CN107381639B - A kind of templated synthesis perovskite oxide MgTaO3Magnesium ion battery negative electrode material and preparation method thereof - Google Patents

A kind of templated synthesis perovskite oxide MgTaO3Magnesium ion battery negative electrode material and preparation method thereof Download PDF

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CN107381639B
CN107381639B CN201710550223.9A CN201710550223A CN107381639B CN 107381639 B CN107381639 B CN 107381639B CN 201710550223 A CN201710550223 A CN 201710550223A CN 107381639 B CN107381639 B CN 107381639B
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negative electrode
ion battery
electrode material
magnesium ion
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CN107381639A (en
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姘存芳
水淼
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HAIMEN HUANGHAI PIONEER PARK SERVICES Co.,Ltd.
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Ningbo Kyrgyzstan Xin New Mstar Technology Ltd
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    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

A kind of templated synthesis perovskite oxide MgTaO3Magnesium ion battery negative electrode material and preparation method thereof, it is characterized in that: using the continuous cellular structure of gel as template, form the continuous poriferous pattern perovskite structure product that particle part is bonded mutually；Such pattern advantageously reduces crystal boundary resistance, improves locomitivity of the magnesium ion in lattice；Continuous electron transfer network is formed, electromigration resistance is reduced；Increase the contact area with electrolyte, accelerates the rate of the magnesium ion transfer ability and redox reaction in electrolyte and lattice；Such structure also has certain structural rigidity, changes to form buffering to form high performance Magnesium ion battery negative electrode material for the material volume in charge and discharge process.

Description

A kind of templated synthesis perovskite oxide MgTaO3Magnesium ion battery negative electrode material and its Preparation method
Technical field
The present invention relates to a kind of perovskite oxide composite magnesium ion battery cathode material manufacturing method technical fields.
Background technique
Lithium ion secondary battery has volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, circulation The absolute advantages such as service life length, power density height, at present global mobile power source market have more than 30,000,000,000 dollar/year shares and with Speed more than 10% gradually increases.Especially in recent years, with the gradual depletion of fossil energy, solar energy, wind energy, biomass The new energy such as energy are increasingly becoming the alternative of traditional energy, and wherein wind energy, solar energy have intermittence, to meet lasting electricity Power in requisition for simultaneously use a large amount of energy-storage battery；Vehicle exhaust bring urban air-quality problem is got worse, electronic Very urgent stage has been arrived in vigorously advocating and developing for vehicle (EV) or hybrid electric vehicle (HEV)；These demands provide Lithium ion battery explosive growth point, while also to the performance of lithium ion battery, more stringent requirements are proposed.
The raising of the capacity of lithium ion battery plus-negative plate material is the primary goal of scientific and technical personnel's research, high capacity positive and negative anodes It is high-leveled and difficult to meet high power consumption and high power that the research and development of material can alleviate big current Li-ion batteries piles volume, heavy weight, price The situation that equipment needs.However since lithium ion battery in 1991 is commercialized, the actual specific capacity of positive electrode is hesitated always It wanders between 100-180mAh/g, positive electrode specific capacity is low to have become the bottleneck for promoting lithium ion battery specific energy.It compares In anode, the room for promotion of anode material capacity is also very big, such as tin and tin alloy material, silicon and silicon alloy material, all kinds of transition Metal oxide [Md.Arafat Rahman, Guangsheng Song, Anand I.Bhatt, Yat Choy Wong, and Cuie Wen, Nanostructured Silicon Anodes for High-Performance Lithium-Ion Batteries, Adv.Funct.Mater. 2016,26,647-678] etc..But high rate performance, circulation such as to take into account material Capacity retention can be still extremely difficult.Wherein main cause has: 1, electrode material is wanted simultaneously when redox reaction occurs It is embedded in deintercalation and electronics conduction with quick lithium ion, i.e., there is good electron conduction and ionic conductivity simultaneously, no Few negative electrode material lithium ion diffusion coefficient with higher, however be electronic body, the negative electrode material also having is good Electronic conductor, however lithium ion diffusivity is weak, so that the polarization of battery increases considerably；2, many electrode materials are in lithium There is biggish volume change during ion insertion and deintercalation, to cause the broken and active electrode material of electrode material granules Expect the loss in cyclic process, big volume change also brings material lattice transformation in charge and discharge process to generate the second phase simultaneously And seriously affect the performance of battery.3, the lithium cell negative pole material of conversion reaction mechanism, the electronic isolation of reaction product lithium compound Property has seriously affected the invertibity of material.
The lithium cell negative pole material of alloy mechanism and the lithium cell negative pole material of conversion reaction mechanism are because there are multielectron transfers Process often shows higher specific capacity, and metal oxide, sulfide, phosphide, carbonate, chloride are as allusion quotation in recent years The conversion alloy reaction mechanism lithium cell negative pole material of type is gradually of concern.With the work of conventional lithium ion battery electrode material Principle is different, and traditional lithium ion cell positive and cathode, which all have lithium ion, can be embedded in or the space of deintercalation, and electric Solve lithium ion in matter insertion and deintercalation and " rocking chair " proposed as Armand etc. that discharge back and forth between a positive electrode and a negative electrode Battery.And material is converted by taking+divalent metal oxide as an example, it may occur that similar following variation:
2Li++MeO+2e-→Li2O+Me0
And after conversion reaction, it is also possible to the alloy process of diversified forms can occur, such as:
Lim+Me0 n→LimMe0 n
It can release during the two more than 1000mAh.g-1Specific capacity, thus it is high to obtain investigation of materials personnel The attention of degree.However as previously mentioned, to take into account the high rate performance of material, circulation volume retention property still extremely difficult.Metal oxygen These conversion negative electrode materials of compound, sulfide, phosphide, carbonate, chloride obtain more research, these conversion alloys Type negative electrode material is all often monometallic compound.In addition, reserves of the elemental lithium in the earth's crust are very low, rare lithium resource makes Following lithium ion battery cost constantly rises.The electrochemical energy storing device for seeking a kind of alternative low cost becomes urgently to be resolved The problem of.The electrochemical properties of magnesium are similar with lithium, and earth rich reserves, are to be expected in future replace most having for lithium ion battery uncommon The selection of prestige.
As lithium ion transition material, the Magnesium ion battery negative electrode material of alloy mechanism is it can also happen that following electrification Learn reaction:
Mg2++MeO+2e-→MgO+Me0
Mgm+Me0 n→MgmMe0 n
And biggish specific capacity can be released, however generally since magnesium ion ionic radius is larger, electrode potential is low, Migration velocity in electrode material is slow, and the battery performances such as energy density, power density still have very big compared with lithium ion battery Gap.And the cathode candidate material of Magnesium ion battery is few, studies at present it also very not enough.
Perovskite structure ABO3Type oxide obtains important application in solar cells recently.Its structure is A The biggish cation of radius is in 12 coordination structures, in the hole being made of octahedron；B are transition metal element class Compared with small cation, octahedral coordination is formed with six oxonium ions.Change the element of A, the element species of B location, A, B location by it All there may be different types of lattice defects for his same valence state or the atomic component of aliovalent state substitution, have so as to become The functional material of different functionalities.ABO3Type oxide can carry out alloy with two kinds of metals and react when carrying out alloy reaction, There may be the Alloy solid solutions of a variety of phases, due to bimetallic interaction, it is also possible to generate completely different with monometallic Electrochemical properties, therefore ABO3Type oxide is likely to become a kind of high-performance Magnesium ion battery negative electrode material, may mention For near or above 300mAh.g-1Specific capacity, magnesium ion enter or abjection material volume variation it is also smaller；However the material Research and development in Magnesium ion battery is substantially at blank.And its main problem are as follows: 1, ionic conductivity and electronic conductance Rate is lower；2, the product magnesia after conversion reaction is electronic body and its magnesium ion Diffusion Activation Energy is also higher, cause compared with Big activation polarization；3, synthesis temperature is higher, be easy to cause growing up and reuniting for crystal grain.
For these problems, the pattern for changing material can extenuate these problems to a certain extent, such as by of material The scale of particle size reduction to nanometer can reduce the approach of magnesium ion diffusion, shorten the diffusion time of magnesium ion to improve material Dynamic performance；Too small granularity also easily causes the difficulty of electronic conduction between particle；Reunion between same particle or Excessive particle easily causes the problems such as infiltration of electrolyte between particles is difficult, and magnesium ion migration velocity is slow.
Therefore developing a kind of perovskite structure oxide with excellent electrochemical performance is that perovskite structure oxide is made For the key of secondary Magnesium ion battery negative electrode material application.
Summary of the invention
The present invention proposes a kind of templated synthesis perovskite oxide MgTaO for existing background technique3Magnesium ion battery Negative electrode material and preparation method thereof, it is characterized in that: using the continuous cellular structure of gel as template, it is mutual to form particle part The continuous poriferous pattern perovskite structure product of bonding；Such pattern advantageously reduces crystal boundary resistance, improves magnesium ion in crystalline substance Locomitivity in lattice；Continuous electron transfer network is formed, electromigration resistance is reduced；Increase the contact surface with electrolyte Product accelerates the rate of the magnesium ion transfer ability and redox reaction in electrolyte and lattice；Such structure also has one Fixed structural rigidity changes to be formed to buffer for the material volume in charge and discharge process and bear to form high performance Magnesium ion battery Pole material.
This templated synthesis perovskite oxide MgTaO3Magnesium ion battery negative electrode material, preparation method are as follows: by six water Magnesium nitrate, tantalum hydroxide are closed in the ratio mixing of the amount 1: 1 of substance, the amount that substance is added is the amount 5.0- of total metal ion species 10.0 times of citric acid simultaneously adds water and stirs the initial aqueous solution for being formed uniformly that total concentration of metal ions is 1.0-2.5molL-1； By 6g acrylamide/100mL water acrylamide and 1gN, N '-methylene-bisacrylamide/100mL water N, N '-are sub- Bisacrylamide and water mixed dissolution, the amount of the substance of acrylamide is total metal ion object in initial aqueous solution in solution 0.5-1.2 times of the amount of matter；After being stirred 5-15 minutes using Teflon stir paddle with the speed of 1500rpm-2000rpm It is risen to 75-85 DEG C with 5-10 DEG C/min of speed and keeps the temperature until it becomes gelatin gel.It will be formed Gel it is dry in the environment of low-temperature high-vacuum degree, which, will using finished product freeze drier currently on the market Gel, which is put into freeze drier sample disc, starts refrigeration machine, is reduced to subzero 50 DEG C of subzero 45- to gelling temp in sample disc, It opens vacuum pump and improves vacuum degree, be reduced to 25-35Pa to gas pressure in system and start to take off hereinafter, opening baffle temperature control Water is dry, other operating parameters take machine preset value, after drying to stable gas pressure in system, the gel after drying is put Enter in initial aqueous solution, stand 10-20 minutes, then rises to 75-90 DEG C and at this temperature with 5-10 DEG C/min of speed It constant temperature 1-3 hours, then puts it into drying in 80 DEG C of -120 DEG C of drying boxes and is put into tube furnace after 10-20 hours, in air Speed in atmosphere with 2-10 DEG C/min is warming up to 950-1050 DEG C and keeps that template conjunction is made within 6-12 hours at this temperature At perovskite oxide MgTaO3Magnesium ion battery negative electrode material.
Compared with the prior art, the advantages of the present invention are as follows: it uses the continuous cellular structure of gel as template, forms particle The continuous poriferous pattern perovskite structure product that part is bonded mutually；Such pattern advantageously reduces crystal boundary resistance, improves magnesium Locomitivity of the ion in lattice；Continuous electron transfer network is formed, electromigration resistance is reduced；Increase and electrolyte Contact area accelerates the rate of the magnesium ion transfer ability and redox reaction in electrolyte and lattice；Such structure is also With certain structural rigidity, change to form buffering to form high performance magnesium ion for the material volume in charge and discharge process Cell negative electrode material.
Detailed description of the invention
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of Fig. 1 material, voltage range 0.1V- 3.0V, charging and discharging currents 0.5C.
The scanning electron microscopic picture of Fig. 2 material.
Specific embodiment
Below in conjunction with embodiment, present invention is further described in detail.
Embodiment 1: magnesium nitrate hexahydrate, tantalum hydroxide are mixed in the ratio of the amount 1: 1 of substance, the amount that substance is added is 5 times of amount of citric acid of total metal ion species simultaneously adds water and stirs that be formed uniformly total concentration of metal ions be 1.0molL-1's Initial aqueous solution；By 6g acrylamide/100mL water acrylamide and 1gN, N '-methylene-bisacrylamide/100mL water The N of amount, N '-methylene-bisacrylamide and water mixed dissolution, the amount of the substance of acrylamide is in initial aqueous solution in solution 0.5 times of the amount of total metal ion species；It is stirred with the speed of 1500rpm after five minutes by it using Teflon stir paddle 75 DEG C are risen to 5 DEG C/min of speed and keep the temperature until it becomes gelatin gel.By the gel of formation in low temperature Dry in the environment of condition of high vacuum degree, which is put into freezing for gel using finished product freeze drier currently on the market Start refrigeration machine in drying machine sample disc, be reduced to subzero 45 DEG C to gelling temp in sample disc, opens vacuum pump and improve vacuum Degree is reduced to 25Pa to gas pressure in system and starts to dehydrate hereinafter, opening baffle temperature control, other operating parameters are adopted Machine preset value is taken, after drying to stable gas pressure in system, the gel after drying is put into initial aqueous solution, stands 10 Minute, 75 DEG C and at this temperature constant temperature 1 hour are then risen to 5 DEG C/min of speed, then put it into 80 DEG C of dryings Drying is put into tube furnace after 10 hours in case, is warming up to 950 DEG C and herein temperature in air atmosphere with 2 DEG C/min of speed Degree is lower to be kept templated synthesis perovskite oxide MgTaO being made in 6 hours3Magnesium ion battery negative electrode material.
Embodiment 2: magnesium nitrate hexahydrate, tantalum hydroxide are mixed in the ratio of the amount 1: 1 of substance, the amount that substance is added is 7 times of amount of citric acid of total metal ion species simultaneously adds water and stirs that be formed uniformly total concentration of metal ions be 2.0molL-1's Initial aqueous solution；By 6g acrylamide/100mL water acrylamide and 1gN, N '-methylene-bisacrylamide/100mL water The N of amount, N '-methylene-bisacrylamide and water mixed dissolution, the amount of the substance of acrylamide is in initial aqueous solution in solution 0.8 times of the amount of total metal ion species；It is stirred with the speed of 1800rpm after ten minutes by it using Teflon stir paddle 80 DEG C are risen to 7 DEG C/min of speed and keep the temperature until it becomes gelatin gel.By the gel of formation in low temperature Dry in the environment of condition of high vacuum degree, which is put into freezing for gel using finished product freeze drier currently on the market Start refrigeration machine in drying machine sample disc, be reduced to subzero 47 DEG C to gelling temp in sample disc, opens vacuum pump and improve vacuum Degree is reduced to 30Pa to gas pressure in system and starts to dehydrate hereinafter, opening baffle temperature control, other operating parameters are adopted Machine preset value is taken, after drying to stable gas pressure in system, the gel after drying is put into initial aqueous solution, stands 15 Minute, 82 DEG C and at this temperature constant temperature 2 hours are then risen to 7 DEG C/min of speed, 100 DEG C is then put it into and does It is put into tube furnace after dry 15 hours in dry case, is warming up to 1000 DEG C and herein in air atmosphere with 7 DEG C/min of speed At a temperature of keep that templated synthesis perovskite oxide MgTaO is made within 8 hours3Magnesium ion battery negative electrode material.
Embodiment 3: magnesium nitrate hexahydrate, tantalum hydroxide are mixed in the ratio of the amount 1: 1 of substance, the amount that substance is added is 10 times of amount of citric acid of total metal ion species simultaneously adds water and stirs that be formed uniformly total concentration of metal ions be 2.5molL-1's Initial aqueous solution；By 6g acrylamide/100mL water acrylamide and 1gN, N '-methylene-bisacrylamide/100mL water The N of amount, N '-methylene-bisacrylamide and water mixed dissolution, the amount of the substance of acrylamide is in initial aqueous solution in solution 1.2 times of the amount of total metal ion species；By it after being stirred 15 minutes using Teflon stir paddle with the speed of 2000rpm 85 DEG C are risen to 10 DEG C/min of speed and keep the temperature until it becomes gelatin gel.By the gel of formation low Dry in the environment of warm condition of high vacuum degree, which is put into gel cold using finished product freeze drier currently on the market Start refrigeration machine in lyophilizer sample disc, be reduced to subzero 50 DEG C to gelling temp in sample disc, opens vacuum pump and improve very Reciprocal of duty cycle is reduced to 35Pa to gas pressure in system and starts to dehydrate hereinafter, opening baffle temperature control, other operating parameters Machine preset value is taken, after drying to stable gas pressure in system, the gel after drying is put into initial aqueous solution, is stood 20 minutes, 90 DEG C and at this temperature constant temperature 3 hours are then risen to 10 DEG C/min of speed, then put it into 120 DEG C Drying is put into tube furnace after 20 hours in drying box, is warming up to 1050 DEG C simultaneously with 10 DEG C/min of speed in air atmosphere It keeps templated synthesis perovskite oxide MgTaO being made in 11 hours at this temperature3Magnesium ion battery negative electrode material.
Embodiment 4: magnesium nitrate hexahydrate, tantalum hydroxide are mixed in the ratio of the amount 1: 1 of substance, the amount that substance is added is 7 times of amount of citric acid of total metal ion species and adding water and stirring be formed uniformly total concentration of metal ions be 2molL-1 just Beginning aqueous solution；By 6g acrylamide/100mL water acrylamide and 1gN, N '-methylene-bisacrylamide/100mL water N, N '-methylene-bisacrylamide and water mixed dissolution, the amount of the substance of acrylamide is total in initial aqueous solution in solution 1.1 times of the amount of metal ion species；After being stirred 13 minutes using Teflon stir paddle with the speed of 1900rpm by its with 10 DEG C/min of speed rises to 85 DEG C and keeps the temperature until it becomes gelatin gel.By the gel of formation in low temperature Dry in the environment of condition of high vacuum degree, which is put into freezing for gel using finished product freeze drier currently on the market Start refrigeration machine in drying machine sample disc, be reduced to subzero 50 DEG C to gelling temp in sample disc, opens vacuum pump and improve vacuum Degree is reduced to 33Pa to gas pressure in system and starts to dehydrate hereinafter, opening baffle temperature control, other operating parameters are adopted Machine preset value is taken, after drying to stable gas pressure in system, the gel after drying is put into initial aqueous solution, stands 20 Minute, 90 DEG C and at this temperature constant temperature 3 hours are then risen to 10 DEG C/min of speed, 120 DEG C is then put it into and does It is put into tube furnace after dry 15 hours in dry case, is warming up to 1020 DEG C and herein in air atmosphere with 8 DEG C/min of speed At a temperature of keep that templated synthesis perovskite oxide MgTaO is made within 10 hours3Magnesium ion battery negative electrode material.
Embodiment 5: magnesium nitrate hexahydrate, tantalum hydroxide are mixed in the ratio of the amount 1: 1 of substance, the amount that substance is added is 8 times of amount of citric acid of total metal ion species simultaneously adds water and stirs that be formed uniformly total concentration of metal ions be 2.2molL-1's Initial aqueous solution；By 6g acrylamide/100mL water acrylamide and 1gN, N '-methylene-bisacrylamide/100mL water The N of amount, N '-methylene-bisacrylamide and water mixed dissolution, the amount of the substance of acrylamide is in initial aqueous solution in solution 1.1 times of the amount of total metal ion species；It is stirred with the speed of 1500rpm after ten minutes by it using Teflon stir paddle 80 DEG C are risen to 8 DEG C/min of speed and keep the temperature until it becomes gelatin gel.By the gel of formation in low temperature Dry in the environment of condition of high vacuum degree, which is put into freezing for gel using finished product freeze drier currently on the market Start refrigeration machine in drying machine sample disc, be reduced to subzero 50 DEG C to gelling temp in sample disc, opens vacuum pump and improve vacuum Degree is reduced to 30Pa to gas pressure in system and starts to dehydrate hereinafter, opening baffle temperature control, other operating parameters are adopted Machine preset value is taken, after drying to stable gas pressure in system, the gel after drying is put into initial aqueous solution, stands 15 Minute, 90 DEG C and at this temperature constant temperature 3 hours are then risen to 8 DEG C/min of speed, 100 DEG C is then put it into and does It is put into tube furnace after dry 15 hours in dry case, is warming up to 1050 DEG C and herein in air atmosphere with 8 DEG C/min of speed At a temperature of keep that templated synthesis perovskite oxide MgTaO is made within 10 hours3Magnesium ion battery negative electrode material.

Claims (1)

1. a kind of templated synthesis perovskite oxide MgTaO3The preparation method of Magnesium ion battery negative electrode material, it is characterized in that: by six Nitric hydrate magnesium, tantalum hydroxide are mixed in the ratio of the amount 1: 1 of substance, and the amount that substance is added is the amount of total metal ion species It is the initial water-soluble of 1.0-2.5molL-1 that 5.0-10.0 times of citric acid and adding water and stirring, which is formed uniformly total concentration of metal ions, Liquid；By 6g acrylamide/100mL water acrylamide and 1gN, N '-methylene-bisacrylamide/100mL water N, N '- Methylene-bisacrylamide and water mixed dissolution, the amount of the substance of acrylamide is total metal ion in initial aqueous solution in solution 0.5-1.2 times of the amount of substance；After being stirred 5-15 minutes using Teflon stir paddle with the speed of 1500rpm-2000rpm It is risen to 75-85 DEG C with 5-10 DEG C/min of speed and keeps the temperature until it becomes gelatin gel；By formation Gel is dry in the environment of low-temperature high-vacuum degree, which will be coagulated using finished product freeze drier currently on the market Glue, which is put into freeze drier sample disc, starts refrigeration machine, is reduced to subzero 50 DEG C of subzero 45- to gelling temp in sample disc, opens It opens vacuum pump and improves vacuum degree, be reduced to 25-35Pa to gas pressure in system and start to be dehydrated hereinafter, opening baffle temperature control Dry, other operating parameters take machine preset value, after drying to stable gas pressure in system, the gel after drying are put into In initial aqueous solution, 10-20 minutes are stood, 75-90 DEG C and at this temperature perseverance are then risen to 5-10 DEG C/min of speed It is 1-3 hours warm, it then puts it into drying in 80 DEG C of -120 DEG C of drying boxes and is put into tube furnace after 10-20 hours, in air gas Speed in atmosphere with 2-10 DEG C/min is warming up to 950-1050 DEG C and keeps the templated synthesis being made in 6-12 hours at this temperature Perovskite oxide MgTaO3Magnesium ion battery negative electrode material.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05330827A (en) * 1991-12-06 1993-12-14 Rhone Poulenc Chim Perovskite wherein tantalum or niobium is base material and preparation thereof
US5683614A (en) * 1996-08-16 1997-11-04 Sandia Corporation Sol-gel type synthesis of Bi2 (Sr,Ta2)O9 using an acetate based system
CN101164891A (en) * 2007-09-14 2008-04-23 东南大学 Method for preparing calcium-titanium ore type nano material used for middle-temperature solid oxide fuel battery
CN101724908A (en) * 2009-12-22 2010-06-09 中国科学技术大学 Controllable and mass production method of perovskite type manganese and oxygen compound polycrystal nano-rod function material
CN102603299A (en) * 2012-03-22 2012-07-25 中北大学 High conductivity nanometer complex phase perovskite type proton conductor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05330827A (en) * 1991-12-06 1993-12-14 Rhone Poulenc Chim Perovskite wherein tantalum or niobium is base material and preparation thereof
US5683614A (en) * 1996-08-16 1997-11-04 Sandia Corporation Sol-gel type synthesis of Bi2 (Sr,Ta2)O9 using an acetate based system
CN101164891A (en) * 2007-09-14 2008-04-23 东南大学 Method for preparing calcium-titanium ore type nano material used for middle-temperature solid oxide fuel battery
CN101724908A (en) * 2009-12-22 2010-06-09 中国科学技术大学 Controllable and mass production method of perovskite type manganese and oxygen compound polycrystal nano-rod function material
CN102603299A (en) * 2012-03-22 2012-07-25 中北大学 High conductivity nanometer complex phase perovskite type proton conductor

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