing evenly, to obtain finely dispersed diluted beta phase nickel hydroxide/graphene composite material powder suspension slurry；So
The beta phase nickel hydroxide/graphene composite material powder suspension slurry is coated in afterwards and is pre-processed in clean nickel foam, it is to be coated equal
Roll-in after even, is placed in a vacuum drying oven drying, solidifies electrode active material, received with obtaining beta phase nickel hydroxide/graphene
Nano composite material.
In the technical solution of the preparation method of the invention, it is preferable that the additional amount of graphene oxide be 1.18~
1.98g, the additional amount of deionized water are 350~450mL, and the concentration of NaOH solution is 1.6M.
In the technical solution of the preparation method of the invention, it is preferable that anti-after NaOH solution is added in step 1)
It is 30~60min between seasonable.
In the technical solution of the preparation method of the invention, it is preferable that in step 1), NiSO4·6H2The additional amount of O
For 0.320mol, the additional amount of 1.6M NaOH solution is 400mL.
In the technical solution of the preparation method of the invention, it is preferable that in step 1), the time of the ultrasound is
2h。
In the technical solution of the preparation method of the invention, it is preferable that anti-in stainless steel high pressure sealing in step 2)
Answering the reaction pressure reacted in kettle is 2~3Mpa, and the temperature of baking oven is 170~190 DEG C, and the reaction time is 5~7h.
In the technical solution of the preparation method of the invention, it is preferable that in step 3), the temperature of freeze-drying is-
52~-50 DEG C.
In the technical solution of the preparation method of the invention, it is preferable that in step 4), exist in a vacuum drying oven
Dry 0.5~1.5h at 100~130 DEG C.
In the technical solution of the preparation method of the invention, it is preferable that in step 4), the time of the ultrasound is
1h。
In the technical solution of the preparation method of the invention, it is preferable that the beta phase nickel hydroxide/graphene is received
Nano composite material electrode coating with a thickness of 0.2 millimeter.
Beneficial effects of the present invention are as follows: a kind of simple hydrothermal synthesis beta phase nickel hydroxide/graphene nanocomposite material and
It is applied, and a kind of preparation method of simple hydrothermal synthesis beta phase nickel hydroxide/graphene nanocomposite material, the preparation are provided
Method is characterized in: being precipitating reagent using graphene oxide colloid and soluble nickel salt as raw material, highly basic sodium hydroxide or potassium, passes through
Then hydrothermal synthesis is freeze-dried, obtain beta phase nickel hydroxide/graphene nano complex coacervation.(1) beta phase nickel hydroxide/graphite
Alkene nano-composite gel has unique three-dimensional net structure and high-specific surface area, can provide for beta phase nickel hydroxide more
Site is grown, restrained effectively the reunion of nanometer beta phase nickel hydroxide, obtains the active site of beta phase nickel hydroxide sufficiently sudden and violent
Dew；(2) graphene film and its excellent electric conductivity of the three-dimensional conductive skeleton constructed are conducive to the transmission of electronics, improve nanometer
The electric conductivity of plural gel entirety；(3) and nano-sized nickel hydroxide particle plays active material, while being also prevented from graphene slice weight
It is new to stack.Nanometer beta phase nickel hydroxide particle itself has higher theoretical capacity, and the specific capacity of plural gel entirety can be improved,
Therefore, nickel hydroxide and graphene film are carried out nano combined, may be implemented to act synergistically well, prepared and have excellent performance
Combination electrode material.The nanocomposite has meso-hole structure, has big specific surface area, and then improve the benefit of active material
The electrification of composite material is finally improved to improve the electrochemical reaction speed of active material with rate and solid liquid phase contact area
It learns performance and promotes the multiplying power and cycle performance of nickel-metal hydride battery.Beta phase nickel hydroxide/graphene nano that the present invention is prepared is multiple
It closes cohesion and is used as nickel-hydrogen battery positive pole material active material, there is electrochemical performance, the especially larger battery that improves
High rate performance.And preparation method is easy to operate, and step is few, is suitble to large-scale commercial production.
Detailed description of the invention:
Fig. 1 (a) indicates beta phase nickel hydroxide (NH) beta phase nickel hydroxide/graphene complex coacervation (XRD spectra of NG20；
The Raman map of Fig. 1 (b) expression GO, NH and NG20；
Fig. 2 (a) and Fig. 2 (b) indicates SEM figure of the beta phase nickel hydroxide under different amplification；
Fig. 2 (c) and Fig. 2 (d) indicates nickel hydroxide/graphene complex coacervation SEM photograph；
Fig. 3 indicates that in scanning speed be 5mVs-1Under three kinds of GO and Ni (OH)2Mass ratio beta phase nickel hydroxide/graphite
Alkene electrode CV curve；
Fig. 4 indicates that in current density be 1Ag-1When three kinds of graphenes and Ni (OH)2The β phase hydroxide of compound different quality ratio
Nickel/Graphene electrodes GCD curve.
Specific embodiment:
It is attached now in conjunction with appended preferred embodiment in order to further appreciate that structure of the invention, feature and other purposes
With attached drawing, detailed description are as follows, this attached drawing embodiment described is only used to illustrate the technical scheme of the present invention, and non-limiting
Invention.
Embodiment 1
The graphene oxide (GO) of 1.49g mass is added in 400mL deionized water, and ultrasound 2h.Then will
0.320mol NiSO4·6H2O is added in above-mentioned solution, after stirring to all dissolutions, dropwise by 400mL 1.6MNaOH solution
It is added, and continues to stir 30min.After uniform clear solution to be formed, mixed solution is transferred to 1000mL with Teflon
Reaction pressure is that 2Mpa is put into baking oven, keeps at 180 DEG C after sealing reaction kettle in the stainless steel autoclave of lining
6h。
After reaction, it is cooled to room temperature to reaction kettle, collects gained sample, for several times with deionized water centrifuge washing, so
It is freeze-dried at -52 DEG C afterwards.
By beta phase nickel hydroxide well prepared in advance/graphene nano complex coacervation, conductive agent acetylene black and binder
60wt% polytetrafluoroethylene (PTFE) concentrate is mixed according to the mass ratio of 8:1:1, and suitable ethanol solution is then added, and stirring is equal
Ultrasound 1h, obtains finely dispersed diluted beta phase nickel hydroxide/graphene composite material powder suspension slurry after even；Then it applies
On pre-processing clean nickel foam, uniformly rear roll-in to be coated is placed in a vacuum drying oven, dry 1h, makes electrode at 110 DEG C
Active material solidification to get arrive beta phase nickel hydroxide/graphene combination electrode material (NG20), electrode coating with a thickness of 0.2 milli
Rice.NG20 has optimal chemical property, in 1Ag-1When specific capacitance be 1975F g-1。
Embodiment 2
The graphene oxide (GO) of 1.98g mass is added in 400mL deionized water, and ultrasound 2h.Then will
0.320mol NiSO4·6H2O is added in above-mentioned solution, after stirring to all dissolutions, dropwise by 400mL 1.6MNaOH solution
It is added, and continues to stir 30min.After uniform clear solution to be formed, mixed solution is transferred to 1000mL with Teflon
The stainless steel high pressure reactor reaction pressure of lining is after sealing reaction kettle, to be put into baking oven, keep at 180 DEG C in 3Mpa
6h。
After reaction, it is cooled to room temperature to reaction kettle, collects gained sample, for several times with deionized water centrifuge washing, so
It is freeze-dried at -50 DEG C afterwards.
By beta phase nickel hydroxide well prepared in advance/graphene nano complex coacervation, conductive agent acetylene black and binder
60wt% polytetrafluoroethylene (PTFE) concentrate is mixed according to the mass ratio of 8:1:1, and suitable ethanol solution is then added, and stirring is equal
Ultrasound 1h, obtains finely dispersed diluted beta phase nickel hydroxide/graphene composite material powder suspension slurry after even；Then it applies
On pre-processing clean nickel foam, uniformly rear roll-in to be coated is placed in a vacuum drying oven, dry 1h, makes electrode at 110 DEG C
Active material solidification to get arrive beta phase nickel hydroxide/graphene combination electrode material (NG15), electrode coating with a thickness of 0.2 milli
Rice.NG15 is in 1A g-1When specific capacitance be 1480F g-1。
Embodiment 3
The graphene oxide (GO) of 1.20g mass is added in 400mL deionized water, and ultrasound 2h.Then will
0.320mol NiSO4·6H2O is added in above-mentioned solution, after stirring to all dissolutions, dropwise by 400mL 1.6MNaOH solution
It is added, and continues to stir 30min.After uniform clear solution to be formed, mixed solution is transferred to 1000mL with Teflon
The stainless steel high pressure reactor reaction pressure of lining is after sealing reaction kettle, to be put into baking oven, protect at 180 DEG C in 2.5Mpa
Hold 6h.
After reaction, it is cooled to room temperature to reaction kettle, collects gained sample, for several times with deionized water centrifuge washing, so
It is freeze-dried at -51 DEG C afterwards.
By beta phase nickel hydroxide well prepared in advance/graphene nano complex coacervation, conductive agent acetylene black and binder
60wt% polytetrafluoroethylene (PTFE) concentrate is mixed according to the mass ratio of 8:1:1, and suitable ethanol solution is then added, and stirring is equal
Ultrasound 1h, obtains finely dispersed diluted beta phase nickel hydroxide/graphene composite material powder suspension slurry after even；Then it applies
On pre-processing clean nickel foam, uniformly rear roll-in to be coated is placed in a vacuum drying oven, dry 1h, makes electrode at 110 DEG C
Active material solidification to get arrive beta phase nickel hydroxide/graphene combination electrode material (NG25), electrode coating with a thickness of 0.2 milli
Rice.NG25 is in 1Ag-1When specific capacitance be 1375F g-1。
Embodiment 4: beta phase nickel hydroxide/graphene nanocomposite material analysis
In order to probe into influence of the additional amount of GO to combination electrode material performance, GO and Ni (OH)2Mass ratio be respectively as follows:
1:15,1:20,1:25, and it is labeled as NG15, NG20, NG25.In order in contrast, under the conditions of above-mentioned same, pure Ni
(OH)2Also it is synthesized, and is labeled as NH.As described in Fig. 1~4.
As shown in Fig. 1 (a), in Fig. 1 (a) two samples of NH and NG20 19.2 °, 33.5 °, 38.7 °, 52.2 °,
59.3 °, 62.8 °, 68.9,69.6 ° and 72.9 ° nearby there is apparent diffraction maximum (using the X-ray powder of Rigaku company, Japan
Last diffractometer (Smartlab X) measures diffraction maximum), with β-Ni (OH)2The characteristic diffraction peak angle of (JCDPDS No.14-0117)
Degree is consistent.Show the Ni (OH) formed in the sample of preparation2Mainly by β-Ni (OH)2Composition.Do not observe that graphene spreads out in figure
Penetrate peak, it may be possible to since the diffracted intensity of graphene in NG20 composite material is relatively low.
As shown in Fig. 1 (b), GO and NG20 has typical graphene D band (about 1346cm in Fig. 1 (b)-1) and G band is (about
1576cm-1), it is related with stretching vibration in the carbon atom face in the breathing vibration and ring and chain of carbon atom on aromatic rings respectively.The peak D
Defect and amorphous structure of the main representative positioned at carbon material edge.In general, the intensity at the peak D and the peak G ratio (ID/IG) big
Cause reflects the defect and unordered degree of material.As seen from the figure, the I of NG20D/IGValue is much smaller than GO, after illustrating hydro-thermal reaction
GO surface oxygen functional group is reduced, and is reduced；And its defect increases, the unordered degree of composite material reduces, this is very beneficial for
Growth of the nickel hydroxide on graphene.In addition, NH and NG20 are in 968cm-1Nearby there is a peak, this is interlayer anion
Vibration peak.The Raman spectrum analysis of comprehensive NH and NG20 is (using the Raman spectrometer (Labram of Reinshaw company, Britain
Spectrometer Raman spectrogram) is measured) it can illustrate that rGO has successfully been combined to Ni (OH)2In.
Fig. 2 (a) and Fig. 2 (b) is that SEM figure of the NH under different amplification (is sent out using the field of Hitachi company, Japan d
Penetrate scanning electron microscope (S-4800) and measure SEM figure), as shown in Fig. 2 (a) and Fig. 2 (b), it can be seen that from Fig. 2 (a) and Fig. 2 (b)
NH shows thick about 20nm, the hexagonal nanosheet of a length of 80-100nm, and gets together and to form the group of irregular shape
Aggressiveness.After graphene-doped, apparent variation is had occurred in the pattern of composite material.
As shown in Fig. 2 (c) and Fig. 2 (d), it can thus be seen that ultra-fine Ni (OH)2Particle high uniformity is grown in graphite
Alkene on piece is conducive to the growth of nickel hydroxide since there are a large amount of oxygen-containing groups for surface of graphene oxide.
As shown in figure 3, Ni (OH)2The electrochemical property test of/rGO combination electrode material typical three-electrode system,
It is carried out in 6M KOH electrolyte.In order to determine the electrochemical behavior type of electrode material, in 6M KOH, with 5mV s-1Scanning
Rate carries out CV test to the electrode prepared in 0~0.55V (vs.Hg/HgO) voltage range and (uses Shanghai Chen Hua limited
The electrochemical workstation (CHI 660E) of company carries out CV test).We are it can be found that all CV curves all have from Fig. 3
A pair of significantly redox peaks (respectively near 0.45V and 0.27V), show typical fake capacitance behavior, main
It is attributed to Ni2+/Ni3+Reversible faraday's reaction.Moreover, the area that the CV curve of NG20 electrode material is surrounded is much larger than
Other electrode materials, this also illustrates that it has bigger specific capacitance.
As shown in figure 4, Fig. 4 expression NH, NG15, NG20 and NG25 is 1Ag in current density-1When constant current charge-discharge
(GCD) curve (being tested using the electrochemical workstation (CHI660E) of Shanghai Chen Hua Co., Ltd).As shown in Figure 4, NG20
Specific capacity be higher than NH, NG15 and NG25.
Therefore, it is multiple by simple hydrothermal synthesis combination freeze-drying to prepare beta phase nickel hydroxide/graphene nano by the present invention
Condensation material.Nickel hydroxide particle is compounded in graphene film layer surface in nano-level, constructs the three-dimensional formed with graphene film
Conducting matrix grain, nano-sized nickel hydroxide particle are dispersed in the Ni (OH) on graphene film surface2/ rGO composite material.In Ni
(OH)2In/rGO composite material, graphene film forms three-dimensional conductive skeleton, plays dispersion and support Ni nanoparticle (OH)2The work of particle
With improving the electric conductivity of composite material, prevent Ni nanoparticle (OH)2The reunion of particle；And nano-sized nickel hydroxide particle rises and lives
Property material effect, while being also prevented from graphene film and stacking again.The nanocomposite has meso-hole structure, has big ratio table
Area, and then the utilization rate and solid liquid phase contact area of active material are improved, to improve the electrochemical reaction speed of active material
Rate, the final chemical property for improving composite material.And the Ni (OH)2/ rGO nanocomposite also can be used as super capacitor
The ideal electrode material of device.
Claims (10)
1. a kind of preparation method of the nanocomposite of simple hydrothermal synthesis beta phase nickel hydroxide/graphene, the preparation method
Include the following steps:
1) add graphene oxide into deionized water that ultrasound is to obtain ultrasonic solution, then by NiSO4·6H2O is added to this
In ultrasonic solution, after stirring to all dissolutions, NaOH solution is added dropwise, and is persistently stirred to react, to obtain a mixing
Solution；
2) after the mixed solution forms uniform clear solution, which is transferred to the height of the stainless steel with Teflon lining
It is reacted in means of press seals reaction kettle, it places into baking oven and heats；
3) it after reaction, is cooled to room temperature to reaction kettle, gained sample in reaction kettle is collected, with deionized water centrifuge washing number
It is secondary, it is then freeze-dried, to obtain beta phase nickel hydroxide/graphene nano complex coacervation；
4) beta phase nickel hydroxide for preparing step 3)/graphene nano complex coacervation, conductive agent acetylene black and binder
60wt% polytetrafluoroethylene (PTFE) concentrate is mixed according to the mass ratio of 8:1:1, then adds appropriate ethanol solution, and stirring is equal
Ultrasound after even, to obtain finely dispersed diluted beta phase nickel hydroxide/graphene composite material powder suspension slurry；Then by the β
Beta-phase nickel hydroxide/graphene composite material powder suspension slurry, which is coated in, to be pre-processed in clean nickel foam, uniform back roller to be coated
Pressure, is placed in a vacuum drying oven drying, solidifies electrode active material, nano combined to obtain beta phase nickel hydroxide/graphene
Material.
2. preparation method as described in claim 1, which is characterized in that in step 1), the additional amount of graphene oxide is 1.18
~1.98g, the additional amount of deionized water are 350~450mL, and the concentration of NaOH solution is 1.6M.
3. preparation method as described in claim 1, which is characterized in that the reaction time in step 1), after NaOH solution is added
For 30~60min.
4. preparation method as described in claim 1, which is characterized in that in step 1), NiSO4·6H2The additional amount of O is
The additional amount of 0.320mol, 1.6M NaOH solution is 400mL.
5. preparation method as described in claim 1, which is characterized in that in step 1), the time of the ultrasound is 2h.
6. preparation method as described in claim 1, which is characterized in that in step 2), in stainless steel high pressure sealing reaction kettle
The reaction pressure reacted is 2~3Mpa, and it is 5~7h that the temperature of baking oven, which is 170~190 DEG C of reaction time,.
7. preparation method as described in claim 1, which is characterized in that in step 3), the temperature of freeze-drying is -52~-50
℃。
8. preparation method as described in claim 1, which is characterized in that in step 4), in a vacuum drying oven 100~130
Dry 0.5~1.5h at DEG C.
9. preparation method as described in claim 1, which is characterized in that in step 4), the time of the ultrasound is 1h.
10. preparation method as described in claim 1, which is characterized in that the beta phase nickel hydroxide/graphene it is nano combined
Material electrodes coating with a thickness of 0.2 millimeter.
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| CN111876007A (en) * | 2020-07-07 | 2020-11-03 | 北京环境特性研究所 | Light high-performance conductive coating and preparation method thereof |
| CN112588331A (en) * | 2020-11-16 | 2021-04-02 | 苏州艾达仕电子科技有限公司 | Method for synthesizing composite conductive material by droplet microfluidics and microfluidic synthesis chip |
| CN112802689A (en) * | 2021-02-22 | 2021-05-14 | 重庆大学 | Porous activated carbon and alpha-Ni (OH)2Nanocomposite and method for preparing same |
| CN114050279A (en) * | 2021-10-26 | 2022-02-15 | 中国科学院宁波材料技术与工程研究所 | Preparation method and application of composite catalyst |
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| CN112802689A (en) * | 2021-02-22 | 2021-05-14 | 重庆大学 | Porous activated carbon and alpha-Ni (OH)2Nanocomposite and method for preparing same |
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| CN114164441A (en) * | 2021-12-29 | 2022-03-11 | 山东省科学院新材料研究所 | Preparation method of nickel hydroxide nanoparticle/graphene composite oxygen precipitation catalyst, product and application thereof |
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