CN105428627A - Preparation method for hydrogen storage alloy and graphene composite material and application of composite material - Google Patents
Preparation method for hydrogen storage alloy and graphene composite material and application of composite material Download PDFInfo
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Abstract
The invention relates to a preparation method for a hydrogen storage alloy and graphene composite material (HSAs@RGO) and application of the composite material serving as a negative electrode material of a nickel-hydrogen battery. The composite material is prepared according to the following steps of (a) smelting a rare earth element and other metal elements to obtain an ingot by an electric arc furnace under a protection condition of argon; (b) carrying out annealing and mechanical grinding on the ingot to obtain alloy powder under the protection of argon, wherein the average particle diameter is 50 micrometers; (c) preparing graphite oxide according to an improved Hummers method; and (d) placing the hydrogen storage alloy in a graphite oxide colloid, reducing the hydrogen storage alloy with hydrazine hydrate, and then carrying out annealing. The HSAs@RGO composite material is synthesized by a simple method from top to bottom. When serving as the negative electrode material of the nickel-hydrogen battery, the composite material has excellent high-rate discharge performance, and the capacity retention rate of the composite material reaches 51.25% at the discharge current density of 3,000Ma/g and is almost four times of that of the independent hydrogen storage alloy. A novel method and idea for further improving the comprehensive performance, particularly the high-rate discharge performance of the nickel-hydrogen battery is provided by the invention.
Description
Technical field:
The present invention relates to the preparation of HSAsRGO composite material and the application as nickel-hydrogen battery negative pole material thereof.
Background technology:
Because environmental problem is increasingly serious, global energy is in short supply, and the energy storage device of clean and effective receives to be paid close attention to widely and study.In existing energy storage device, nickel metal hydride (Ni-MH) battery has certain advantage because it has good fail safe, thermal adaptability and environment friendly in market competition.Ni-MH battery has been widely used in mobile electronic device, electric tool, hybrid vehicle etc.But in order to improve the market competitiveness of Ni-MH battery further and meet the demand of market to high-power battery, its power density still needs further raising.The power density of Ni-MH battery is mainly determined by the high-rate discharge ability (HRD) of its negative material-hydrogen bearing alloy (HSAs).In recent years, researcher has carried out large quantifier elimination in the high-rate discharge ability improving hydrogen bearing alloy, makes some progress.
The method of current raising hydrogen bearing alloy high-rate discharge ability mainly contains: in hydrogen bearing alloy, add some additives large with specific area that conduct electricity very well to improve electric conductivity and the high-rate discharge ability of electrode; Ball milling is carried out to improve the electrochemical reaction rates of electrode after being mixed with graphite, magnesium-yttrium-transition metal, carbon nano-tube by hydrogen bearing alloy; Use surface-treated method, fluorination treatment, plating, alkali treatment etc., improve the conductivity of alloy surface.But said method is limited for the lifting of high-rate discharge ability, but also there are some shortcomings: ball milling easily makes alloy amorphousization, must be very accurate to the control of thickness of coating during plating etc.Therefore the Novel anode material developing high-capacity nickel-hydrogen battery is imperative.Graphene is a kind of two-dimensional material with bigger serface, shows excellent conductivity, thermal conductivity, chemical stability and structure adaptability simultaneously.These advantages make graphene-based composite material have electronics quickly and ion transfer speed and excellent electrochemical reaction dynamic performance.
Summary of the invention:
The object of this invention is to provide the preparation method of a kind of hydrogen bearing alloy and graphene composite material (HSAsRGO) and the application as nickel-hydrogen battery negative pole material thereof.This invention has prepared HSAsRGO composite material by simple top-to-bottom method.The architectural characteristic of this composite material uniqueness makes it have the hydrogen atom diffusion velocity of electrode surface electrochemical reaction rates and electrode interior faster, thus substantially increases its high-rate discharge ability.
The present invention relates to a kind of preparation of HSAsRGO composite material and the application as nickel-hydrogen battery negative pole material thereof.
Particular content is as follows:
The preparation method of a kind of hydrogen bearing alloy and graphene composite material (HSAsRGO), comprises the following steps:
A, under argon shield condition, by purity be 99.5% rare earth element (La, Ce, Y) and purity be 99.9% other metallic elements (Ni, Mn, Co, Al) melting in arc furnace, obtain its ingot casting;
B, to be annealed under argon shield by ingot casting and mechanical lapping obtains master alloy powder, average particulate diameter is 50 μm;
C, according to improve Hummers method synthesis graphite oxide;
D, hydrogen bearing alloy is placed in graphite oxide colloid, with hydrazine hydrate reduction, then anneals in argon hydrogen gaseous mixture, by simple top-to-bottom method synthesis HSAsRGO composite material.
In described step a, the composition of ingot casting comprises AB
5, AB
2, AB
3type hydrogen storage alloy.
With before hydrazine hydrate reduction in steps d, first add ammoniacal liquor, the pH value of adjustment graphite oxide, to obtain homodisperse redox graphene.
Annealed in argon hydrogen gaseous mixture by ingot casting described in steps d, object is a part of group making also not reduce in Graphene, comprises hydroxyl, carboxyl, carbonyl group, is reduced, and strengthens the reciprocation between HSAs and RGO further.
The hydrogen bearing alloy prepared according to said method and graphene composite material (HSAsRGO), it carries out electro-chemical test as electrode material, comprises the following steps:
A, first 0.25 ~ 0.255g active material is mixed with 1.0 ~ 1.02g carbonyl nickel powder after, then make at the pressure of 8 ~ 20MPa the electrode slice that diameter is 10 ~ 15mm by tablet press machine, described active material comprises HSAsRGO composite material or foundry alloy;
B, using electrode slice prepared in step a as work electrode, the Ni (OH) of sintering
2/ NiOOH sheet is as to electrode, and mercuric oxide electrode is as reference electrode, and the KOH solution of 25 ~ 35wt% is electrolyte, and the three-electrode system of composition standard carries out electro-chemical test;
C, when carrying out volume test with described HSAsRGO combination electrode as work electrode, charging and discharging currents density is 60mA/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 300mA/g (1C), and discharge current density is respectively 300,600,900,1200,1500,2400,3000mA/g (10C);
D, electrochemical property test carry out on IVIUM electrochemical workstation.Carry out ac impedance measurement when the amplitude relative to OCP is 5mV, the frequency range of test is by 100kHz to 5mHz; Under 50% depth of discharge condition, when the potential scan scope relative to OCP is-5 to 5mV, carries out sweeping speed for the linear polarisation curves of 0.05mV/s and test; Under 50% depth of discharge condition, when the potential scan scope relative to OCP is 0 to 1.5V, carries out sweeping speed for the anodic polarization curves of 5mV/s and test; Under 100% charged state, under the electromotive force step of+500mV relative to Hg/HgO, carry out the test of the current versus time curve of 4000s;
E, described electrode material, as the negative material of Ni-MH battery, have excellent high-rate discharge ability.
Technique effect of the present invention is:
The HSAsRGO composite material that the present invention obtains has large specific area, high conductivity, fast electronics and ion transfer speed, fast electrode surface electrochemical reaction rates and the hydrogen atom diffusion velocity of electrode interior, significantly improve its high-rate discharge ability.
Accompanying drawing illustrates:
High-rate discharge ability curve under Fig. 1, different discharge current density.
The optical photograph preparing schematic diagram and electrode slice of Fig. 2, HSAsRGO composite material, wherein:
Preparation method's schematic diagram of a, HSAsRGO composite material;
The optical photograph of b, use for electrochemical tests electrode slice.
The SEM photo of Fig. 3, HSAsRGO composite material.
The SEM photo of Fig. 4, foundry alloy.
The SEM photo of Fig. 5, Graphene.
The TEM photo of Fig. 6, Graphene, illustration is its low power TEM photo.
The XRD collection of illustrative plates of Fig. 7, HSAsRGO composite material and foundry alloy.
The Raman collection of illustrative plates of Fig. 8, HSAsRGO composite material and graphite.
Fig. 9, discharge capacity curve.
Figure 10, electrochemical impedance collection of illustrative plates under 50% depth of discharge.
Figure 11, linear polarisation curves under 50% depth of discharge.
Figure 12, anodic polarization curves under 50% depth of discharge.
Figure 13, anodic current density are to the current versus time curve that discharges under 100% charged state.
Embodiment
After now embodiments of the invention being set forth in:
Embodiment
Preparation process in the present embodiment and step as follows:
(1) under argon shield condition, by purity be 99.5% rare earth element (La, Ce, Y) and purity be 99.9% other metallic elements (Ni, Mn, Co, Al) melting in arc furnace, obtain its ingot casting; Anneal ingot casting at 1273K temperature under argon shield 5h afterwards, and finally mechanical lapping obtains alloy powder again, and average particulate diameter is 50 μm; According to the Hummers method synthesis graphite oxide improved; Hydrogen storing alloy powder is placed in graphite oxide, adds ammoniacal liquor and hydrazine hydrate, then anneal in argon hydrogen gaseous mixture, make graphite oxide be reduced into Graphene.By simple top-to-bottom method synthesis HSAsRGO composite material.
(2) 0.25gHSAsRGO composite material or foundry alloy and 1.0g carbonyl nickel powder are mixed, then make at 8MPa pressure the electrode slice that diameter is 15mm, using this electrode slice as work electrode, Ni (OH)
2/ NiOOH sheet is as to electrode, and mercuric oxide electrode is as reference electrode, and the KOH solution of 30wt% is electrolyte, and the three-electrode system of composition standard carries out electro-chemical test;
(3) when carrying out volume test with described HSAsRGO combination electrode as work electrode, charging and discharging currents density is 60mA/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 300mA/g (1C), and discharge current density is respectively 300,600,900,1200,1500,2400,3000mA/g (10C);
(4) electrochemical property test carries out on IVIUM electrochemical workstation.Carry out ac impedance measurement when the amplitude relative to OCP is 5mV, the frequency range of test is by 100kHz to 5mHz; Under 50% depth of discharge condition, when the potential scan scope relative to OCP is-5 to 5mV, carries out sweeping speed for the linear polarisation curves of 0.05mV/s and test; Under 50% depth of discharge condition, when the potential scan scope relative to OCP is 0 to 1.5V, carries out sweeping speed for the anodic polarization curves of 5mV/s and test; Under 100% charged state, under the electromotive force step of+500mV relative to Hg/HgO, carry out the test of the current versus time curve of 4000s.
The pattern of HSAsRGO composite material and structural characterization:
The surface topography of HSAsRGO composite material, foundry alloy and Graphene is observed by ESEM (SEM), see Fig. 3-5, as can be seen from Figure 3, hydrogen bearing alloy Surface coating Graphene, thus makes it have larger specific area and more avtive spot.Compared with smooth alloy surface (see Fig. 4), this composite material exhibits has gone out the surface characteristics (see Fig. 5) similar to Graphene, graphene sheet layer that is thin, that have fold is randomly dispersed in alloy surface, arrange irregular between lamella but can closely be connected, thus forming coarse surface.Fig. 6 is the transmission electron microscope photo (TEM) of Graphene, can find out that Graphene is two-dimensional layered structure, surface has fold and graphene nanometer sheet is interconnected, thus makes it have large specific area, good electric conductivity and more avtive spot.Fig. 7 is the XRD diffracting spectrum of HSAsRGO composite material and foundry alloy, can find out that HSAsRGO composite material still remains CaCu
5the hexagonal structure of type, consistent with the crystal structure of foundry alloy, this is because the amount of Graphene is little in composite material, through ICP test, in composite material, the mass fraction of Graphene is only 1.3%.Fig. 8 is the Raman spectrum comparison diagram of graphite and HSAsRGO composite material.Can be found out at 1580cm by the Raman spectrum of graphite
-1place has an obvious G to be with peak, this and E
2gthe single order scattering phase of vibration mode is corresponding, at 1348cm
-1there is a little D band peak at place, shows to there are some defects in graphite.And G band obviously broadens and has transferred to 1595cm in the Raman collection of illustrative plates of composite material
-1place, D band is positioned at 1350cm
-1place, and the peakedness ratio that G band and D are with diminishes, this shows increase and the sp of composite material defect and unordered degree
2the reduction of the average-size of domain.
The Electrochemical Characterization of HSAsRGO composite material:
When carrying out electro-chemical test, composite material and these two electrodes of foundry alloy all than being easier to activation, circulating and can reach maximum discharge capacity in 4 weeks, see the discharge capacity curve of two kinds of electrodes in Fig. 9.In addition, we it can also be seen that: although the maximum discharge capacity (C of HSAsRGO composite material
max) less than foundry alloy, 220.07mAh/gvs.302.62mAh/g, but the former discharge voltage plateau is but apparently higher than the latter, and this shows that HSAsRGO composite material has less polarization and better electrochemical reaction dynamics.The C that composite material is less
maxvalue is caused by the conductivity that Graphene is good.The conductivity that Graphene is good accelerates the electrochemical reaction rates of electrode surface, and accelerates Hydrogen evolving reaction (HER) further.HER is unfavorable for the diffusion of Surface Hydrogen atom to alloy inside, and electrode discharge capacity is reduced.Although the discharge capacity of HSAsRGO electrode is lower than foundry alloy when 0.2C, when 10C, its discharge capacity is 112.79mAh/g, is 2.76 times of foundry alloy discharge capacity, see the high-rate discharge ability curve of Fig. 1 two kinds of electrodes.In addition, can also see from Fig. 1: at all discharge current density I
cunder, the high-rate discharge ability of HSAsRGO electrode is all good than foundry alloy, and both gaps are at I
cmore obvious time larger.When discharge current density is 3000mA/g, the capacity retention rate of composite material, up to 51.25%, is almost 4 times of independent hydrogen bearing alloy.Figure 10 is the test result of electrochemical impedance collection of illustrative plates, can find out that each collection of illustrative plates is all made up of two semicircles of high frequency region and the straight line of low frequency range.Contact resistance (the R that what little and large semicircle reflected respectively is between alloying pellet or between alloying pellet and current collector
c) and the charge transfer resistance (R of electrode
ct).The straight line portion of low frequency range is then main owing to Warburg impedance.Half circular diameter is less, and its impedance is less.Therefore, HSAsRGO composite electrode has less R
cand R
cTvalue, thus reduce the polarization in charge and discharge process, be conducive to the carrying out of electrochemical reaction.Figure 11 is the linear polarisation curves of two electrodes under 50% depth of discharge.Surface exchange current density value I
0can be calculated by the slope of figure cathetus.The I of composite electrode
0value is comparatively large, namely to be bordering on its electrochemical reaction rates under poised state faster than foundry alloy electrode.Figure 12 is the anodic polarization curves of composite electrode and foundry alloy electrode, can find out that oxidation current density increases along with the increase of overpotential, until reach maximum, i.e. and limiting current density (I
l).I
lbe worth larger, hydrogen atom is faster in the diffusion velocity of alloy inside.As seen from the figure, composite material has larger I
lvalue, therefore on HSAsRGO electrode, the diffusion rate of hydrogen atom is faster.Figure 13 is electromotive force step figure, and can find out, initial period, current density sharply declines, and along with the prolongation of time, current density linearly declines.Large than foundry alloy electrode of the hydrogen atom diffusion coefficient that can calculate HSAsRGO combination electrode by the linear segment in fitted figure.To sum up, HSAsRGO composite electrode has fast surface electrochemistry reaction speed and alloy internal hydrogen atomic diffusion rates, effectively improves its high-rate discharge ability.This composite material can be used as the negative material of Ni-MH battery, has good application prospect in high-power battery field.The preparation method that the present invention relates to can also be extended to other hydrogen bearing alloy systems, provides new method and thinking for improving Ni-MH battery high-rate discharge ability further.
Claims (5)
1. a preparation method for hydrogen bearing alloy and graphene composite material (HSAsRGO), comprises the following steps:
A, under argon shield condition, by purity be 99.5% rare earth element (La, Ce, Y) and purity be 99.9% other metallic elements (Ni, Mn, Co, Al) melting in arc furnace, obtain its ingot casting;
B, to be annealed under argon shield by ingot casting and mechanical lapping obtains master alloy powder, average particulate diameter is 50 μm;
C, according to improve Hummers method synthesis graphite oxide;
D, hydrogen bearing alloy is placed in graphite oxide colloid, with hydrazine hydrate reduction, then anneals in argon hydrogen gaseous mixture, by simple top-to-bottom method synthesis HSAsRGO composite material.
2. the preparation method of hydrogen bearing alloy according to claim 1 and graphene composite material (HSAsRGO), is characterized in that: in step a, the composition of ingot casting comprises AB
5, AB
2, AB
3type hydrogen storage alloy.
3. the preparation method of hydrogen bearing alloy according to claim 1 and graphene composite material (HSAsRGO), it is characterized in that: with before hydrazine hydrate reduction in steps d, first add ammoniacal liquor, the pH value of adjustment graphite oxide, to obtain homodisperse redox graphene.
4. the preparation method of hydrogen bearing alloy according to claim 1 and graphene composite material (HSAsRGO), it is characterized in that: described in steps d, ingot casting is annealed in argon hydrogen gaseous mixture, object is a part of group making also not reduce in Graphene, comprise hydroxyl, carboxyl, carbonyl group, reduced, and strengthened the reciprocation between HSAs and RGO further.
5. the hydrogen bearing alloy obtained according to the preparation method described in claim 1 and graphene composite material (HSAsRGO), it carries out electro-chemical test as electrode material, comprises the following steps:
A, first 0.25 ~ 0.255g active material is mixed with 1.0 ~ 1.02g carbonyl nickel powder after, then make at the pressure of 8 ~ 20MPa the electrode slice that diameter is 10 ~ 15mm by tablet press machine, described active material comprises HSAsRGO composite material or foundry alloy;
B, using electrode slice prepared in step a as work electrode, the Ni (OH) of sintering
2/ NiOOH sheet is as to electrode, and mercuric oxide electrode is as reference electrode, and the KOH solution of 25 ~ 35wt% is electrolyte, and the three-electrode system of composition standard carries out electro-chemical test;
C, when carrying out volume test with described HSAsRGO combination electrode as work electrode, charging and discharging currents density is 60mA/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 300mA/g (1C), and discharge current density is respectively 300,600,900,1200,1500,2400,3000mA/g (10C);
D, electrochemical property test carry out on IVIUM electrochemical workstation, and carry out ac impedance measurement when the amplitude relative to OCP (Open Circuit Potential) is 5mV, the frequency range of test is by 100kHz to 5mHz; Under 50% depth of discharge condition, when the potential scan scope relative to OCP is-5 to 5mV, carries out sweeping speed for the linear polarisation curves of 0.05mV/s and test; Under 50% depth of discharge condition, when the potential scan scope relative to OCP is 0 to 1.5V, carries out sweeping speed for the anodic polarization curves of 5mV/s and test; Under 100% charged state, under the electromotive force step of+500mV relative to Hg/HgO, carry out the test of the current versus time curve of 4000s;
E, described electrode material, as the negative material of Ni-MH battery, have excellent high-rate discharge ability.
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| CN105895884A (en) * | 2016-06-13 | 2016-08-24 | 吉林大学 | Method for surface modification on hydrogen storage alloy by molybdenum disulfide, and application thereof |
| CN105895884B (en) * | 2016-06-13 | 2018-05-15 | 吉林大学 | A kind of method and its application for carrying out surface modification to hydrogen bearing alloy using molybdenum disulfide |
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| CN106654212A (en) * | 2016-12-29 | 2017-05-10 | 吉林大学 | Preparation method and application of cobaltosic oxide/graphene composite material (Co<3>O<4>/N-RGO) |
| CN106654212B (en) * | 2016-12-29 | 2019-07-30 | 吉林大学 | A kind of Co3O4The preparation method and application of/N-RGO/HSAs composite material |
| CN107164657A (en) * | 2017-06-15 | 2017-09-15 | 燕山大学 | A kind of preparation method of graphene/La Fe B systems low temperature hydrogen storage composite |
| CN108054369A (en) * | 2017-12-15 | 2018-05-18 | 淄博君行电源技术有限公司 | A kind of preparation method of hydrogen bearing alloy and graphene composite material |
| CN108063231A (en) * | 2017-12-15 | 2018-05-22 | 淄博君行电源技术有限公司 | A kind of preparation method of nickel-hydrogen battery negative pole hydrogen bearing alloy/graphene composite material |
| CN108063231B (en) * | 2017-12-15 | 2020-05-26 | 淄博君行电源技术有限公司 | Preparation method of hydrogen storage alloy/graphene composite material for nickel-metal hydride battery cathode |
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