CN106654212A - Preparation method and application of cobaltosic oxide/graphene composite material (Co<3>O<4>/N-RGO) - Google Patents
Preparation method and application of cobaltosic oxide/graphene composite material (Co<3>O<4>/N-RGO) Download PDFInfo
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Abstract
The invention relates to a preparation method of a cobaltosic oxide/graphene composite material (Co<3>O<4>/N-RGO), and an application of the composite material in a nickel-metal hydride battery and a lithium ion battery. The composite material is prepared by the steps as follows: a, preparing graphite oxide according to an improved Hummers method; b, performing hydrolysis and oxidization of cobalt acetate under the regulation effect of ammonium hydroxide, and carrying out in-situ growth of extra-small Co<3>O<4> nanoparticles on the surface of the graphite oxide; and c, performing further crystallization of the Co<3>O<4> nanoparticles and reduction of the graphite oxide. When the Co<3>O<4>/N-RGO composite material is used as an electrode material, due to the unique structural characteristic and the synergistic effect between the Co<3>O<4> and the N-RGO, the high-rate discharging performance of the nickel-metal hydride battery and the lithium ion battery is obviously improved; for the nickel-metal hydride battery, at discharge current density of 3A/g, the discharge capacity can be as high as 223.1mAh/g which is 3.2 times (68.7mAh/g) of that of a commercial hydrogen storage alloy; and for the lithium ion battery, at discharge current density of 10A/g, relatively high discharge capacity which is 423.6mAh/g is still maintained. A new thought is provided for research and development of a high-power type battery.
Description
Technical field：
The present invention relates to cobalt oxide/graphene composite (Co3O4/ N-RGO) preparation and its as Ni-MH battery
With the application of lithium ion battery negative material.
Background technology：
New-energy automobile, electric tool and military equipment etc. increasingly increase to the demand of high power type battery.Therefore, in a large number
Research work concentrate on exploitation with excellent high rate performance electrode material on.Transition group metallic oxide is considered as battery
One of with the ideal material of capacitor.Wherein, Co3O4Due to its high power capacity, inexpensive and high catalysis activity and cause extensively
Concern.However, its chemical property is normally subject to low conductance and slow ion diffusion rates.Researchers propose
Several effective methods are alleviating these problems：Prepare nano material to shorten ion diffusion length, increase specific surface area；With carbon
Material carries out compound electric conductivity to improve electrode etc..Here, we are based on cooperative effect, are prepared for Co3O4Nanocube with
The composite of nitrogen-doped graphene, and be applied in Ni-MH 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 improving 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 form, favorably
In ion diffusion length is shortened, the diffusion rate of ion and electronics is improved.
The content of the invention：
The purpose of the present invention is to be related to cobalt oxide/graphene composite (Co3O4/ RGO) preparation method and conduct
The application of Ni-MH battery and lithium ion battery negative material.By Co3O4Nanocube causes this with the cooperative effect of N-RGO
Co3O4/ N-RGO composites have less electrode internal resistance, faster electronics and ion diffusion rates, used as battery electrode material
Material shows excellent multiplying power discharging property.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of cobalt oxide/graphene composite (Co3O4/ RGO) preparation method, comprise the following steps：
A, according to improved Hummers methods synthesize graphite oxide；
B, at 22～25 DEG C, by the cobalt acetate of 1～2ml 0.2M, the graphite oxide of 1～2ml 4.5mg/ml is added to 34
In the absolute ethyl alcohol of～36ml, 20～30min of ultrasonic disperse, then 9～10h is heated at 75～85 DEG C makes cobalt acetate hydrolysis, oxygen
Change and grow extra small Co in graphite oxide surface in situ3O4Nano-particle；
C, heat 2.5～3.5h at 145～155 DEG C with the method for hydro-thermal and make Co3O4The further crystallization of nano-particle, oxidation
Graphite reduction, afterwards by the inorganic membrane filtration that product aperture is 0.1～0.2 μm, respectively with second alcohol and water thoroughly cleaning 4～6
It is secondary, in vacuum drying chamber 22～25 DEG C of 10～12h of drying.
By adjusting the amount of ethanol and hydrolysis and the oxidation rate of controlling reaction temperature cobalt acetate in step b.
Co is controlled in step c by adjusting the temperature of hydro-thermal3O4Crystallization shape.
In step c before 145～155 DEG C of hydro-thermal reactions add 0.5～1g hydrogen storing alloy powders, prepare cobaltosic oxide/
The composite Co of Graphene and hydrogen bearing alloy3O4/RGO/HSAs。
0.5～0.8ml ammoniacal liquor is added in step b, cobalt acetate hydrolyzed under the adjustment effect of ammoniacal liquor, aoxidized, prepare four
Co 3 O/nitrogen-doped graphene composite Co3O4/N-RGO。
0.5～0.8ml ammoniacal liquor is added in step b, cobalt acetate hydrolyzed under the adjustment effect of ammoniacal liquor, aoxidized, in step c
0.5～1g hydrogen storing alloy powders were added before 145～155 DEG C of hydro-thermal reactions, cobaltosic oxide/nitrogen-doped graphene is prepared with storage
The composite Co of hydrogen alloy3O4/N-RGO/HSAs。
The cobalt oxide/graphene obtained according to above-mentioned preparation method and the composite Co of hydrogen bearing alloy3O4/
The composite Co of RGO/HSAs and cobaltosic oxide/nitrogen-doped graphene and hydrogen bearing alloy3O4/ N-RGO/HSAs, both as
The electrode material of Ni-MH battery carries out electrochemical property test, comprises the following steps：
A, 0.25～0.255g active materials are well mixed with 1.0～1.02g carbonyl nickel powders, by tablet press machine 8～
The electrode slice of a diameter of 10～15mm is pressed under the pressure of 20MPa；
B, using electrode slice prepared in step a as working electrode, the Ni (OH) of sintering2/ NiOOH pieces are used as to electricity
Pole, used as reference electrode, the KOH solution of 25～35wt% is electrolyte to mercuric oxide electrode, and the three-electrode system for constituting standard enters
Row electro-chemical test；
C, when carrying out volume test, charging and discharging currents density is 0.06A/g (0.2C), and the activation number of turns is 4；Carry out high power
When rate discharge performance is tested, the density of charging current is 0.3A/g (1C), and discharge current density is respectively 0.3,0.6,0.9,1.2,
1.5,2.4 with 3A/g (10C)；
D, electrochemical property test are carried out on IVIUM electrochemical workstations, relative to OCP (OCP)
Amplitude carries out ac impedance measurement when being 5mV, and the frequency range of test is by 100kHz to 5mHz；In 50% depth of discharge condition
Under, when the potential scan scope relative to OCP is -5 to 5mV, carry out sweeping linear polarisation curves test of the speed for 0.05mV/s；
Under the conditions of 50% depth of discharge, when the potential scan scope relative to OCP is 0 to 1.5V, carry out sweeping sun of the speed for 5mV/s
Pole polarization curve test；Under 100% charged state, under the potential step of+500mV relative to Hg/HgO, 4000s is carried out
Current versus time curve test.
According to the cobalt oxide/graphene composite (Co that above-mentioned preparation method is obtained3O4/ RGO) and four oxidations three
Cobalt/nitrogen-doped graphene composite (Co3O4/ N-RGO), carry out electrochemistry both as the electrode material of lithium ion battery
Can test, comprise the following steps：
A, using active material as working electrode, used as to counter/reference electrode, barrier film is Celgard 2500 to lithium piece
Film, electrolyte is the LiPF of 1M6Volume ratio is dissolved in for 1:1:1 ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate
In mixed liquor, in the glove box ([O full of argon gas2]<1ppm,[H2O]<CR2016 type button cells are assembled in 1ppm)；
B, the preparation method of working electrode are by active material, 10% super P and 10% that mass fraction is 80%
Binding agent polyvinylidene fluoride PVDF be homogenously mixed together, in being dissolved in METHYLPYRROLIDONE NMP, by mixture
30min is ground with agate mortar, then slurries is uniformly coated on Copper Foil, the quality of each Copper Foil load is 0.5-0.6mg,
10h is dried under conditions of 100 DEG C；
C, charge-discharge test are carried out on LAND CT2001A battery test systems, and its potential interval is relative to Li+/Li0.01-3.0V；Cyclic voltammetry curve is carried out on IVIUM electrochemical workstations, and its potential interval is relative to Li+/
Li0.01-3.0V, sweeps speed for 0.2mV/s；Carry out ac impedance measurement when amplitude is 10mV, the frequency range of test by
100kHz to 10mHz.
The solution have the advantages that：
Obtained Co of the invention3O4/ N-RGO composites have larger specific surface area, excellent electric conductivity and faster
Electrochemical reaction speed, as battery electrode material excellent multiplying power discharging property is shown.
Description of the drawings：
Fig. 1, HS3, high rate performance curves of the HS4 from commercial hydrogen bearing alloy under different discharge current densities.
Fig. 2, HS1's prepares schematic diagram.
The Raman collection of illustrative plates of Fig. 3, HS1 and HS2.
The Raman collection of illustrative plates 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 curves of Fig. 7, HS1 and HS2.
The XPS of Fig. 8, HS1 is composed entirely.
The high-resolution Co 2p spectrums of Fig. 9, HS1.
The high-resolution N 1s spectrums of Figure 10, HS1.
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 photos of Figure 16, HS1.
The TEM photos of Figure 17, HS2.
The HRTEM photos of Figure 18, HS1.
The HRTEM photos of Figure 19, HS2.
The discharge capacity curve of Figure 20, HS3, HS4 and commercial hydrogen bearing alloy.
The linear polarisation curves of Figure 21, HS3, HS4 and commercial hydrogen bearing alloy.
The electrochemical impedance collection of illustrative plates of Figure 22, HS3, HS4 and commercial hydrogen bearing alloy.
The anodic polarization curves of Figure 23, HS3, HS4 and commercial hydrogen bearing alloy.
Figure 24, HS3, discharge current-time graphs of the HS4 with 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 0.1A/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 5A/g.
Specific embodiment:
The particular content and specific embodiment of the present invention, but the embodiment are further illustrated with reference to embodiment
Only implement in the present invention, it is impossible to constitute the restriction to technical solution of the present invention.
Embodiment
Preparation process and step in the present embodiment is as follows：
(1) graphite oxide is synthesized according to improved Hummers methods；By 1.77ml concentration for 0.2M cobalt acetate,
0.74ml ammoniacal liquor and 1.77ml graphite oxides are added in 35.4ml absolute ethyl alcohols, ultrasonic disperse 30min, then in 80 DEG C of heating
10h, makes cobalt acetate hydrolyze and aoxidize, and in graphite oxide surface in situ extra small Co is grown3O4Nano-particle；Then, reaction is produced
Thing is transferred in 40ml reactors, and 3h is heated at 150 DEG C with the method for hydro-thermal, makes Co3O4The further crystallization of nano-particle, oxidation
Graphite reduction, prepares Co3O4/ N-RGO composites.Then by inoranic membrane mistake that obtained composite aperture is 0.2- μm
Filter, respectively with second alcohol and water thoroughly cleaning.Finally product is dried into 12h in vacuum drying chamber at a temperature of 25 DEG C.It is anti-at 80 DEG C
At once ammoniacal liquor is added without, Co is prepared3O4/ RGO composites；0.8g hydrogen storing alloy powders were added before hydro-thermal reaction
(MmNi3.55Co0.75Mn0.4Al0.3) prepare Co3O4/ N-RGO/HSAs composites；Ammoniacal liquor is added without in 80 DEG C of reactions, in water
0.8g hydrogen storing alloy powders are added before thermal response, Co is prepared3O4/ RGO/HSAs composites.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 50 ± 10 μm.We use respectively HS1, and HS2, HS3 and HS4 are representing above-mentioned Co3O4/ N-RGO, Co3O4/ RGO, Co3O4/N-
RGO/HSAs and Co3O4/ RGO/HSAs these four composites.The preparation flow figure of HS1 is referring to Fig. 2.
(2) it is when carrying out Ni-MH battery electrochemical property test, the mixing of 0.25g HS3 or HS4 and 1.0g carbonyl nickel powder is equal
It is even, the electrode slice of a diameter of 15mm is pressed under 8MPa pressure, using this electrode slice as working electrode, Ni (OH)2/NiOOH
Used as to electrode, used as reference electrode, the KOH solution of 30wt% is electrolyte to mercuric oxide electrode to piece, constitutes three electrodes of standard
System carries out electro-chemical test；When carrying out volume test, charging and discharging currents density is 0.06A/g (0.2C), and the activation number of turns is
4；When carrying out high-rate discharge ability test, the density of charging current is 0.3A/g (1C), and discharge current density is respectively 0.3,
0.6,0.9,1.2,1.5,2.4 with 3A/g (10C)；Electrochemical property test is carried out on IVIUM electrochemical workstations.
Relative to OCP amplitude be 5mV when carry out ac impedance measurement, the frequency range of test is by 100kHz to 5mHz；Put 50%
Under electric depth conditions, when the potential scan scope relative to OCP is -5 to 5mV, carry out sweeping linear pole of the speed for 0.05mV/s
Change curve test；Under the conditions of 50% depth of discharge, when the potential scan scope relative to OCP is 0 to 1.5V, carry out sweeping speed
Anodic polarization curves for 5mV/s are tested；Under 100% charged state, in the potential step of+500mV relative to Hg/HgO
Under, carry out the test of the current versus time curve of 4000s.
(3) in order to carry out lithium ion battery chemical property test, first in the glove box ([O full of argon gas2]<1ppm,
[H2O]<Assembling CR2016 type button cells in 1ppm).Here, used as to counter/reference electrode, barrier film is lithium piece
Celgard2500 films, electrolyte is the LiPF of 1M6Volume ratio is dissolved in for 1:1:1 ethylene carbonate, dimethyl carbonate and carbon
In the mixed liquor of sour methyl ethyl ester.The preparation method of working electrode is to lead HS1 that mass fraction is 80% or HS2,10%
The binding agent 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 is ground into 30min with agate mortar, then slurries is uniformly coated on Copper Foil, each Copper Foil
The quality of load is 0.5-0.6mg, and under conditions of 100 DEG C 10h is dried；Charge-discharge test is surveyed in LAND CT2001A batteries
Carry out on test system, its potential interval is relative to Li+/Li 0.01-3.0V；Cyclic voltammetry curve is in IVIUM electrochemistry
Carry out on work station, its potential interval is relative to Li+/ Li 0.01-3.0V, sweep speed for 0.2mV/s；It is 10mV in amplitude
Shi Jinhang ac impedance measurements, the frequency range of test is by 100kHz to 10mHz.
The structure and morphology characterization of composite：
Fig. 3 is the Raman collection of illustrative plates of HS1 and HS2, wherein 194,482,524,619 and 691cm-1Corresponding is have point brilliant
The Co of stone structure3O4F2g,Eg,F2g,F2gAnd A1gVibration mode.The characteristic peak of HS2 is similar with HS1, but its A1gPeak is offset to
709cm-1, and narrow, show Co in HS23O4Size ratio it is big in HS1.Graphene shows typically in Fig. 3
D band (1353cm-1) and G band (1604cm-1).The I of HS1 and HS2D/IGValue is respectively 1.49 and 1.25, shows in HS1 because N mixes
It is miscellaneous and cause increasing for topological defect.Fig. 4 is the Raman spectrum comparison diagram of HS3 and HS4.As can be seen that HS3, HS4
Raman characteristic peaks are similar with HS1, HS2.Fig. 5 is X-ray diffraction (XRD) collection of illustrative plates of HS1 and HS2, it can be seen that in composite
There are the characteristic peak of Graphene and the Co of spinel structure3O4Characteristic peak.The XRD spectrum of HS3, HS4 and commercial hydrogen bearing alloy is as schemed
Shown in 6, it can be seen that HS3 and HS4 remains CaCu5The hexagonal structure of type, this is because Co in composite3O4With RGO
Content it is all very low, Jing ICP test, Co in HS3 (or HS4)3O4And the mass fraction of RGO is respectively 0.9wt% and 1.8wt%.
The content of RGO is about 26wt% (referring to Fig. 7) in knowing HS1 and HS2 by thermogravimetric analysis (TGA), and the wherein thermogravimetric curve of HS1 exists
248,300 and 473 DEG C have obvious weight loss at 3, and 248 and 300 DEG C of weight loss may be attributed to the nothing that N doping causes
The oxidation of sequence carbon, 473 DEG C of weight loss may be attributed to the oxidation of carbon in Graphene skeleton.Fig. 8 is the full spectrograms of XPS of HS1,
Known by the figure and contain in composite Elements C, N, O and Co, the wherein content of N atoms are 3.31at%.Fig. 9 is the high-resolution of Co
2p XPS collection of illustrative plates, shows that Co elements are present in the form of the oxide in the composite.High-resolution 1s XPS collection of illustrative plates such as Figure 10 of N
It is shown, show that N is made up of pyridine nitrogen and pyrroles's nitrogen.The surface topography of HS1 and HS2 is observed by ESEM (SEM), referring to
Figure 11 and 12.As seen from the figure, Co3O4Nanocube is pinned on graphene sheet layer, and graphene sheet layer is coated with Co3O4。
Co in HS13O4The length of side of nanocube is 50-80nm, and Co in HS23O4The length of side of nanocube is 150-200nm.
The SEM patterns of HS3 and HS4 are referring to Figure 13 and 14, it can be seen that Co3O4It is pinned on graphene nanometer sheet, this is closed with commercial hydrogen storage
Surface difference that golden light is slided (referring to Figure 15).It is apparent to can be seen that compared with HS4, Co in HS33O4The distribution of nanocube
It is more uniform, and without obvious segregation.This is likely due to N functional groups in HS3 and introduces 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 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 for being formed3)6]2+
Can be used as Co3O4A kind of nucleus).High-resolution-ration transmission electric-lens (HRTEM) photo of HS1 and HS2 is referring to Figure 18 and 19.Crystal face
Spacing 0.286,0.244 and 0.202nm correspond to respectively Co3O4(220), (311) and (400) crystal face.The illustration of Figure 18 is indicated
Co3O4Good contact between N-RGO.
The Ni-MH battery Electrochemical Characterization of HS3 and HS4：
Figure 20 gives the discharge curve of HS3, HS4 and commercial hydrogen-bearing alloy electrode, and as seen from the figure three has phase
Near discharge capacity.The high rate performance of three electrodes can be seen referring to Fig. 1 by the figure：In all of discharge current density Id
Under, the high-rate discharge ability of HS3 electrodes is good than other two electrodes, in IdBecome apparent from when larger.In discharge current
When density is 3A/g, the capacity of HS3 is up to 223.1mAh/g, is 3.2 times (68.7mAh/g) of commercial hydrogen bearing alloy.Metallic hydrogen
The high-rate discharge ability of compound electrode is by the hydrogen atom diffusion velocity inside the electrochemical reaction rates and alloy of electrode surface
Determine, the former can be by exchange current density I0, contact resistance RcAnd charge transfer resistance R of electrodectCharacterize, the latter can be by
Limiting current density ILWith hydrogen atom diffusion coefficient DHAssessment.Figure 21 is HS3, HS4 and commercial hydrogen bearing alloy in 50% depth of discharge
Under linear polarisation curves.I0Value can be calculated by the slope of figure cathetus.Figure 22 is the test of electrochemical impedance collection of illustrative plates
As a result, RcAnd RctCan be obtained according to the fitting of the equivalent circuit diagram in the figure.IL(referring to Figure 23) and DH(referring to Figure 24) can be used
To characterize speed of the hydrogen by alloy diffusion inside to surface.Know that HS3 electrodes have maximum I by calculating0, ILAnd DH, while having
Minimum RcAnd Rct, indicate its best high-rate discharge ability.The advantage of HS3 electrodes is：(1) heteroatom defect,
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)
Undersized Co3O4Nanocube improves Co in being uniformly distributed for N-RGO surfaces3O4Volmer is reacted：H2O+e-→H+
OH-Catalysis activity, improve discharge capacity；(3) hydrogen bearing alloy and Co3O4The Seamless integration- of/N-RGO reduces electrode internal resistance.
The lithium ion battery chemical property of HS1 and HS2 is characterized：
Figure 25 is cyclic voltammetric (CV) curve of HS1 and HS2, and for HS1 electrodes, first time cathodic scan has one by force
The weak acromion (1.31V) of peak (0.68V) and one, corresponds to respectively amorphous Li2The formation of O and by Co3O4To the multi-step transition of Co.
Additionally, the strong peak also correspond to the formation of irreversible solid electrolyte interface film (SEI films).From the beginning of the second circle, weak acromion
Position is basically unchanged, but strong peak is offset to 0.89V, and simultaneous current density is remarkably decreased.The CV curves of HS1 electrodes
The 3rd circle with second enclose essentially coincide, indicate its good cyclical stability.Additionally, the sun in the CV curves of HS1 electrodes
Pole part changes less in cyclic process, and two anode peak 1.37V and 2.12V correspond to respectively Co to CoO and Co3O4Transformation.
The CV curves of HS2 are similar with HS1, and except for the difference that two negative electrode peaks are offset to respectively 0.66V and 1.21V, two anode peak difference
1.46V and 2.16V is offset to, HS2 electrodes is reflected with bigger activation polarization.Constant current charge-discharge curve also demonstrates this
A bit (referring to Figure 26).Know that HS1 electrodes have the discharge platform higher than HS2 electrode by the figure, show HS1 in electrochemical reaction
In have less activation polarization.Can also be seen that by the figure and be respectively provided with higher initial discharge capacity by two electrodes (HS1 is
1493.5mAh/g, HS2 are 1492.7mAh/g).But the second of HS2 electrodes circle discharge capacity be just decreased obviously to
806.2mAh/g, have lost 46%.By contrast, the discharge capacity of HS1 is in the second circle, the 3rd circle, or even the 50th circle all bases
This holding is constant, and respectively 1305.0,1297.5 and 1251.2mAh/g.Additionally, the first circle coulombic efficiency of HS1 electrodes
(87.8%) apparently higher than HS2 (51.2%).This shows that N doping can to a certain extent suppress the decomposition of electrolyte, improves
The invertibity of lithium storage.Cycle performance curves of the Figure 27 for HS1 and HS2 when current density is 0.1A/g, the storehouse of two electrodes
Human relations efficiency is held in close 100%, indicates good reversible lithium storage characteristic.HS1 circulation 50 circle after capacity be
1251.2mAh/g, have lost 4.1% (compared with the second circle discharge capacity), and the capacity after the circle of HS2 circulations 50 is only
753.9mAh/g.HS1 has excellent multiplying power discharging property, referring to Figure 28.HS1 electrodes are close in the different electric currents of 0.2 to 10A/g
Average discharge capacity under degree is respectively 1174.5,1058.4,934.6,800.3,658.4,538.1 and 423.6mAh/g, when
When electric current returns to 0.2A/g, its discharge capacity is recovered rapidly to 1088.2mAh/g, and protects substantially in subsequent charge and discharge cycles
It is fixed to keep steady.HS1 electrodes show excellent multiplying power discharging property, and this is mainly due to Co3O4Synergy between N-RGO：
(1) smaller size of Co in HS13O4Bigger electrochemical surface area can be provided, shorten ion diffusion length；(2)N-RGO
With more preferable electrode/electrolyte wetability, the good contact of electrolyte and electrode active material can be promoted, strengthen Li+'s
Transmission dynamics；(3) N-RGO has more topological defects, can provide more avtive spots, is conducive to Li+Suction
Echo diffusion；(4)Co3O4There is higher interaction and preferably electrical contact between N-RGO, electrode conductivuty is improve.
This is consistent with the test result of AC impedance (referring to Figure 29), and it is charge transfer resistance that wherein semicircle is corresponding, line correspondences
It is the Warburg impedances for characterizing diffusion.Half diameter of a circle is less, then charge transfer resistance is less, and the electrochemistry of electrode is anti-
Answer dynamic performance better.Compared with HS2, HS1 electrodes have less charge transfer resistance (91.2vs.122.8 Ω), less
Activation polarization.Figure 30 is cycle characteristics curve of the HS1 and HS2 electrodes under the current density of 5A/g.HS1 electrodes have more
High discharge capacity and more preferable cyclical stability.This is also attributable to Co3O4Cooperative effect between N-RGO.On the one hand,
Co3O4It is pinned on graphene sheet layer, or Graphene is supported, is coated with Co3O4, Graphene not only can provide elastic deformation
Buffering area, alleviates Co3O4In Li+The Volume Changes produced during insertion/abjection, can also suppress the Co in cyclic process3O4
The reunion of nanocube, prevents the efflorescence of electrode material；On the other hand, Co3O4Nanocube is pinned at the lamella of Graphene
Between, stacking of the graphene sheet layer in cyclic process can be suppressed as nanometer pad, it is to avoid the graphitization of Graphene, make
The high specific surface area of its holding, loose three-dimensional conductive network structure and the quick electronics of holding and ion transmission.HS1 is good
High rate performance and cyclical stability show that the composite that we prepare has one in terms of the practical application of high power type battery
Fixed potentiality.
Claims (8)
1. a kind of cobalt oxide/graphene composite (Co3O4/ RGO) preparation method, comprise the following steps：
A, according to improved Hummers methods synthesize graphite oxide；
B, at 22～25 DEG C, by the cobalt acetate of 1～2ml 0.2M, the graphite oxide of 1～2ml 4.5mg/ml is added to 34～
In the absolute ethyl alcohol of 36ml, 20～30min of ultrasonic disperse, then 9～10h is heated at 75～85 DEG C makes cobalt acetate hydrolysis, oxidation
And grow extra small Co in graphite oxide surface in situ3O4Nano-particle；
C, heat 2.5～3.5h at 145～155 DEG C with the method for hydro-thermal and make Co3O4The further crystallization of nano-particle, graphite oxide
Reduction, afterwards by the inorganic membrane filtration that product aperture is 0.1～0.2 μm, respectively with second alcohol and water thoroughly cleaning 4～6 times,
22～25 DEG C of 10～12h of drying in vacuum drying chamber.
2. cobalt oxide/graphene composite (Co according to claim 13O4/ RGO) preparation method, its feature
It is：By adjusting the amount of ethanol and hydrolysis and the oxidation rate of controlling reaction temperature cobalt acetate in step b.
3. cobalt oxide/graphene composite (Co according to claim 13O4/ RGO) preparation method, its feature
It is：Co is controlled in step c by adjusting the temperature of hydro-thermal3O4Crystallization shape.
4. cobalt oxide/graphene composite (Co according to claim 13O4/ RGO) preparation method, its feature
It is：0.5～1g hydrogen storing alloy powders were added before 145～155 DEG C of hydro-thermal reactions in step c, cobaltosic oxide/graphite is prepared
The composite Co of alkene and hydrogen bearing alloy3O4/RGO/HSAs。
5. cobalt oxide/graphene composite (Co according to claim 13O4/ RGO) preparation method, its feature
It is：0.5～0.8ml ammoniacal liquor is added in step b, cobalt acetate hydrolyzed under the adjustment effect of ammoniacal liquor, aoxidized, prepared four and aoxidize
Three cobalts/nitrogen-doped graphene composite Co3O4/N-RGO。
6. cobalt oxide/graphene composite (Co according to claim 13O4/ RGO) preparation method, its feature
It is：In step b add 0.5～0.8ml ammoniacal liquor, cobalt acetate hydrolyzed under the adjustment effect of ammoniacal liquor, aoxidized, in step c
0.5～1g hydrogen storing alloy powders are added before 145～155 DEG C of hydro-thermal reactions, cobaltosic oxide/nitrogen-doped graphene and hydrogen storage is prepared
The composite Co of alloy3O4/N-RGO/HSAs。
7. the preparation method according to claim 4 or 6 is obtained cobalt oxide/graphene and the composite wood of hydrogen bearing alloy
Material Co3O4The composite Co of/RGO/HSAs and cobaltosic oxide/nitrogen-doped graphene and hydrogen bearing alloy3O4/ N-RGO/HSAs,
Electrochemical property test is carried out both as the electrode material of Ni-MH battery, is comprised the following steps：
A, 0.25～0.255g active materials are well mixed with 1.0～1.02g carbonyl nickel powders, by tablet press machine 8～20MPa's
The electrode slice of a diameter of 10～15mm is pressed under pressure；
B, using electrode slice prepared in step a as working electrode, the Ni (OH) of sintering2/ NiOOH pieces are used as to electrode, oxidation
Used as reference electrode, the KOH solution of 25～35wt% is electrolyte to mercury electrode, and constituting the three-electrode system of standard carries out electrochemistry
Test；
C, when carrying out volume test, charging and discharging currents density is 0.06A/g (0.2C), and the activation number of turns is 4；Carry out high magnification to put
During electric performance test, the density of charging current is 0.3A/g (1C), and discharge current density is respectively 0.3,0.6,0.9,1.2,1.5,
2.4 and 3A/g (10C)；
D, electrochemical property test are carried out on IVIUM electrochemical workstations, in the amplitude relative to OCP (OCP)
For 5mV when carry out ac impedance measurement, the frequency range of test is by 100kHz to 5mHz；Under the conditions of 50% depth of discharge,
When relative to the potential scan scope of OCP being -5 to 5mV, carry out sweeping speed and test for the linear polarisation curves of 0.05mV/s；
Under the conditions of 50% depth of discharge, when the potential scan scope relative to OCP is 0 to 1.5V, carry out sweeping anode of the speed for 5mV/s
Polarization curve is tested；Under 100% charged state, under the potential step of+500mV relative to Hg/HgO, carry out 4000s's
The test of current versus time curve.
8. the cobalt oxide/graphene composite that the preparation method according to any one of claims 1 to 3 or 5 is obtained
(Co3O4/ RGO) and cobaltosic oxide/nitrogen-doped graphene composite (Co3O4/ N-RGO), both as lithium ion battery
Electrode material carries out electrochemical property test, comprises the following steps：
A, using active material as working electrode, used as to counter/reference electrode, barrier film is the films of Celgard 2500 to lithium piece, electricity
Solution liquid is the LiPF of 1M6Volume ratio is dissolved in for 1:1:The mixed liquor of 1 ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate
In, in the glove box ([O full of argon gas2]<1ppm,[H2O]<CR2016 type button cells are assembled in 1ppm)；
B, the preparation method of working electrode be by active material that mass fraction is 80%, 10% super P and 10% it is viscous
Knot agent polyvinylidene fluoride PVDF is homogenously mixed together, in being dissolved in METHYLPYRROLIDONE NMP, by mixture agate
Nao mortar grinder 30min, are then uniformly coated on slurries on Copper Foil, and the quality of each Copper Foil load is 0.5-0.6mg,
10h is dried under conditions of 100 DEG C；
C, charge-discharge test are carried out on LAND CT2001A battery test systems, and its potential interval is relative to Li+/Li
0.01-3.0V；Cyclic voltammetry curve is carried out on IVIUM electrochemical workstations, and its potential interval is relative to Li+/Li
0.01-3.0V, sweeps speed for 0.2mV/s；Ac impedance measurement is carried out when amplitude is 10mV, the frequency range of test is by 100kHz
To 10mHz.
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