CN100386148C - Reduced catalyst of mono fluorin, and preparation method and usage - Google Patents
Reduced catalyst of mono fluorin, and preparation method and usage Download PDFInfo
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- CN100386148C CN100386148C CNB2006100190980A CN200610019098A CN100386148C CN 100386148 C CN100386148 C CN 100386148C CN B2006100190980 A CNB2006100190980 A CN B2006100190980A CN 200610019098 A CN200610019098 A CN 200610019098A CN 100386148 C CN100386148 C CN 100386148C
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Abstract
The present invention discloses a preparation method for oxygen reduction catalysts, which uses lanthanum oxide, praseodymium oxide, strontium oxide, calcium oxide, manganese dioxide, manganese sesquioxide, ferric oxide, cobalto-cobaltic oxide, nickel oxide, chromium oxide, etc. as raw materials. In an air or oxygen atmosphere, the oxygen reduction catalysts are prepared by the method that the raw materials react for 0.5 to 12 hours at room temperature by swinging and vibrating a ball mill. A sample is in a perovskite type, and a chemical formula is ABO3 or A<1-x>M<x>B<1-y>N<y>O3. An air electrode prepared by the use of the perovskite oxide as catalysts has an oxygen reduction capacity of 290 mAh/cm<2> in the air atmosphere, and the oxygen reduction catalysts have good stability in alkaline media and are good oxygen reduction catalysts. A method by swinging and vibrating the ball mill does not need complicated and expensive devices, a preparation process does not need any solutions, and nanometer superfine products can be obtained without the complicated processes such as filtration, wash, desiccation, high temperature sintering, pulverization, etc. The process has the advantages of energy saving, time saving, labor saving, simplicity, reliability and easy scale production.
Description
Technical field
The invention discloses a kind of novel oxygen reduction catalyst and its production and use, it belongs to technical field of electrochemistry, also belongs to technical field of inorganic material synthesis.
Background technology
Zinc/air fuel cell, have advantages such as specific energy height (theoretical specific energy reaches 1350Wh/kg), stable operating voltage, the operating temperature range of broad, raw material be cheap and easy to get, environmentally friendly, and the easy regeneration of cell reaction product, in the present age of energy scarcity, be one of important energy source of extremely paying close attention to of people, being referred to as is " green energy resource geared to the 21st century ".It is widely used in fields such as navigation light, unmanned observation station, radio relay station, transceiver, electric vehicle, mobile communication equipment.The appearance of the emerge in multitude of portable electricity consuming products and world wide electric automobile heat is for new field has been opened up in the application of high-energy-density zinc-air battery.
In zinc/air fuel cell, the hydrogen reduction catalytic capability of air electrode is the key factor of decision battery performance quality, and the catalyst of therefore seeking Cheap highly effective is the focus of zinc and air cell research.In order to reduce the activation polarization in the air electrode course of reaction, people have carried out extensive studies to oxygen reduction catalyst.What be used as oxygen reduction catalyst in early days is carbon, but its catalytic activity is very low.Platinum is that research is maximum up to now, and catalytic activity and the best catalyst of stability.But, thereby make it be difficult to realize the scale application owing to its scarcity of resources costs an arm and a leg.Silver has good electrical conductivity and better physical chemical stability, be used as for platinum catalyst in the air electrode of being everlasting, but cost is still apparent too high.Mn oxide is the more single metal oxides catalyst of research, but the discharge current density of the zinc-air battery that the oxide of common manganese is a catalyst to be made 30～50mA/cm only
2, can only be used to make low power zinc-air battery, the transition metal that contains four N atoms is integrated the oxygen reduction catalyst that thing is considered to get a good chance of, as porphyrin, phthalocyanine and derivative thereof.With tetraphenylporphyrin network cobalt (CoTPP) be the air electrode made of catalyst at 20 ℃ with 50mA/cm
2But discharge steady operation 7000h.RE perovskite type catalyst not only has good catalytic performance, and more stable in alkaline solution, the more important thing is the cheap of it, is subjected to extensive concern, has a extensive future in fuel cell and metal-air battery.The RE perovskite type catalyst synthetic method mainly contains solid reaction process and liquid phase reactor method.Wang Qiu spinach etc. adopt solid phase method, with carbonate and nitrate thermal decomposition, have prepared La
0.2Ca
0.8MnO
3(catalysis journal, Vol.19No.2 (1998) 116～120); Liu Yuan etc. (catalysis journal, Vol.19No.2 (1998) 173～176) are raw material with nitrate, use NaCO
3-NaOH and ammoniacal liquor are that precipitating reagent has synthesized LaMnO
3And La
1-xSr
xMnO
3Catalyst; Kahoul A, et al (Materials Research Bulletin, 35 (2000) 1955～1966) and Hermann V, etal (Electrochimica Acta, 46 (2000) 365～372) etc. have synthesized La with the auxiliary sol-gel process of tartaric acid
1-xCa
xCoO
3Nae-Lih Wu et al (Electrochimica Acta 48 (2003) 1567～1571) is a part with the citric acid, has prepared La by sol-gel process
0.6Ca
0.4CoO
3-xDifunctional oxygen reduction catalyst.The solid reaction process of above-mentioned preparation RE perovskite type catalyst and liquid phase reactor method all need be at the crushing screenings after a few hours of sintering under 500～900 ℃ the high temperature.And the liquid phase reactor method more needs through precipitation-overanxious-washing-drying-high temperature sintering-processes such as pulverizing, and preparation technology is numerous and diverse time-consuming, also will consume a large amount of energy.The present invention attempts to prepare the RE perovskite type oxygen reduction catalyst of high performance-price ratio by machining process-be the rocking vibration ball-milling method.
Summary of the invention:
The objective of the invention is: a kind of new compound, the preparation method and its usage of this material are provided, this material should have the hydrogen reduction catalytic action, can be used as oxygen reduction catalyst, be used to prepare once or the positive pole of secondary zinc-air battery, lithium-air battery, iron-air cell and fuel cell.Its raw material sources are abundant, inexpensive during preparation, and technology is simple, is suitable for large-scale production, guarantee sintetics quality of stability, uniformity and reliability.
For achieving the above object, the technical measures that the present invention taked are:
A kind of general formula is A
1-xM
xB
1-yN
yO
3Compound, its crystalline structure is a Ca-Ti ore type, A is a kind of in lanthanum, praseodymium, strontium, the calcium constituent in the formula, M is at least a kind of in strontium or the calcium constituent, B, N are at least a kind of in manganese, iron, cobalt, nickel, chromium, the copper, the scope of X, Y is 0～1.
A kind ofly be used to prepare above-claimed cpd A
1-xM
xB
1-yN
yO
3Method:
Stoichiometric composition by molecular formula, accurately take by weighing the corresponding raw material of A, M, B, N, put into the rocking vibration ball grinder, put into the stainless steel balls of two kinds of different sizes or agate nodule number, the weight that adds ball in the retort is 20 to 1 to 8 to 1 with the raw-material weight ratio, retort is placed on the rocking vibration ball mill, rocking vibration speed is 1000～2000 rev/mins, under 0-45 ℃ of environment temperature, rocking vibration ball-milling reaction 0.5～12 hour static 1 hour, is rejected stainless steel ball or agate ball, take out and promptly get product, sealed storage is standby.
According to technical scheme of the present invention, described raw material is and chemically common accordingly oxide, hydroxide, nitrate or the carbonate of A, M, B, N.As lanthana (La
2O
3), lanthanum nitrate (La (NO
3)
36H
2O), praseodymium oxide (Pr
6O
11), praseodymium nitrate (Pr (NO
3)
36H
2O), strontium oxide strontia (SrO), strontium nitrate (Sr (NO
3)
2), strontium carbonate (SrCO
3), calcium oxide (CaO), calcium carbonate (CaCO
3), manganese dioxide (MnO
2), manganese sesquioxide managnic oxide (Mn
2O
3), di-iron trioxide (Fe
2O
3), cobalt sesquioxide (Co
2O
3), nickel oxide (NiO), nickel hydroxide (Ni (OH)
2), chromium oxide (Cr
2O
3), cupric oxide (CuO) etc.
According to technical scheme of the present invention, be media such as oxygen, air, nitrogen, argon gas charging into jar medium during the rocking vibration ball-milling reaction.
According to technical scheme of the present invention, the ball-milling reaction time is 1～8 hour in the rocking vibration ball grinder.
According to technical scheme of the present invention, the ball-milling reaction environment temperature is 5～30 ℃.
According to technical scheme of the present invention, the speed during the rocking vibration ball milling is 1200～1500 rev/mins.
According to technical scheme of the present invention, the diameter of sizes of balls is respectively 9～11mm and diameter is 5～7mm during ball milling, and the quantity ratio of sizes of balls is 1 to 1 to 1 to 8.
Preparation in accordance with the present invention products therefrom crystalline structure is a Ca-Ti ore type, as oxygen reduction catalyst, can be used for preparing once or the positive pole of secondary zinc-air battery, lithium-air battery, iron-air cell and fuel cell.
With preparation LaMnO
3, La
1-xCa
xMnO
3, La
1-xSr
xMnO
3And LaCo
1-yFe
yO
3Be example, its basic synthetic reaction is:
LaMnO
3：La
2O
3+Mn
2O
3＝2LaMnO
3
La
1-xCa
xMnO
3：(1-x)/2La
2O
3+(1-x)/2Mn
2O
3+xCaO+xMnO
2＝La
1-xCa
xMnO
3
La
1-xSr
xMnO
3：
(1-x)/2La
2O
3+(1-x)/2Mn
2O
3+xSrO+xMnO
2＝La
1-xSr
xMnO
3
LaCo
1-yFe
yO
3：(1).y/2La
2O
3+y/2Fe
2O
3＝yLaFeO
3
(2).(1-y)/2La
2O
3+(1-y)/2Co
2O
3＝(1-y)LaCoO
3
(1)+(2)：y/2La
2O
3+y/2Fe
2O
3+(1-y)/2La
2O
3+(1-y)/2Co
2O
3＝LaCo
1-yFe
yO
3
Compare the effect that technical scheme of the present invention has reached and have characteristics with existing technology of preparing:
1. the perovskite material of the present invention preparation, function admirable, discharge current density can reach 290mA/Cm
2
2. the perovskite oxygen reduction catalyst of the inventive method preparation is pressed the raw material of stoichiometric, reacts completely, and X-ray powder diffraction figure proves: the catalyst characteristics diffraction maximum is obvious, and impurity peaks is few, complete in crystal formation.
3. the inventive method technology is simple, is easy to grasp, and is suitable for large-scale production.
4. cleanliness without any pollution is saved time, energy savings.
Description of drawings
Fig. 1 is the synthetic LaMnO of the inventive method
3, La
0.8Sr
0.2MnO
3, La
0.8Ca
0.2MnO
3, LaCo
0.4Fe
0.6O
3X-ray powder diffraction figure, very identical with standard diagram.
Fig. 2 is the synthetic LaMnO of the inventive method
3(a), La
0.8Ca
0.2MnO
3(b), LaCo
0.4Fe
0.6O
3(c), La
0.8Sr
0.2MnO
3(d), sem photograph, multiplication factor are 20000 times, and granularity is in 30～300 nanometers.
Fig. 3 is the synthetic LaMnO of the inventive method
3, La
0.8Ca
0.2MnO
3, La
0.8Sr
0.2MnO
3, LaCo
0.4Fe
0.6O
3The discharge polarization curve.Relative LaMnO during zinc reference electrode current potential 1.0V
3, La
0.8Ca
0.2MnO
3, LaCo
0.4Fe
0.6O
3.La
0.8Sr
0.2MnO
3Current density reach 225mA/Cm respectively
2, 240mA/Cm
2, 275mA/Cm
2And 290mA/Cm
2
The specific embodiment
Embodiment 1:
LaMnO
3Synthetic, accurately take by weighing Mn
2O
31.578g, La
2O
32.826g in the adding ball grinder, putting into 12 diameters is 8mm and 8 stainless steel balls that diameter is 10mm, and retort is placed on the rocking vibration ball mill, at room temperature, rocking vibration ball milling 6 hours is rejected stainless steel ball, and it is standby to take out catalyst seal.
Embodiment 2:
La
0.8Sr
0.2MnO
3Synthetic, accurately take by weighing La
2O
33.258g, Mn
2O
31.578g, SrO 0.518g, MnO
20.435g.Rocking vibration ball milling 2 hours, other step such as embodiment 1.
Embodiment 3:
La
0.8Ca
0.2MnO
3Synthetic, accurately take by weighing La
2O
33.258g, Mn
2O
31.578g, CaO 0.28g, MnO
20.435g.Rocking vibration ball milling 2 hours, other step such as embodiment 1.
Embodiment 4:
LaCo
0.4Fe
0.6O
3Synthetic, accurately take by weighing La
2O
34.075g, Co
2O
30.83g, Fe
2O
31.2g.Rocking vibration ball milling 4 hours, other step such as embodiment 1.
Embodiment 5:
La
0.6Sr
0.4Co
0.8Fe
0.2O
3Synthetic, accurately take by weighing La
2O
32.175g, SrO 0.922g, Co
3O
41.446g, Fe
2O
30.355g.Rocking vibration ball milling 8 hours, other step such as embodiment 1.
Claims (6)
1. a general formula is A
1-xM
xB
1-yN
yO
3The preparation method of composite oxides, in the general formula, A represents a kind of in rare earth element such as lanthanum, praseodymium, strontium, the calcium constituent; M represents a kind of in strontium or the calcium; A kind of in the similar and different transition metal of expression such as manganese, iron, cobalt, nickel, chromium, the copper of B, N; The scope of x, y is 0-1; The crystalline structure of described composite oxides is the Ca-Ti ore type crystalline structure, it is characterized in that: the composition of pressing composite oxides, accurately take by weighing A, M, B, the corresponding raw material of N, put into the rocking vibration ball grinder, put into the stainless steel balls of two kinds of different sizes or agate nodule number, the weight of ball is 20 to 1 to 8 to 1 with the raw-material weight ratio in the retort, retort is placed on the rocking vibration ball mill, rocking vibration speed is 1000～2000 rev/mins, under 0-45 ℃ of environment temperature, rocking vibration ball-milling reaction 0.5～12 hour, static 1 hour, stainless steel ball or agate ball are rejected, take out and promptly get product; Described raw material is common oxide, hydroxide, nitrate or the carbonate of the corresponding chemistry of A, M, B, N.
2. method according to claim 1 is characterized in that, rocking vibration ball grinder medium is a kind of in oxygen, air, nitrogen, the argon gas.
3. method according to claim 1 is characterized in that, the ball-milling reaction time is 1～8 hour in the rocking vibration ball grinder.
4. method according to claim 1 is characterized in that, the ball-milling reaction environment temperature is 5～30 ℃.
5. method according to claim 1 is characterized in that, the speed during the rocking vibration ball milling is 1200～1500 rev/mins.
6. method according to claim 1 is characterized in that the diameter of sizes of balls is respectively 9～11mm and 5～7mm during ball milling, and the quantity of sizes of balls is 1 to 1 to 1 to 8.
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|---|---|---|---|
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| CN100386148C true CN100386148C (en) | 2008-05-07 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569830A (en) * | 2011-12-19 | 2012-07-11 | 上海尧豫实业有限公司 | Metal air battery anode catalyst and preparation method thereof |
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| CN103050701B (en) * | 2011-10-17 | 2015-04-01 | 中国科学院大连化学物理研究所 | Electrode material for lithium-air battery and preparation method of electrode material |
| CN103700907A (en) * | 2014-01-15 | 2014-04-02 | 湖南桑顿新能源有限公司 | Preparation method of zinc metal-air battery |
| CN107464936A (en) * | 2017-06-13 | 2017-12-12 | 北京大学深圳研究生院 | A kind of catalyst of air electrode of zinc-air cell and its preparation method and application |
| CN112484217A (en) * | 2020-11-13 | 2021-03-12 | 武汉威蒙环保科技有限公司 | Someone space inner loop ozone disinfection purifier |
| CN113862719B (en) * | 2021-11-05 | 2023-07-11 | 上海交通大学 | Transition metal oxide catalyst and preparation method and application thereof |
| CN114583193B (en) * | 2022-02-21 | 2023-03-31 | 浙江工业大学 | Positive electrode catalyst for metal-air secondary battery and metal-air secondary battery based on same |
| CN115382553B (en) * | 2022-08-24 | 2024-05-24 | 中国环境科学研究院 | Lanthanum iron nickel composite metal oxide and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3861961A (en) * | 1972-02-25 | 1975-01-21 | Hitachi Ltd | Gas electrode |
| CN85101848A (en) * | 1985-04-01 | 1986-10-08 | 中国科学院长春应用化学研究所 | The composite oxide of rare-earth elements for preparation of nitric acid by oxidation of Ammonia catalyst |
| CN1529374A (en) * | 2003-10-08 | 2004-09-15 | 华南理工大学 | Zinc-air battery electrocatalyst and preparation method thereof |
| US6939630B2 (en) * | 2001-08-29 | 2005-09-06 | Matsushita Electric Industrial Co., Ltd. | Composite electrode for reducing oxygen |
-
2006
- 2006-05-18 CN CNB2006100190980A patent/CN100386148C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3861961A (en) * | 1972-02-25 | 1975-01-21 | Hitachi Ltd | Gas electrode |
| CN85101848A (en) * | 1985-04-01 | 1986-10-08 | 中国科学院长春应用化学研究所 | The composite oxide of rare-earth elements for preparation of nitric acid by oxidation of Ammonia catalyst |
| US6939630B2 (en) * | 2001-08-29 | 2005-09-06 | Matsushita Electric Industrial Co., Ltd. | Composite electrode for reducing oxygen |
| CN1529374A (en) * | 2003-10-08 | 2004-09-15 | 华南理工大学 | Zinc-air battery electrocatalyst and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569830A (en) * | 2011-12-19 | 2012-07-11 | 上海尧豫实业有限公司 | Metal air battery anode catalyst and preparation method thereof |
| CN102569830B (en) * | 2011-12-19 | 2016-12-07 | 上海尧豫实业有限公司 | Metal air battery anode catalyst and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1872414A (en) | 2006-12-06 |
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