CN104466203A - Composite catalyst of air electrode of lithium-air cell - Google Patents
Composite catalyst of air electrode of lithium-air cell Download PDFInfo
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- CN104466203A CN104466203A CN201310432313.XA CN201310432313A CN104466203A CN 104466203 A CN104466203 A CN 104466203A CN 201310432313 A CN201310432313 A CN 201310432313A CN 104466203 A CN104466203 A CN 104466203A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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Abstract
The invention relates to a composite catalyst of an air electrode of a lithium-air cell. The composite catalyst comprises a metal catalyst, and a support for performing synergic catalysis with the metal catalyst. The metal catalyst is uniformly distributed on the surface of the support via in-situ loading. The metal catalyst accounts for 0.01 wt%-99.9 wt% of the composite catalyst, preferably 0.1 wt%-60 wt%, and more preferably 0.5 wt%-5 wt%. By utilizing the metal catalyst and the support with synergic effect on the metal catalyst, the composite catalyst of the air electrode is formed, the dispersibility and the stability of the original metal catalyst are improved, and also the catalytic activity not owned or unreached by the single metal catalyst is induced to generate.
Description
Technical field
The present invention relates to the catalyst that a class can be used for the air electrode of lithium-air battery, belong to field of chemical power source.
Background technology
No matter portable type electronic product or the development of electric automobile, all in the urgent need to a kind of more frivolous than existing battery system, the energy-storage battery that energy density is higher is supported.Current lithium ion battery, due to the restriction of its structure, specific capacity is lower, and the limited space promoted further.Therefore, new battery system instead product must be found.Lithium-air battery is exactly a kind of strong candidate, and its positive active material is oxygen, without the need to storage in the battery, is directly provided by the air in environment, decrease the gross mass of battery system, thus improve energy density in discharge process.Its theoretical energy density can reach 13200Wh/kg, is the highest in electrochemical cell up to now, equally matched with alcohol fuel cell, and can match in excellence or beauty with gasoline, becomes the focus of research both at home and abroad gradually.Lithium-air battery is a kind of secondary apparatus for storing electrical energy, is again a kind of fuel cell; Both can use as primary cell, again can as filling secondary cell.
But the actual accumulate performance of lithium-air battery and efficiency for charge-discharge restricted by air electrode (positive pole), general air electrode primarily of catalyst, catalyst carrier and binding agent three part form.The positive active material of battery is the oxygen in air, in discharge process, the oxygen in air with from the Li in electrolyte
+there is cell reaction in positive pole side, produce discharging product; When charging, discharging product, is produced oxygen and Li by electrochemical decomposition at side of the positive electrode
+.Concrete cell reaction is Li+e
-+ O
2=Li
2o
2(E
o=2.96V).Although this reaction theory is reversible, but in fact because discharging product all needs higher activation energy (american chemical association periodical " J.Am.Chem.Soc. " 128 (2006) 1390-1393.) in the process producing (oxygen reduction reaction) and decomposition (oxygen evolution reaction), thus cause actual lithium-air battery in cyclic process, there is high voltage polarizing, it is namely actual that can to export discharge voltage lower, and needing higher for charging voltage reversible for battery, this will cause producing comparatively macro-energy loss in actual discharge and recharge application.Discharge voltage plateau is low in addition, guiding discharge premature termination, affects its actual discharge capacity; Charging voltage is too high, can cause electrolyte decomposition, and carbon support material is oxidized, and finally affects the long-time stability of battery.
The introducing of catalyst not only can reduce cell reaction overactivity energy existing in discharge process to a certain extent, thus actual discharge voltage and discharge capacity can be improved, but also whether decide lithium-air battery reversible, by promoting that discharging product is decomposed when charging, invertibity and the cycle life of battery can be improved.The catalyst of research air electrode is very meaningful to the application of lithium-air battery.
At present, the catalyst applied in air electrode for lithium air battery is that noble metal or metal oxide: Yi-ChunLu (American Chemical Society's periodical " Journal of American Chemical Society " 132 (2010) 12170 – 12171) etc. proposes using the alloy of precious metals pt and Au as catalyst substantially, although reduce the charging voltage (~ 3.6V) of lithium-air battery to a certain extent, but discharge voltage is still lower, and due to the large usage quantity (40wt%) of catalyst, cost is higher, be difficult to be applied in practical lithium-air battery production.And metal oxide, such as MnO
x/ C (energy and material periodical " Journal of PowerSources " 195(2010) 1370 – 1374.), λ-MnO
2(electrochemical society's periodical " J.Electrochem.Soc. " 149(2002) A1190 – A1195.), α-MnO
2nano wire (German applied chemistry " Angew.Chem., Int.Ed. " 47(2008) 4521 – 4524.), Co
3o
4with NiO(energy and material periodical " Journal of Power Sources " 174 (2007) 1177 – 1182) etc. charging voltage all need at more than 4.0V, and discharge voltage is the highest also only has 2.6V.Generally can be had the catalyst of high catalytic activity by the charge-discharge battery reaction of preparation to lithium-air battery, or design can make the technology of catalyst high degree of dispersion to reduce voltage polarizing, improves the cycle efficieny of lithium-air battery.Therefore key and focus that a kind of suitable air electrode catalyst becomes exploitation high-performance lithium air cell is designed.At present, method about the catalytic efficiency improving lithium-air battery electrode catalyst has and is carried on different carriers such as various material with carbon element, metallic organic framework etc. by catalytic active substance, but these carriers itself are catalytically inactive also, the catalytic activity that can not act synergistically with catalytic active substance to improve catalyst.In addition, different catalytic active substances is carried out compound makes composite catalyst to improve catalytic activity in addition, such as Chinese patent CN102306808A discloses a kind of carbon and carries manganese oxide and silver-colored composite catalyst, Chinese patent CN102694185A discloses the catalytic composite material that a kind of top layer at transition metal oxide is modified with transition metal nitride, it take Mn-Ni as the composite catalyst of catalytic active substance that Chinese patent CN103199274A discloses a kind of, but the catalytic effect of these composite catalysts is only the simple superposition of multiple catalysts, without concerted catalysis effect, all can not increase substantially the performance of lithium-air battery.
In sum, this area lacks a kind of lithium air electrode catalyst material of the low cost that the performance of lithium-air battery can be made to increase substantially, and this area is in the urgent need to developing this lithium air electrode catalyst material making the performance of lithium-air battery increase substantially.
Summary of the invention
Large for the polarization of actual lithium-air battery reaction charging/discharging voltage, cycle efficieny low with stability the problem such as difference, but although and noble metal catalyst catalytic activity large compared with high consumption, the shortcomings such as cost height and poor stability, the first object of the present invention is to obtain a kind of air electrode catalyst that the performance of lithium-air battery can be made to increase substantially.The second object of the present invention is the air electrode obtaining the lithium-air battery that a kind of performance increases substantially.The third object of the present invention is to obtain the lithium-air battery that a kind of performance increases substantially.
In a first aspect of the present invention, provide a kind of catalyst of air electrode for lithium air battery, described composite catalyst comprises: metallic catalyst and carry out the supporter of concerted catalysis with described metallic catalyst, wherein said metallic catalyst is distributed in the surface of described supporter by original position Load Balanced, the percentage by weight of described metallic catalyst in described composite catalyst is 0.01% ~ 99.9%, preferably 0.1% ~ 60%, be more preferably 0.5% ~ 5%.
The present invention utilizes metallic catalyst to have with to metallic catalyst the composite catalyst that synergistic supporter forms air electrode, improve on the one hand dispersiveness and the stability of original metallic catalyst, also can bring out produce independent metallic catalyst do not have or not and catalytic activity.Thus under the prerequisite ensureing certain catalytic capability, the content of metallic catalyst expensive in air electrode is dropped to minimum, and then reduces the cost of final catalyst.And the catalytic activity of described composite catalyst makes lithium-air battery have lower discharge and recharge polarization and cyclical stability, finally improves the combination property of lithium-air battery.
Preferably, described metallic catalyst can be selected from the metal simple-substance and their alloy with electrochemical catalysis hydrogen reduction and oxidation activity, described in there is electrochemical catalysis hydrogen reduction and oxidation activity metal simple-substance can be selected from Pt, Au, Ag, Rh, Pd, Re, Os, Ir, Hg, Ti, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Cd, Hf, Ta, W, Be, Mg, Ca, Sr, B and Ra.Preferably, described metallic catalyst is Au.
Preferably, the pattern of described metallic catalyst can be selected from particle, sheet, bar-shaped, fiber, tubulose and other there is the pattern of high-specific surface area, be preferably graininess.
Preferably, the volume diameter of described metallic catalyst can be 0.1nm ~ 1000nm, preferably 0.1 ~ 500nm, is more preferably 1 ~ 50nm.
Preferably, the specific area of described metallic catalyst can be 1m
2/ g ~ 5000m
2/ g, preferred 5m
2/ g ~ 1000m
2/ g, more preferably 10m
2/ g ~ 200m
2/ g.
Preferably, described supporter can for having the metal oxide of Lacking oxygen.
Preferably, described supporter is selected from the Y with Lacking oxygen
2o
3, TiO
2, CeO
2, ZrO
2, SiO
2, CoO, Co
3o
4, ZnO, CeO
2, FeO, Cu
2o, CuO, Fe
2o
3, Fe
3o
4, NiO, MgO, Al
2o
3, SnO
2, Mn
2o
3, MnO
2, Mn
3o
4, La
2o
3, MoO
3, Cr
2o
3, ThO
2; Their nonstoichiometric compound; Their alloy; And the combination of above each compound.
More preferably, described supporter is the CeO with Lacking oxygen
2, Y
2o
3, TiO
2and/or Fe
xti
1-xo
2, wherein 0<x<0.9.
Preferably, the specific area of described supporter is 1m
2/ g ~ 2000m
2the preferred 5m of/g
2/ g ~ 1000m
2/ g, more preferably 10m
2/ g ~ 500m
2/ g.
A second aspect of the present invention provide containing air electrode for lithium air battery catalyst of the present invention air electrode.
A third aspect of the present invention provides the lithium-air battery containing air electrode of the present invention.
Accompanying drawing explanation
Fig. 1 is the supporter CeO of comparative example 3
2and the metallic catalyst Au of embodiment 1 is at supporter CeO
2the composite catalyst Au/CeO obtained after original position load
2x ray diffracting spectrum;
Fig. 2 is the supporter CeO that comparative example 3 obtains
2and the composite catalyst Au/CeO in embodiment 1
2transmission electron microscope photo, wherein, in Fig. 2 a) is supporter CeO
2transmission electron microscope photo, the b in Fig. 2) be composite catalyst Au/CeO
2transmission electron microscope photo;
Fig. 3 is the composite catalyst Au/CeO that embodiment 1 obtains
2in Au distribution diagram of element;
Fig. 4 (a) and Fig. 4 (b) is respectively the composite catalyst Au/CeO that embodiment 1 obtains
2raman and IR spectra;
Fig. 5 be comparative example 1 without catalysis electrode, the composite catalyst Au/CeO in comparative example 3 supporter catalysis electrode and embodiment 1
2catalysis electrode is 0.1mA/cm in lithium-air battery
2under first charge-discharge curve;
Fig. 6 is the composite catalyst Au/CeO in embodiment 1
2the high rate performance of catalysis electrode in lithium-air battery;
Fig. 7 be comparative example 1 without the composite catalyst Au/CeO in catalysis electrode and embodiment 1
2catalysis electrode is 0.3mA/cm in lithium-air battery
2lower charging and discharging capacity is with the situation of change of cycle-index;
Fig. 8 is gained composite catalyst Au/CeO in embodiment 1
2catalysis electrode is 0.3mA/cm in lithium-air battery
2lower first week with the charging and discharging curve of the 5th week.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following execution mode, should be understood that following accompanying drawing and/or execution mode are only for illustration of the present invention, and unrestricted the present invention.
The present inventor is through extensive and deep research, and by research catalytic mechanism, and Curve guide impeller technique, unexpectedly obtains the lithium air electrode that the performance of lithium-air battery is increased substantially.Complete the present invention on this basis.
Technical conceive of the present invention is as follows.
The present inventor is large for the polarization of actual lithium-air battery reaction charging/discharging voltage, cycle efficieny low with stability the problem such as difference, but although and noble metal catalyst catalytic activity large compared with high consumption, the shortcomings such as cost height and poor stability, provide a kind of catalyst of air electrode of lithium-air battery.The present inventor explores the basic reason that lithium-air battery actual performance is subject to the catalytic activity restriction of catalyst in air electrode, proposes a kind of catalyst of novelty.Metallic catalyst is utilized to have with to metallic catalyst the composite catalyst that synergistic supporter forms air electrode, improve on the one hand dispersiveness and the stability of original metallic catalyst, also can bring out produce independent metallic catalyst do not have or not and catalytic activity.Thus under the prerequisite ensureing certain catalytic capability, the content of metallic catalyst expensive in air electrode is dropped to minimum, and then reduces the cost of final catalyst.The lithium-air battery of this kind of composite catalyst catalysis is at 0.1mA/cm
2under obtain almost minimum charging voltage (3.23V) and the highest discharge voltage (2.86V), first discharge specific capacity reaches 2720mAh/g.At 0.02mA/cm
2under be more that of obtaining efficiency for charge-discharge (discharge voltage 2.90V/ charging voltage 3.21V) up to 90.6% and the specific capacity up to 3320mAh/g; Under higher current density, this catalysis electrode shows capability retention the highest at present, when electric current increases by 500 (from 0.02 to 0.1mA/cm
2) capability retention is 81.9% (2720/3320), (from 0.02 to 0.3mA/cm when 15 times
2) when being 78.3%, 25 times (from 0.02 to 0.5mA/cm
2) be 75.66%.The cyclical stability of composite catalyst catalysis electrode is also improved, at 0.3mA/cm
2electric current under first discharge capacity be 2604mAh/g, circulating after five times, capacity is still up to 2563mAh/g, and in cyclic process, the charging/discharging voltage platform of composite catalyst catalysis electrode does not almost change.Above-mentioned performance is all obviously better than uncatalyzed dose of electrode, simple metals catalysis electrode and simple supporter catalysis electrode, increase substantially the charge and discharge efficiency of lithium-air battery, capacity, high current charge-discharge, and the combination property such as cyclical stability, obtain unexpected technique effect.The catalyst of this Novel air electrode improves noble metal dispersiveness wherein simultaneously, reduces content and cost, is applicable to large-scale production.
In the present invention, described " nonstoichiometric compound " refers to the compound that can not represent with several little ratio of integers at the relative number of all kinds of atom, or in compound, a certain atom is short or too much; Or between the interlayer of compound structure, embed some neutral molecule or metallic atom; Be optimized for oxygen atom shortage, cation is too much.
In the present invention, described " alloy " refers to and in supporter, introduces some other have different valence state or element of different nature, be convenient to improve the defect density in supporter, be preferably Lacking oxygen, thus increase supporter catalytic activity or with the synergy ability of metallic catalyst or electron conduction.
In the present invention, described " original position load " refers at supporting body surface reaction in-situ generation metallic catalyst.The structure of described original position load makes metallic catalyst and supporter form the composite catalyst of integrated design.Preferably, described metallic catalyst is uniformly distributed in the surface of supporter, and supporter has enrichment to metallic catalyst, and metallic catalyst and supporter form the catalyst of air electrode for lithium air battery jointly.
In the present invention, described " air electrode " refers to by catalyst, the porous electrode that binding agent and carrier three part form jointly, for the transmission of the electrolyte from the oxygen in air and inside battery provides passage, for the reaction in air electrode provides space.
In the present invention, described " lithium-air battery " refers to that metal Li or protected metal Li or Li alloy do negative pole, and the oxygen in air does positive pole, the battery formed with organic or inorganic electrolyte liquid.Described organic or inorganic electrolyte liquid is not specifically limited, and only otherwise to goal of the invention of the present invention produces and limits.Described organic or inorganic electrolyte liquid is known for those skilled in the art.
Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the meaning be familiar with identical.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Below describe in detail to various aspects of the present invention, as no specific instructions, various raw material of the present invention all can be obtained by commercially available; Or prepare according to the conventional method of this area.
catalyst
The metallic catalyst that the present invention adopts can adopt conventional fuel-cell catalyst, in order to obtain the coordination on catalytic activity and cost, and the composite catalyst that the present invention adopts the supporter metallic catalyst by metallic catalyst and load to form.
Described metallic catalyst is selected from all metal simple-substance or alloys with electrochemical catalysis hydrogen reduction and oxidation activity in the periodic table of elements; Preferably, described metallic catalyst is selected from:
(I) noble metal, preferred Pt, Au, Ag, Rh, Pd, Re, Os, Ir, Hg; Or
(II) transition metal: Ti, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Cd, Hf, Ta, W; Or
(III) alkaline-earth metal: Be, Mg, Ca, Sr, Ba, Ra;
Or its combination;
More preferably, metallic catalyst is Au.
In a preference, metallic catalyst is uniformly distributed in the surface of supporter, and metallic catalyst is particle, and sheet is bar-shaped, fiber, tubulose; Be preferably graininess.Metallic catalyst plays to catalyst the catalyst that synergistic supporter forms air electrode for lithium air battery jointly compared with high-ratio surface with having.
In a preference, the volume diameter of described metallic catalyst is 0.1nm ~ 1000nm, is preferably 0.1 ~ 500nm, is more preferably 1 ~ 50nm, thus has nanoscale effect.
In a preference, the specific area of described metallic catalyst is 1m
2/ g ~ 5000m
2/ g, preferred 5m
2/ g ~ 1000m
2/ g, more preferably 10m
2/ g ~ 200m
2/ g.
In a preference, described supporter is the catalytic activity that can improve metallic catalyst, dispersed and stability thus can reduce the compound of the use amount of metallic catalyst.Preferably, described supporter has higher oxygen vacancy concentration; More preferably, one or more compounds following are selected from: Y
2o
3, TiO
2, CeO
2, ZrO
2, SiO
2, CoO, Co
3o
4, ZnO, CeO
2, FeO, Cu
2o, CuO, Fe
2o
3, Fe
3o
4, NiO, MgO, Al
2o
3, SnO
2, Mn
2o
3, MnO
2, Mn
3o
4, La
2o
3, MoO
3, Cr
2o
3, ThO
2; Or its nonstoichiometric compound; Or its several combination; Or its alloy.More preferably, described supporter is CeO
2, Y
2o
3, TiO
2, Fe
xti
1-xo
2, wherein 0<x<0.9.
In a preference, the specific area that described supporter has is 1m
2/ g ~ 2000m
2the preferred 5m of/g
2/ g ~ 1000m
2/ g, more preferably 10m
2/ g ~ 500m
2/ g.
In a preference, described metallic catalyst weight portion in composite catalyst is 0.01 ~ 99.9, is preferably 0.1 ~ 60, is more preferably 0.5% ~ 5%.
The material of described supporter can be obtained by commercially available, such as can purchased from Degussa (Degussa, Inc.), Nyacol nanosecond science and technology company (Nyacol, Nano Technologies Inc.) etc.The material of described supporter also can obtaining by the various methods of this area.
The present inventor finds, by by the load of metallic catalyst original position on described supporter, the cycle efficieny of battery can be improved, such as significantly reduce lithium-air battery charging time platform voltage and polarization, improve platform voltage when discharging and capacity, improve cyclical stability etc.The load of metallic catalyst original position, on supporter, can improve the catalytic activity of metallic catalyst, dispersed and catalytic life, thus reduces the consumption of metallic catalyst.Described original position load can be such as mixed with supporter by the predecessor of described metallic catalyst, makes metallic catalyst deposit on supporter or grow, obtain composite catalyst by in-situ compositing.Wherein, the predecessor of described metallic catalyst can be such as the soluble-salt possessing metal catalyst ion, includes but not limited to nitrate, carbonate, phosphate etc.Described in-situ compositing includes but not limited to solvent-thermal method, template, electrophoretic deposition, electroplating deposition method and electrostatic spray sedimentation etc.
binding agent
Binding agent of the present invention is not specifically limited, and only otherwise to goal of the invention of the present invention produces and limits.The document can quoted see background technology of the present invention.
carrier
Carrier of the present invention is not specifically limited, and only otherwise to goal of the invention of the present invention produces and limits.The document can quoted see background technology of the present invention.
air electrode
The present invention also provides a kind of air electrode of the lithium-air battery containing catalyst of the present invention.
In the air electrode of lithium-air battery of the present invention, other various components described, carrier and binding agent are determined as required.
The air electrode preparation method of lithium-air battery of the present invention does not have specific requirement, only otherwise to goal of the invention of the present invention produces and limits.
lithium-air battery
The present invention also provides a kind of lithium-air battery containing air electrode for lithium air battery of the present invention.
Described lithium-air battery can contain other admissible component, such as negative poles, electrolyte etc.These components do not have specific requirement, only otherwise to goal of the invention of the present invention produce and limit.
All the other compositions of described lithium-air battery are known.Such as Abraham etc., electrochemical society's periodical " Journal ofThe Electrochemical Society " 143(1996) 1-5 and Read etc., electrochemical society's periodical " Journal of TheElectrochemical Society " 149(2002) described in A1190-A1195.
Provided by the inventionly obtain following effect for the catalyst of air electrode in lithium-air battery:
(1) metallic catalyst in composite catalyst has less yardstick, thus has high specific surface and Adsorption, has better catalytic activity than general catalyst;
(2) due to the advantage of lower cost of supporter, in the metallic catalyst that cost is higher, the cost that supporter can reduce composite catalyst is introduced;
(3) supporter has higher specific area, load for metallic catalyst provides enough regions, prevent the reunion producing metallic catalyst in Kaolinite Preparation of Catalyst process, thus the metallic catalyst with smaller szie can be obtained, the dispersion of metallic catalyst is maximized, utilizes and maximize;
(4) there is synergy between supporter and catalyst, supporter produces new or more high catalytic activity by some bonding action together with metallic catalyst;
(5) supporter has higher stability, alleviates the catalyst activity decline that metallic catalyst causes because occurring to reunite in cyclic process to a certain extent;
(6) catalytic activity of composite catalyst makes lithium-air battery have lower discharge and recharge polarization and cyclical stability, finally improves the combination property of lithium-air battery.
Compared with existing various air electrode catalyst material, feature of the present invention is:
(1) composite catalyst has the catalytic activity higher than oxide-based catalyst, the cost lower than noble metal catalyst;
(2) metallic catalyst in composite catalyst has the structure of more disperseing than conventional metallic catalyst, thus obtains higher catalyst utilization;
(3) metallic catalyst in composite catalyst than conventional metallic catalyst evenly, size is less, thus more Adsorption, better catalytic activity;
(4) metallic catalyst in composite catalyst and act synergistically by some between supporter, make to have than independent metal or separately supporter as renewal during catalyst or higher catalytic activity;
(5) existence of supporter makes composite catalyst have longer catalytic life;
(6) cost is lower, easily processes, and is applicable to large-scale industrial production.
Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all numbers are weight portion, and all percentage is weight percentage.
Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the meaning be familiar with identical.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
For setting forth content of the present invention, substantive features and marked improvement further, hereby enumerate following comparative example and embodiment is described in detail as follows, but be not limited only to embodiment.
Comparative example 1
Do not add any catalyst, take acetylene black as carrier and Kynoar (PVDF) for binding agent makes slurry by the mass ratio of 11:15 in 1-METHYLPYRROLIDONE (NMP) medium, coat Ni online and carry out drying, make electrode film thus as positive pole.Take metallic lithium foil as negative pole, Celgard company of U.S. polypropylene screen is barrier film, and 1M LITFSI/DME is electrolyte assembling lithium-air battery, in the voltage range of 2-4.5V, and 0.1mA/cm
2current density under carry out charge-discharge test in 1atm pure oxygen environment.The experimental result of gained is as shown in table 1.
Comparative example 2
With HAuCl
4solution is predecessor, and adjustment PH is 10, and Au is precipitated, and by Au particle, (diameter is 100nm, and specific area is 10m
2/ g), acetylene black and Kynoar (PVDF) prepare electrode by the mass ratio of 19:11:15 according to the method for comparative example 1.Battery assembling and test condition are with comparative example 1.The experimental result of gained is as shown in table 1.As can be seen from the data of table 1, charge and discharge platform comparatively obtains optimization without catalysis electrode in comparative example 1, illustrates that the cell reaction of metallic catalyst Au to lithium-air battery has certain catalytic activity.
Comparative example 3
By Ce (NO
3)
4acid solution carry out pyrolysis, obtain CeO
2it is nanocrystalline that (diameter is 4nm, and specific area is 180m
2/ g), to obtain CeO
2nanocrystalline as catalyst, with acetylene black and Kynoar (PVDF) by the mass ratio of 19:11:15, prepare electrode according to the method for comparative example 1.Battery assembling and test condition are with comparative example 1.The experimental result of gained is as shown in table 1.As can be seen from the data of table 1, charge and discharge platform comparatively obtains optimization without catalysis electrode in comparative example 1, and CeO is described
2to the cell reaction of lithium-air battery, there is certain catalytic activity.
Comparative example 4
By Y
2o
3the colloidal sol drying of (Nyacol, Nano Technologies Inc.) obtains Y
2o
3it is nanocrystalline that (diameter is 6nm, and specific area is 70m
2/ g) with acetylene black and Kynoar (PVDF) by the mass ratio of 19:11:15, prepare electrode with the method for comparative example 1.Battery assembling and test condition are with comparative example 1.The experimental result of gained is as shown in table 1.As can be seen from the data of table 1, charge and discharge platform comparatively obtains optimization without catalysis electrode in comparative example 1, and Y is described
2o
3to the cell reaction of lithium-air battery, there is certain catalytic activity.
Comparative example 5
By TiO
2(Degussa P25, diameter is 25nm, specific area 55m
2/ g) as catalyst and acetylene black and Kynoar (PVDF) by the mass ratio of 19:11:15, prepare electrode with the method for comparative example 1.Battery assembling and test condition are with comparative example 1.The experimental result of gained is as shown in table 1.As can be seen from the data of table 1, charge and discharge platform comparatively obtains optimization without catalysis electrode in comparative example 1, and TiO is described
2to the cell reaction of lithium-air battery, there is certain catalytic activity.
Comparative example 6
By TiO
2(Degussa P25, diameter is 25nm, specific area 55m
2/ g), with Fe(NO
3)
3be scattered in a small amount of water, and then be stirred to dry at 100 DEG C, and then roasting obtains Fe at 400 DEG C
xti
1-xo
2(the i.e. TiO of Fe doping
2, diameter is 100nm, and specific area is 15m
2/ g).By Fe
xti
1-xo
2as catalyst and acetylene black and Kynoar (PVDF) by the mass ratio of 19:11:15, prepare electrode with the method for comparative example 1.Battery assembling and test condition are with comparative example 1.The experimental result of gained is as shown in table 1.As can be seen from the data of table 1, charge and discharge platform comparatively in comparative example 1 without TiO in catalysis electrode and comparative example 5
2catalysis electrode obtains optimization, and Fe is described
xti
1-xo
2have than pure TiO the cell reaction of lithium-air battery
2higher catalytic activity.
Embodiment 1
With HAuCl
4for predecessor, the CeO obtained in comparative example 3
2it is nanocrystalline that (diameter is 4nm, and specific area is 180m
2/ g) be scattered in water and in the colloidal sol that formed, adjustment PH is 10, make Au original position be carried on CeO
2on nanocrystalline, obtain composite catalyst (Au/CeO
2).Wherein Au is metallic catalyst, and CeO
2nanocrystalline is supporter.Fig. 1 is the supporter CeO of comparative example 3
2and the metallic catalyst Au of the present embodiment is at supporter CeO
2the composite catalyst Au/CeO obtained after original position load
2x ray diffracting spectrum, be loaded to CeO see the known Au of Fig. 1
2on nanocrystalline.Fig. 2 is the supporter CeO that comparative example 3 obtains
2and the composite catalyst Au/CeO in the present embodiment
2transmission electron microscope photo, the pattern see the known Au of Fig. 2 is the particle of about 3nm, and load capacity is 3wt%.Fig. 3 is the composite catalyst Au/CeO that the present embodiment obtains
2in Au distribution diagram of element, Au is uniformly distributed in supporter CeO as known in the figure
2on.Fig. 4 (a) and Fig. 4 (b) is respectively the composite catalyst Au/CeO that the present embodiment obtains
2raman and IR spectra.With Au/CeO
2as catalyst and acetylene black and Kynoar (PVDF) mass ratio by 19:11:15, with the method for comparative example 1, battery assembling and test condition are all with comparative example 1.Measurement result is in table 1.Data as can be seen from table 1, compare ratio 1, and comparative example 2 and comparative example 4, comprise composite catalyst Au/CeO
2air electrode (Au accounts for whole 1.26wt%) make lithium-air battery have than in comparative example 1 without catalysis electrode, pure supporter CeO in pure noble metal Au catalysis electrode (Au accounts for whole 42wt%) and comparative example 3 in comparative example 2
2the better charge-discharge performance of catalysis electrode, show as discharge voltage and improve, charging voltage reduces, and charge/discharge capacity improves.Wherein, comparative example 1 without the supporter catalysis electrode of catalysis electrode, comparative example 3 and the composite catalyst Au/CeO of the present embodiment
2catalysis electrode is at 0.1mA/cm in lithium-air battery
2under first charge-discharge curve can see Fig. 5, as known in the figure, the lithium-air battery of this composite catalyst catalysis is at 0.1mA/cm
2under obtain almost minimum charging voltage (3.23V) and the highest discharge voltage (2.86V), first discharge specific capacity reaches 2720mAh/g.Known see Fig. 6, at 0.02mA/cm
2the lithium-air battery of this composite catalyst catalysis lower is more that of obtaining the efficiency for charge-discharge (discharge voltage 2.90V/ charging voltage 3.21V) up to 90.6% and the specific capacity up to 3320mAh/g; Under higher current density, this catalysis electrode shows capability retention the highest at present, when electric current increases by 500 (from 0.02 to 0.1mA/cm
2) capability retention is 81.9% (2720/3320).Known see Fig. 7, the cyclical stability of composite catalyst catalysis electrode is also improved, at 0.3mA/cm
2electric current under first discharge capacity be 2604mAh/g, the capacity that to circulate after five times is still up to 2563mAh/g.Known see Fig. 8, in cyclic process, the charging/discharging voltage platform of composite catalyst catalysis electrode does not almost change.
Embodiment 2
With HAuCl
4for predecessor, the Y obtained in comparative example 4
2o
3it is nanocrystalline that (diameter is 6nm, and specific area is 70m
2/ g) be scattered in the colloidal sol of water formation, adjustment PH is 10, makes Au original position be carried on Y
2o
3on nanocrystalline, obtain composite catalyst (Au/Y
2o
3).Wherein Au is metallic catalyst, and Y
2o
3nanocrystalline is supporter.The pattern of Au is the particle of about 5nm, and load capacity is 2.5wt%.With Au/Y
2o
3as catalyst and acetylene black and Kynoar (PVDF) mass ratio by 19:11:15, with the method for comparative example 1, battery assembling and test condition are all with comparative example 1.Measurement result is in table 1.Data as can be seen from table 1, compare ratio 1, and comparative example 2 and comparative example 4, comprise composite catalyst Au/Y
2o
3air electrode (Au accounts for whole 1.05wt%) make lithium-air battery have than in comparative example 1 without catalysis electrode, pure supporter Y in pure noble metal Au catalysis electrode (Au accounts for whole 42wt%) and comparative example 4 in comparative example 2
2o
3the better charge-discharge performance of catalysis electrode, show as discharge voltage and improve, charging voltage reduces, and charge/discharge capacity improves.
Embodiment 3
With HAuCl
4for predecessor, the TiO obtained in comparative example 5
2(Degussa P25, diameter is 25nm, specific area 55m
2/ g) in dispersion soln, adjustment PH is 9, makes Au original position be carried on TiO
2upper (Au/TiO
2).Wherein Au is metallic catalyst, and TiO
2nanocrystalline is supporter.The pattern of Au is the particle of about 4nm, and load capacity is 1.5wt%.With Au/TiO
2as catalyst and acetylene black and Kynoar (PVDF) mass ratio by 19:11:15, with the method for comparative example 1, battery assembling and test condition are all with comparative example 1.Measurement result is in table 1.Data as can be seen from table 1, compare ratio 1, and comparative example 2 and comparative example 5, comprise composite catalyst Au/TiO
2air electrode (Au accounts for whole 0.63wt%) make lithium-air battery have than in comparative example 1 without catalysis electrode, pure supporter TiO in pure noble metal Au catalysis electrode (Au accounts for whole 42wt%) and comparative example 5 in comparative example 2
2the better charge-discharge performance of catalysis electrode, show as discharge voltage and improve, charging voltage reduces, and charge/discharge capacity improves.
Embodiment 4
With HAuCl
4for predecessor, the Fe obtained in comparative example 6
xti
1-xo
2(diameter is 100nm, and specific area is 15m
2/ g) in dispersion soln, adjustment PH is 9, makes Au original position be carried on Fe
xti
1-xo
2upper (Au/Fe
xti
1-xo
2).Wherein Au is metallic catalyst, and Fe
xti
1-xo
2for supporter.The pattern of Au is the particle of about 5nm, and load capacity is 2wt%.With Au/Fe
xti
1-xo
2as catalyst and acetylene black and Kynoar (PVDF) mass ratio by 19:11:15, with the method for comparative example 1, battery assembling and test condition are all with comparative example 1.Measurement result is in table 1.Data as can be seen from table 1, compare ratio 1, and comparative example 2 and comparative example 5, comprise composite catalyst Au/Fe
xti
1-xo
2air electrode (Au accounts for whole 0.84wt%) make lithium-air battery have than in comparative example 1 without catalysis electrode, pure supporter Fe in pure noble metal Au catalysis electrode (Au accounts for whole 42wt%) and comparative example 6 in comparative example 2
xti
1-xo
2the better charge-discharge performance of catalysis electrode, show as discharge voltage and improve, charging voltage reduces, and charge/discharge capacity improves.
PERFORMANCE EXAMPLES
Table 1: the performance measurement of embodiment and comparative example
discuss
Data listed as can be seen from table 1, prepared novel composite catalyst, all have than metallic catalyst (even if content is very high) corresponding in comparative example and the better catalytic cell of corresponding supporter active, show as energy efficiency and improve, specific capacity improves.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read foregoing of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (11)
1. the composite catalyst of an air electrode for lithium air battery, it is characterized in that, described composite catalyst comprises: metallic catalyst and carry out the supporter of concerted catalysis with described metallic catalyst, wherein said metallic catalyst is distributed in the surface of described supporter by original position Load Balanced, the percentage by weight of described metallic catalyst in described composite catalyst is 0.01% ~ 99.9%, preferably 0.1% ~ 60%, be more preferably 0.5 % ~ 5%.
2. composite catalyst according to claim 1, is characterized in that, described metallic catalyst is selected from the metal simple-substance and their alloy with electrochemical catalysis hydrogen reduction and oxidation activity, described in there is electrochemical catalysis hydrogen reduction and oxidation activity metal simple-substance be selected from Pt, Au, Ag, Rh, Pd, Re, Os, Ir, Hg, Ti, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Ru, Cd, Hf, Ta, W, Be, Mg, Ca, Sr, B and Ra.
3. composite catalyst according to claim 1 and 2, is characterized in that, the pattern of described metallic catalyst is selected from particle, sheet, bar-shaped, fiber and tubulose.
4. composite catalyst according to any one of claim 1 to 3, is characterized in that, the volume diameter of described metallic catalyst is 0.1 ~ 1000 nm, and preferably 0.1 ~ 500 nm, is more preferably 1 ~ 50 nm.
5. composite catalyst according to any one of claim 1 to 4, is characterized in that, the specific area of described metallic catalyst is 1 m
2/ g ~ 5000 m
2/ g, preferably 5 m
2/ g ~ 1000 m
2/ g, more preferably 10 m
2/ g ~ 200m
2/ g.
6. composite catalyst according to any one of claim 1 to 5, is characterized in that, described supporter is the metal oxide with Lacking oxygen.
7. composite catalyst according to claim 6, is characterized in that, described supporter is selected from the Y with Lacking oxygen
2o
3, TiO
2, CeO
2, ZrO
2, SiO
2, CoO, Co
3o
4, ZnO, CeO
2, FeO, Cu
2o, CuO, Fe
2o
3, Fe
3o
4, NiO, MgO, Al
2o
3, SnO
2, Mn
2o
3, MnO
2, Mn
3o
4, La
2o
3, MoO
3, Cr
2o
3, ThO
2; Their nonstoichiometric compound; Their alloy; And the combination of above each compound.
8. composite catalyst according to claim 7, is characterized in that, described supporter is the CeO with Lacking oxygen
2, Y
2o
3, TiO
2and/or Fe
xti
1-xo
2, wherein 0<x<0.9.
9. composite catalyst according to any one of claim 1 to 8, is characterized in that, the specific area of described supporter is 1 m
2/ g ~ 2000 m
2/ g, preferred 5m
2/ g ~ 1000 m
2/ g, more preferably 10m
2/ g ~ 500m
2/ g.
10. the air electrode containing composite catalyst according to any one of claim 1 to 9.
11. 1 kinds of lithium-air batteries containing air electrode according to claim 10.
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