CN106654212B - A kind of Co3O4The preparation method and application of/N-RGO/HSAs composite material - Google Patents
A kind of Co3O4The preparation method and application of/N-RGO/HSAs composite material Download PDFInfo
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Abstract
The present invention relates to a kind of cobalt oxide/graphene composite material (Co3O4/ N-RGO) preparation method and its application in nickel-metal hydride battery and lithium ion battery.The composite material is prepared according to the following steps: a, preparing graphite oxide according to improved Hummers method；B, cobalt acetate is hydrolyzed under the adjustment effect of ammonium hydroxide, is aoxidized and grows extra small Co in graphite oxide surface in situ3O4Nanoparticle；c,Co3O4The further crystallization of nanoparticle and the reduction of graphite oxide.Co3O4/ N-RGO composite material is as electrode material, unique architectural characteristic and Co3O4Synergistic effect between N-RGO significantly improves the high-rate discharge ability of nickel-metal hydride battery and lithium ion battery.For nickel-metal hydride battery, it is 3.2 times (68.7mAh/g) of commercial hydrogen bearing alloy that when discharge current density is 3A/g, its discharge capacity, which is up to 223.1mAh/g,.For lithium ion battery, higher discharge capacity is still kept when current density is 10A/g, is 423.6mAh/g.The present invention provides new thinking for research and development high power type battery.
Description
Technical field
The present invention relates to cobalt oxide/graphene composite material (Co3O4/ N-RGO) preparation and its as nickel-metal hydride battery
With the application of lithium ion battery negative material.
Background technique
The demand to high power type battery such as new-energy automobile, electric tool and military equipment increasingly increases.Therefore, largely
Research work concentrate on exploitation have excellent high rate performance electrode material on.Transition group metallic oxide is considered as battery
One of with the ideal material of capacitor.Wherein, Co3O4It is caused due to its high capacity, low cost and high catalytic activity extensively
Concern.However, its chemical property is normally subject to low conductance and slow ion diffusion rates.Researchers propose
Several effective methods alleviate these problems: preparation nano material increases specific surface area to shorten ion diffusion length；With carbon
Material carries out the compound electric conductivity etc. to improve electrode.Here, we are based on synergistic effect, are prepared for Co3O4Nanocube with
The composite material of nitrogen-doped graphene, and be applied in nickel-metal hydride battery and lithium ion battery as electrode material.It is multiple at this
In condensation material, nitrogen-doped graphene can uniform load C o as conductive substrates3O4Nanocube is to improve Co3O4Conduction
Property；Meanwhile Co3O4Nanocube can provide high discharge capacity and electro catalytic activity.In addition, Co3O4Nanocube pinning
On nitrogen-doped graphene, and nitrogen-doped graphene supports Co3O4, a three-dimensional conductive network structure is together formed, favorably
In shortening ion diffusion length, the diffusion rate of ion and electronics is improved.
Summary of the invention
The purpose of the present invention is be related to cobalt oxide/graphene composite material (Co3O4/ RGO) preparation method and conduct
The application of nickel-metal hydride battery and lithium ion battery negative material.Pass through Co3O4Nanocube and the synergistic effect of N-RGO make this
Co3O4/ N-RGO composite material has lesser electrode internal resistance, faster electronics and ion diffusion rates, as battery electrode material
Material shows excellent multiplying power discharging property.
Above-mentioned purpose of the invention is achieved through the following technical solutions:
A kind of cobalt oxide/graphene composite material (Co3O4/ RGO) preparation method, comprising the following steps:
A, graphite oxide is synthesized according to improved Hummers method；
B, at 22 ~ 25 °C, the graphite oxide of the cobalt acetate of 1 ~ 2 ml, 0.2 M, 1 ~ 2 ml, 4.5 mg/ml is added to
In the dehydrated alcohol of 34 ~ 36 ml, 20 ~ 30 min of ultrasonic disperse, then 75 ~ 85 °C of 9 ~ 10 h of heating make cobalt acetate hydrolysis,
It aoxidizes and grows extra small Co in graphite oxide surface in situ3O4Nanoparticle；
C, make Co in 145 ~ 155 °C of 2.5 ~ 3.5 h of heating with the method for hydro-thermal3O4The further crystallization of nanoparticle, oxidation
Graphite reduction, the inorganic membrane filtration for being later 0.1 ~ 0.2 μm by product aperture, thoroughly cleans 4 ~ 6 with second alcohol and water respectively
Secondary, 22 ~ 25 °C of 10 ~ 12 h of drying in a vacuum drying oven.
By adjusting the amount of ethyl alcohol and the hydrolysis and oxidation rate of controlling reaction temperature cobalt acetate in step b.
Co is controlled by adjusting the temperature of hydro-thermal in step c3O4Crystallization shape.
0.5 ~ 1 g hydrogen storing alloy powder is added in step c before 145 ~ 155 °C of hydro-thermal reactions, prepare cobaltosic oxide/
The composite material Co of graphene and hydrogen bearing alloy3O4/RGO/HSAs。
0.5 ~ 0.8 ml ammonium hydroxide is added in step b, cobalt acetate is made to hydrolyze, aoxidize under the adjustment effect of ammonium hydroxide, preparation four
Co 3 O/nitrogen-doped graphene composite material Co3O4/N-RGO。
0.5 ~ 0.8 ml ammonium hydroxide is added in step b, so that cobalt acetate hydrolyzed, aoxidized under the adjustment effect of ammonium hydroxide, in step c
0.5 ~ 1 g hydrogen storing alloy powder is added before 145 ~ 155 °C of hydro-thermal reactions, prepares cobaltosic oxide/nitrogen-doped graphene and storage
The composite material Co of hydrogen alloy3O4/N-RGO/HSAs。
The composite material Co of the cobalt oxide/graphene and hydrogen bearing alloy that are obtained according to above-mentioned preparation method3O4/
The composite material Co of RGO/HSAs and cobaltosic oxide/nitrogen-doped graphene and hydrogen bearing alloy3O4/ N-RGO/HSAs, both as
The electrode material of nickel-metal hydride battery carries out electrochemical property test, comprising the following steps:
A, 0.25 ~ 0.255 g active material is uniformly mixed with 1.0 ~ 1.02 g carbonyl nickel powders, by tablet press machine 8 ~ 20
The electrode slice that diameter is 10 ~ 15 mm is pressed under the pressure of MPa；
B, using electrode slice prepared in step a as working electrode, the Ni (OH) of sintering2/ NiOOH piece is used as to electricity
Pole, mercuric oxide electrode are electrolyte as reference electrode, the KOH solution of 25 ~ 35 wt%, and the three-electrode system for forming standard carries out
Electro-chemical test；
C, when carrying out volume test, charging and discharging currents density is 0.06 A/g (0.2 C), and activating ring number is 4；It carries out
When high-rate discharge ability is tested, the density of charging current is 0.3 A/g (1 C), and discharge current density is respectively 0.3,0.6,
0.9,1.2,1.5,2.4 with 3 A/g (10 C)；
D, electrochemical property test is carried out on IVIUM electrochemical workstation, relative to open circuit potential (OCP)
Amplitude carries out ac impedance measurement when being 5 mV, and the frequency range of test is by 100 kHz to 5 mHz；In 50% depth of discharge condition
Under, when the potential scan range relative to OCP is -5 to 5 mV, carry out sweeping the linear polarisation curves survey that speed is 0.05 mV/s
Examination；Under the conditions of 50% depth of discharge, when the potential scan range relative to OCP is 0 to 1.5 V, carry out sweeping speed being 5 mV/s
Anodic polarization curves test；Under 100% charged state, under the potential step relative to the mV of+the 500 of Hg/HgO, into
The test of the current versus time curve of 4000 s of row.
Cobalt oxide/graphene composite material (the Co obtained according to above-mentioned preparation method3O4/ RGO) and four oxidations
Three cobalts/nitrogen-doped graphene composite material (Co3O4/ N-RGO), electrochemistry is carried out both as the electrode material of lithium ion battery
Performance test, comprising the following steps:
A, using active material as working electrode, lithium piece is used as to counter/reference electrode, and diaphragm is Celgard 2500
Film, electrolyte are the LiPF of 1M6Volume ratio is dissolved in as the ethylene carbonate of 1:1:1, dimethyl carbonate and methyl ethyl carbonate
In mixed liquor, in the glove box ([O for being full of argon gas2]<1 ppm, [H2O] < 1 ppm) in be assembled into CR2016 type button cell；
B, the preparation method of working electrode be by mass fraction 80% active material, 10% super P and 10% it is viscous
Knot agent polyvinylidene fluoride PVDF is homogenously mixed together, and is dissolved in n-methyl-2-pyrrolidone NMP, by mixture Ma
Slurries, are then uniformly coated on copper foil by 30 min of Nao mortar grinder, and the quality of each copper foil load is 0.5-0.6 mg,
Dry 10 h under conditions of 100 °C；
C, charge-discharge test is carried out on LAND CT2001A battery test system, and potential section is relative to Li+/Li 0.01-3.0 V；Cyclic voltammetry curve is carried out on IVIUM electrochemical workstation, potential section be relative to
Li+/ Li 0.01-3.0 V, sweeping speed is 0.2 mV/s；Ac impedance measurement, the frequency model of test are carried out when amplitude is 10 mV
It encloses by 100 kHz to 10 mHz.
The solution have the advantages that:
Co produced by the present invention3O4/ N-RGO composite material has biggish specific surface area, excellent electric conductivity and faster
Electrochemical reaction speed shows excellent multiplying power discharging property as battery electrode material.
Detailed description of the invention:
Fig. 1, HS3, high rate performance curve of the HS4 from commercial hydrogen bearing alloy under different discharge current densities.
Fig. 2, HS1's prepares schematic diagram.
The Raman map of Fig. 3, HS1 and HS2.
The Raman map of Fig. 4, HS3 and HS4.
The XRD spectrum of Fig. 5, HS1 and HS2.
The XRD spectrum of Fig. 6, HS3 and HS4.
The TGA curve of Fig. 7, HS1 and HS2.
The XPS of Fig. 8, HS1 are composed entirely.
The high-resolution Co 2p of Fig. 9, HS1 are composed.
The high-resolution N 1s of Figure 10, HS1 are composed.
The SEM photograph of Figure 11, HS1.
The SEM photograph of Figure 12, HS2.
The SEM photograph of Figure 13, HS3.
The SEM photograph of Figure 14, HS4.
The SEM photograph of Figure 15, commercial hydrogen bearing alloy.
The TEM photo of Figure 16, HS1.
The TEM photo of Figure 17, HS2.
The HRTEM photo of Figure 18, HS1.
The HRTEM photo of Figure 19, HS2.
Figure 20, HS3, the discharge capacity curve of HS4 and commercial hydrogen bearing alloy.
Figure 21, HS3, the linear polarisation curves of HS4 and commercial hydrogen bearing alloy.
Figure 22, HS3, the electrochemical impedance map of HS4 and commercial hydrogen bearing alloy.
Figure 23, HS3, the anodic polarization curves of HS4 and commercial hydrogen bearing alloy.
Figure 24, HS3, the discharge current-time graph of HS4 and commercial hydrogen bearing alloy under 100% charged state.
The cyclic voltammetry curve of Figure 25, HS1 and HS2.
The constant current charge-discharge curve of Figure 26, HS1 and HS2.
The cycle performance curve of Figure 27, HS1 and HS2 when current density is 0.1 A/g.
The high rate performance curve of Figure 28, HS1 from HS2 under different discharge current densities.
The ac impedance spectroscopy of Figure 29, HS1 and HS2.
The cycle performance curve of Figure 30, HS1 and HS2 when current density is 5 A/g.
Specific embodiment:
Further illustrate particular content and specific embodiment of the invention below with reference to embodiment, however the embodiment
Only implement an example in the present invention, the restriction to technical solution of the present invention cannot be constituted.
Embodiment
Preparation process in the present embodiment and steps are as follows:
(1) graphite oxide is synthesized according to improved Hummers method；By 1.77 ml concentration be 0.2 M cobalt acetate,
0.74 ml ammonium hydroxide and 1.77 ml graphite oxides are added in 35.4 ml dehydrated alcohols, 30 min of ultrasonic disperse, then at 80 °C
10 h are heated, so that cobalt acetate is hydrolyzed and is aoxidized, extra small Co is grown in graphite oxide surface in situ3O4Nanoparticle；Then, will
Reaction product is transferred in 40 ml reaction kettles, with the method for hydro-thermal in 150 °C of 3 h of heating, makes Co3O4Nanoparticle is further
Crystallization, graphite oxide reduction, prepare Co3O4/ N-RGO composite material.Then it is with aperture by composite material obtained
Inorganic membrane filtration, thoroughly cleaned with second alcohol and water respectively.Finally by a temperature of product in a vacuum drying oven 25 °C dry 12
h.It is added without ammonium hydroxide in 80 °C of reactions, prepares Co3O4/ RGO composite material；The conjunction of 0.8 g hydrogen storage is added before hydro-thermal reaction
Bronze (MmNi3.55Co0.75Mn0.4Al0.3) preparation Co3O4/ N-RGO/HSAs composite material；Ammonia is added without in 80 °C of reactions
0.8 g hydrogen storing alloy powder is added in water before hydro-thermal reaction, prepares Co3O4/ RGO/HSAs composite material.Here,
MmNi3.55Co0.75Mn0.4Al0.3Hydrogen bearing alloy is prepared by the method for radio frequency induction melting, the average diameter of alloying pellet
It is.We use HS1, HS2, HS3 and HS4 respectively to indicate above-mentioned Co3O4/ N-RGO, Co3O4/ RGO, Co3O4/
N-RGO/HSAs and Co3O4These four composite materials of/RGO/HSAs.The preparation flow figure of HS1 is referring to fig. 2.
(2) when carrying out nickel-metal hydride battery electrochemical property test, 0.25 g HS3 or HS4 and 1.0 g carbonyl nickel powders are mixed
Uniformly, the electrode slice that diameter is 15 mm is pressed under 8 MPa pressure, using this electrode slice as working electrode, Ni (OH)2/
NiOOH piece is used as to electrode, and for mercuric oxide electrode as reference electrode, the KOH solution of 30 wt% is electrolyte, forms the three of standard
Electrode system carries out electro-chemical test；When carrying out volume test, charging and discharging currents density is 0.06 A/g (0.2 C), activation
Enclosing number is 4；When carrying out high-rate discharge ability test, the density of charging current is 0.3 A/g (1 C), discharge current density difference
For 0.3,0.6,0.9,1.2,1.5,2.4 and 3 A/g (10 C)；Electrochemical property test is in IVIUM electrochemistry
It is carried out on work station.Ac impedance measurement is carried out when the amplitude relative to OCP is 5 mV, the frequency range of test is by 100
KHz to 5 mHz；Under the conditions of 50% depth of discharge, when the potential scan range relative to OCP is -5 to 5 mV, carry out sweeping speed
It is tested for the linear polarisation curves of 0.05 mV/s；Under the conditions of 50% depth of discharge, it is in the potential scan range relative to OCP
When 0 to 1.5 V, carry out sweeping the anodic polarization curves test that speed is 5 mV/s；Under 100% charged state, relative to Hg/HgO
+ 500 mV potential step under, carry out 4000 s current versus time curve test.
(3) in order to carry out lithium ion battery chemical property test, first in the glove box ([O for being full of argon gas2]<1
ppm, [H2O] < 1 ppm) in assemble CR2016 type button cell.Here, lithium piece is used as to counter/reference electrode, and diaphragm is
2500 film of Celgard, electrolyte are the LiPF of 1M6Be dissolved in volume ratio be the ethylene carbonate of 1:1:1, dimethyl carbonate and
In the mixed liquor of methyl ethyl carbonate.The preparation method of working electrode be by mass fraction be 80% HS1 or HS2,10% lead
The binder polyvinylidene fluoride PVDF of dielectric super P and 10% is homogenously mixed together, and is dissolved in N- methyl -2- pyrroles
In alkanone NMP.Said mixture agate mortar is ground into 30 min, then slurries are uniformly coated on copper foil, Mei Getong
The quality of foil load is 0.5-0.6 mg, dry 10 h under conditions of 100 °C；Charge-discharge test is in LAND CT2001A
It is carried out on battery test system, potential section is relative to Li+/Li 0.01-3.0 V；Cyclic voltammetry curve be
It is carried out on IVIUM electrochemical workstation, potential section is relative to Li+/ Li 0.01-3.0 V, sweeping speed is 0.2 mV/s；
Ac impedance measurement is carried out when amplitude is 10 mV, the frequency range of test is by 100 kHz to 10 mHz.
The structure and morphology characterization of composite material:
Fig. 3 is the Raman map of HS1 and HS2, wherein 194,482,524,619 and 691 cm-1Corresponding is tool
There is the Co of spinel structure3O4F2g, Eg, F2g, F2gAnd A1gVibration mode.The characteristic peak of HS2 is similar with HS1, however its
A1gPeak is offset to 709 cm-1, and narrow, show Co in HS23O4Size than big in HS1.Graphene table in Fig. 3
Typical D band (1353 cm are revealed-1) and G band (1604 cm-1).HS1's and HS2I D/I GValue is respectively 1.49 and 1.25, table
Increasing for topological defect is caused since N is adulterated in bright HS1.Fig. 4 is the Raman spectrum comparison diagram of HS3 and HS4.It can see
Out, the Raman characteristic peak of HS3, HS4 are similar with HS1, HS2.Fig. 5 is X-ray diffraction (XRD) map of HS1 and HS2, can be seen
There are the characteristic peak of graphene and the Co of spinel structure in composite material out3O4Characteristic peak.HS3, HS4 and commercial hydrogen bearing alloy
XRD spectrum it is as shown in Figure 6, it can be seen that HS3 and HS4 remain CaCu5The hexagonal structure of type, this is because composite wood
Co in material3O4It is all very low with the content of RGO, it is tested through ICP, Co in HS3 (or HS4)3O4And the mass fraction of RGO is respectively 0.9
Wt% and 1.8 wt%.The content that RGO in HS1 and HS2 is known by thermogravimetric analysis (TGA) is about 26 wt% (referring to Fig. 7), wherein HS1
Thermogravimetric curve have apparent weight loss at 3 at 248,300 and 473 °C, 248 and 300 °C of weight loss may attribution
The oxidation of the disordered carbon caused by N is adulterated, 473 °C of weight loss may be attributed to the oxidation of carbon in graphene skeleton.Fig. 8
For the full spectrogram of XPS of HS1, known by the figure and contain Elements C in composite material, N, O and Co, wherein the content of N atom is 3.31
at%.Fig. 9 is the high-resolution 2p XPS map of Co, shows that Co element exists in the form of the oxide in the composite.The height of N
It is as shown in Figure 10 to differentiate 1s XPS map, shows that N is made of pyridine nitrogen and pyrroles's nitrogen.HS1 is observed by scanning electron microscope (SEM)
With the surface topography of HS2, referring to Figure 11 and 12.As seen from the figure, Co3O4Nanocube is pinned on graphene sheet layer, stone
Black alkene lamella is coated with Co3O4.Co in HS13O4The side length of nanocube is 50-80 nm, and Co in HS23O4Nanocube
Side length be 150-200 nm.The SEM pattern of HS3 and HS4 is referring to Figure 13 and 14, it can be seen that Co3O4It is pinned at graphene nano
On piece, this (referring to Figure 15) different from the smooth surface of commercial hydrogen bearing alloy.It is apparent to can be seen that compared with HS4, in HS3
Co3O4The distribution of nanocube is more uniform, and without obvious segregation.This may be since N functional group introduces in HS3
More forming core sites.Figure 16 and 17 is transmission electron microscope (TEM) photo of HS1 and HS2.It can also be seen that graphene nanometer sheet
It is coated with Co3O4Nanocube, and HS1 has smaller size of Co3O4.This is attributed in HS1 more forming core site (Co2+
With NH3[Co (the NH formed3)6]2+It can be used as Co3O4A kind of nucleus).The high-resolution-ration transmission electric-lens (HRTEM) of HS1 and HS2
Photo is referring to Figure 18 and 19.Interplanar distance 0.286,0.244 and 0.202 nm respectively correspond Co3O4(220), (311) and
(400) crystal face.The illustration of Figure 18 shows Co3O4Well contacting between N-RGO.
The nickel-metal hydride battery Electrochemical Characterization of HS3 and HS4:
Figure 20 gives HS3, and the discharge curve of HS4 and commercial hydrogen-bearing alloy electrode, three has phase as seen from the figure
Close discharge capacity.The high rate performance of three electrodes can be seen that by the figure in all discharge current densities referring to Fig. 1I d
Under, the high-rate discharge ability of HS3 electrode is got well than other two electrodes,I dIt is more obvious when larger.In discharge current
When density is 3 A/g, the capacity of HS3 is up to 223.1 mAh/g, is 3.2 times (68.7 mAh/g) of commercial hydrogen bearing alloy.Metal
The high-rate discharge ability of hydride electrode spreads speed by the hydrogen atom inside the electrochemical reaction rates and alloy of electrode surface
Degree determines that the former can be by exchange current densityI 0, contact resistanceR cAnd the charge transfer resistance of electrodeR ctCharacterization, the latter can be with
By limiting current densityI LWith hydrogen atom diffusion coefficientD HAssessment.Figure 21 is that HS3, HS4 and commercial hydrogen bearing alloy are deep in 50% electric discharge
Linear polarisation curves under degree.I 0Value can be calculated by the slope of straight line in figure.Figure 22 is the survey of electrochemical impedance map
Test result,R cWithR ctIt can be fitted to obtain according to the equivalent circuit diagram in the figure.I L(referring to fig. 2 3) andD H(referring to fig. 2 4) can be with
For characterizing hydrogen by diffusing to the rate on surface inside alloy.It is maximum to know that HS3 electrode has by calculatingI 0,I LWithD H, have simultaneously
Have the smallestR cWithR ct, show its best high-rate discharge ability.The advantages of HS3 electrode is: (1) heteroatom lacks
It falls into, the high conductance of N-RGO and excellent electrode/electrolyte wetability are conducive to the absorption of H and the transmission of electronics and ion；
(2) Co of small size3O4Nanocube improves Co in being uniformly distributed for the surface N-RGO3O4Volmer is reacted: H2O + e- → H+ OH-Catalytic activity, improve discharge capacity；(3) hydrogen bearing alloy and Co3O4The Seamless integration- of/N-RGO reduces electricity
Pole internal resistance.
The lithium ion battery chemical property of HS1 and HS2 characterizes:
Figure 25 is cyclic voltammetric (CV) curve of HS1 and HS2, and for HS1 electrode, first time cathodic scan has one strong
Peak (0.68 V) and a weak acromion (1.31 V), respectively correspond amorphous Li2The formation of O and by Co3O4Turn to the multistep of Co
Become.In addition, the strong peak also corresponds to the formation of irreversible solid electrolyte interface film (SEI film).Since the second circle, weak shoulder
Peak position is basically unchanged, however strong peak is offset to 0.89 V, and simultaneous current density is remarkably decreased.The CV of HS1 electrode
The third circle of curve is essentially coincided with the second circle, shows its good cyclical stability.In addition, in the CV curve of HS1 electrode
Anode part change in cyclic process less, two anode peaks 1.37 V and 2.12 V respectively correspond Co to CoO and Co3O4
Transformation.The CV curve of HS2 is similar with HS1, the difference is that two cathode peaks are offset to 0.66 V and 1.21 V, two sun respectively
Pole peak is offset to 1.46 V and 2.16 V respectively, reflects HS2 electrode with bigger activation polarization.Constant current charge-discharge curve
Also this point (referring to fig. 2 6) are demonstrated.Know that HS1 electrode has discharge platform more higher than HS2 electrode by the figure, shows that HS1 exists
There is smaller activation polarization in electrochemical reaction.It can also be seen that two electrodes all have higher initial discharge by the figure
Capacity (HS1 is 1493.5 mAh/g, and HS2 is 1492.7 mAh/g).However under the second of HS2 electrode the circle discharge capacity is just obvious
806.2 mAh/g are down to, have lost 46%.By contrast, the discharge capacity of HS1 is in the second circle, third circle or even the 50th circle
It is all held essentially constant, respectively 1305.0,1297.5 and 1251.2 mAh/g.In addition, the first circle coulombic efficiency of HS1 electrode
(87.8%) it is apparently higher than HS2 (51.2%).This shows that N doping can inhibit the decomposition of electrolyte to a certain extent, improves lithium
The invertibity of storage.Figure 27 is HS1 and cycle performance curve of the HS2 when current density is 0.1 A/g, the coulomb of two electrodes
Efficiency is held in close to 100%, shows good reversible lithium storage characteristic.Capacity of the HS1 after the circle of circulation 50 is 1251.2
MAh/g has lost 4.1% (compared with the second circle discharge capacity), and the capacity after 50 circle of HS2 circulation is only 753.9 mAh/g.
HS1 has an excellent multiplying power discharging property, and referring to fig. 28.HS1 electrode being averaged under the different current densities of 0.2 to 10 A/g
Discharge capacity is respectively 1174.5,1058.4,934.6,800.3,658.4,538.1 and 423.6 mAh/g, works as electric current
When returning to 0.2 A/g, discharge capacity is restored rapidly to 1088.2 mAh/g, and is kept substantially in subsequent charge and discharge cycles
Stablize.HS1 electrode shows excellent multiplying power discharging property, this is mainly due to Co3O4Synergistic effect between N-RGO:
(1) smaller size of Co in HS13O4Bigger electrochemical surface area can be provided, ion diffusion length is shortened；(2) N-
RGO has better electrode/electrolyte wetability, and electrolyte can be promoted to contact with the good of electrode active material, enhance Li+
Transmission kinetic characteristics；(3) N-RGO has more topological defects, can provide more active sites, be conducive to Li+'s
Absorption and diffusion；(4) Co3O4There is stronger interaction and preferably electrical contact between N-RGO, improve electrodes conduct
Property.This is consistent with the test result of AC impedance (referring to fig. 2 9), and it is charge transfer resistance, line correspondences that wherein semicircle is corresponding
Be characterize diffusion Warburg impedance.Half diameter of a circle is smaller, then charge transfer resistance is smaller, the electrochemistry of electrode
Kinetics performance is better.Compared with HS2, HS1 electrode has smaller charge transfer resistance (91.2vs. 122.8
Ω), smaller activation polarization.Figure 30 is cycle characteristics curve of the HS1 and HS2 electrode under the current density of 5 A/g.HS1
Electrode has higher discharge capacity and better cyclical stability.This is also attributable to Co3O4Synergistic effect between N-RGO.
On the one hand, Co3O4It is pinned on graphene sheet layer or graphene supports, is coated with Co3O4, graphene can not only provide bullet
Property deformation buffer area, alleviate Co3O4In Li+The volume change generated during insertion/abjection, can also inhibit in cyclic process
Middle Co3O4The reunion of nanocube prevents the dusting of electrode material；On the other hand, Co3O4Nanocube is pinned at graphite
Between the lamella of alkene, stacking of the graphene sheet layer in cyclic process can be inhibited as nanometer gasket, avoid graphene
Graphitization makes it keep high specific surface area, loose three-dimensional conductive network structure and the quick electronics of holding and ion transmission.
The good high rate performance of HS1 and cyclical stability show the composite material of our preparations in the practical application side of high power type battery
Face has certain potentiality.
Claims (2)
1. a kind of cobaltosic oxide nano cube/nitrogen-doped graphene and hydrogen bearing alloy as negative electrode of lithium ion battery is answered
The preparation method of condensation material, comprising the following steps:
A, graphite oxide is synthesized according to improved Hummers method；
B, at 22 ~ 25 DEG C, by the cobalt acetate of 1 ~ 2 ml, 0.2 M, 0.5 ~ 0.8 ml ammonium hydroxide, the oxidation of 1 ~ 2 ml, 4.5 mg/ml
Graphite is added in the dehydrated alcohol of 34 ~ 36 ml, 20 ~ 30 min of ultrasonic disperse, then in 75 ~ 85 DEG C of 9 ~ 10 h of heating, is made
Cobalt acetate is hydrolyzed under the adjustment effect of ammonium hydroxide, is aoxidized and in N doping surface of graphene oxide growth in situ Co3O4Nanoparticle
Son prepares cobaltosic oxide nano cube/N doping graphene oxide composite material, and wherein nitrogen atom content is no more than 5
At%, including pyridine nitrogen and pyrroles's nitrogen, by adjusting the amount of ethyl alcohol and the hydrolysis and oxidation speed of controlling reaction temperature cobalt acetate
Degree；
C, 0.5 ~ 1 g hydrogen storing alloy powder is first added, then makes Co in 145 ~ 155 DEG C of 2.5 ~ 3.5 h of heating with the method for hydro-thermal3O4
The further crystallization of nanoparticle, the reduction of N doping graphene oxide, the inoranic membrane for being later 0.1 ~ 0.2 μm by product aperture
Filtering, thoroughly cleans 4 ~ 6 times, in a vacuum drying oven 22 ~ 25 DEG C 10 ~ 12 h of drying with second alcohol and water respectively, passes through adjusting
The temperature of hydro-thermal controls Co3O4Crystallization shape, prepare the composite wood of cobaltosic oxide/nitrogen-doped graphene and hydrogen bearing alloy
Expect Co3O4/ N-RGO/HSAs。
2. cobaltosic oxide nano cube/nitrogen-doped graphene that preparation method according to claim 1 obtains and storage
The composite material Co of hydrogen alloy3O4/N-RGO/HSAs。
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| CN109590008B (en) * | 2018-12-25 | 2021-06-25 | 天津大学 | Preparation method of laser-synthesized oxygen vacancy adjustable cobaltosic oxide nitrogen-doped graphene |
| CN112481652B (en) * | 2020-11-20 | 2022-01-21 | 河南大学 | Graphene modified CoOOH/Fe2O3Composite electrode material and preparation method thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103490044A (en) * | 2012-06-11 | 2014-01-01 | 海洋王照明科技股份有限公司 | Preparation method of cobalt oxide (II,III)-graphene composite material |
| CN105152161A (en) * | 2015-06-30 | 2015-12-16 | 华南理工大学 | Heteroatom doped surface perforated hollow sphere graphene material, preparation method and application thereof |
| CN105244175A (en) * | 2015-09-21 | 2016-01-13 | 福州大学 | N-doped graphene/cobaltosic oxide nanocomposite |
| CN105406032A (en) * | 2015-12-28 | 2016-03-16 | 吉林大学 | Preparation method of hydrogen storage alloy and nano-porous nickel composite (HSAs/NPNi) and application thereof |
| CN105428627A (en) * | 2015-12-28 | 2016-03-23 | 吉林大学 | Preparation method for hydrogen storage alloy and graphene composite material and application of composite material |
| CN105609319A (en) * | 2016-01-29 | 2016-05-25 | 西北师范大学 | Flaky titanium carbide-loaded manganese dioxide composite material for super capacitor electrode material and preparation of flaky titanium carbide-loaded manganese dioxide composite material |
| CN105680010A (en) * | 2016-01-18 | 2016-06-15 | 吉林大学 | Method and application for improving discharge capacity and high rate discharge performance of hydrogen storage alloy through Co3O4 in-site compounding |
-
2016
- 2016-12-29 CN CN201611242926.7A patent/CN106654212B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103490044A (en) * | 2012-06-11 | 2014-01-01 | 海洋王照明科技股份有限公司 | Preparation method of cobalt oxide (II,III)-graphene composite material |
| CN105152161A (en) * | 2015-06-30 | 2015-12-16 | 华南理工大学 | Heteroatom doped surface perforated hollow sphere graphene material, preparation method and application thereof |
| CN105244175A (en) * | 2015-09-21 | 2016-01-13 | 福州大学 | N-doped graphene/cobaltosic oxide nanocomposite |
| CN105406032A (en) * | 2015-12-28 | 2016-03-16 | 吉林大学 | Preparation method of hydrogen storage alloy and nano-porous nickel composite (HSAs/NPNi) and application thereof |
| CN105428627A (en) * | 2015-12-28 | 2016-03-23 | 吉林大学 | Preparation method for hydrogen storage alloy and graphene composite material and application of composite material |
| CN105680010A (en) * | 2016-01-18 | 2016-06-15 | 吉林大学 | Method and application for improving discharge capacity and high rate discharge performance of hydrogen storage alloy through Co3O4 in-site compounding |
| CN105609319A (en) * | 2016-01-29 | 2016-05-25 | 西北师范大学 | Flaky titanium carbide-loaded manganese dioxide composite material for super capacitor electrode material and preparation of flaky titanium carbide-loaded manganese dioxide composite material |
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