CN107394189A - A kind of one-step synthesis double-perovskite Magnesium ion battery negative material and preparation method - Google Patents

A kind of one-step synthesis double-perovskite Magnesium ion battery negative material and preparation method Download PDF

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CN107394189A
CN107394189A CN201710550218.8A CN201710550218A CN107394189A CN 107394189 A CN107394189 A CN 107394189A CN 201710550218 A CN201710550218 A CN 201710550218A CN 107394189 A CN107394189 A CN 107394189A
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ion battery
magnesium ion
battery negative
negative material
step synthesis
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姘存芳
水淼
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Ningbo Kyrgyzstan Xin New Mstar Technology Ltd
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Ningbo Kyrgyzstan Xin New Mstar Technology Ltd
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Abstract

A kind of one-step synthesis double-perovskite Magnesium ion battery negative material and preparation method, it is characterized in that：The composition of the negative material is MgNd0.8Li0.2Fe0.9Cu0.1Nb0.9Zn0.1O6Reaction raw materials being carried using air-flow in preparation process and unevenly adhering to sintering aid quickly through the sintering aid region of atomization, then a step continuously obtains product and product grain part adhesive is turned into continuous poriferous pattern by unevenly adhering to sintering aid in high temperature process furnances；Such pattern advantageously reduces crystal boundary resistance and electromigration resistance；Accelerate the speed of redox reaction；Also there is certain structural rigidity；Further occupied jointly by the Mg and Nd of A positions and the Zn of B positions, Cu doping ultimately form high performance Magnesium ion battery negative material.

Description

A kind of one-step synthesis double-perovskite Magnesium ion battery negative material and preparation method
Technical field
The present invention relates to a kind of Magnesium ion battery negative material manufacture method technical field.
Background technology
Lithium rechargeable battery have volume, weight energy than it is high, voltage is high, self-discharge rate is low, memory-less effect, circulation The absolute advantages such as long lifespan, power density height, had more than at present in global portable power source market 30,000,000,000 dollar/year shares and with Speed more than 10% gradually increases.Particularly in recent years, petering out with 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 has intermittence, to meet lasting electricity Power supply needs to use substantial amounts of energy-storage battery simultaneously；The urban air-quality problem getting worse that vehicle exhaust is brought, it is electronic Very urgent stage has been arrived in vigorously advocating and developing for car (EV) or hybrid electric vehicle (HEV)；These demands provide Lithium ion battery explosive growth point, while higher requirement also is proposed to the performance of lithium ion battery.
The raising of the capacity of lithium ion battery plus-negative plate material be scientific and technical personnel research primary goal, high power capacity both positive and negative polarity It is high-leveled and difficult to meet high power consumption and high power that the research and development of material can alleviate current Li-ion batteries piles volume big, heavy weight, price The situation that equipment needs.But since lithium ion battery in 1991 is commercialized, the actual specific capacity of positive electrode is hesitated all the time Wander between 100-180mAh/g, positive electrode specific capacity is low to have become bottleneck of the lifting lithium ion battery than energy.Compare In positive pole, the room for promotion of negative 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：1st, electrode material simultaneously will when redox reaction occurs Conducted with quick Lithium-ion embeding deintercalation and electronics, i.e., there is good electron conduction and ionic conductivity simultaneously, no Few negative material has higher lithium ion diffusion coefficient, but is electronic body, and the negative material also having is good Electronic conductor, but lithium ion diffusivity is weak, so that the polarization of battery increases considerably；2nd, many electrode materials are in lithium Ion has larger Volume Changes during being embedded in deintercalation, so as to cause the broken and active electrode material of electrode material granules Expect the loss in cyclic process, big Volume Changes also bring material lattice transformation in charge and discharge process to produce the second phase simultaneously And have a strong impact on the performance of battery.3rd, the lithium cell negative pole material of conversion reaction mechanism, the electronic isolation of reaction product lithium compound Property has had a strong impact on the invertibity of material.
Because multielectron transfer be present in the lithium cell negative pole material of alloy mechanism and the lithium cell negative pole material of conversion reaction mechanism 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 negative pole, which all have lithium ion, can be embedded in or the space of deintercalation, and electric Solve lithium ion in matter embedded back and forth and deintercalation and " rocking chair " proposed as Armand etc. that discharge between a positive electrode and a negative electrode Battery.And material is changed by taking+divalent metal oxide as an example, it may occur that similar following change：
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 be discharged more than 1000mAh.g during the two-1Specific capacity, thus obtain investigation of materials personnel height The attention of degree.But as it was previously stated, to take into account the high rate performance of material, circulation volume retention property still extremely difficult.Metal oxygen These conversion negative materials of compound, sulfide, phosphide, carbonate, chloride obtain more research, these conversion alloys Type negative material is all often single metallization compound.In addition, reserves of the elemental lithium in the earth's crust are very low, rare lithium resource causes Following lithium ion battery cost constantly rises.Seeking a kind of alternative inexpensive electrochemical energy storing device turns into urgently to be resolved hurrily The problem of.The electrochemical properties of magnesium are similar with lithium, and earth rich reserves, are to be expected in future substitute most having for lithium ion battery uncommon The selection of prestige.
As lithium ion transition material, the Magnesium ion battery negative 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 larger specific capacity can be discharged, but generally because magnesium ion ionic radius is larger, electrode potential is low, Migration velocity in electrode material is slow, and the battery performance such as energy density, power density still has very big compared with lithium ion battery Gap.And the negative pole candidate material of Magnesium ion battery is few, it is studied at present also very inadequate.
Perovskite structure ABO3Type oxide obtains important application in solar cells recently.Its structure is that A positions are The larger cation of radius, in 12 coordination structures, in the hole being made up of octahedron；B positions are transition metal class Compared with small cation, octahedral coordination is formed with six oxonium ions.Change A, the element species of B location, A, the element of B location by it His same valence state or the atomic component of aliovalent state are substituted all there may be different types of lattice defect, so as to as with The functional material of different functionalities.ABO3Type oxide can carry out alloy reaction when carrying out alloy reaction with two kinds of metals, its There may be the Alloy solid solution of a variety of phases, due to bimetallic interaction, it is also possible to produce completely different with monometallic Electrochemical properties, therefore ABO3Type oxide is likely to become a kind of high-performance Magnesium ion battery negative material, and it may be carried For near or above 300mAh.g-1Specific capacity, magnesium ion enter or abjection material volume change it is also smaller；But the material The research and development in Magnesium ion battery be substantially at blank.And its subject matter is：1st, ionic conductivity and electronics electricity Conductance is relatively low；2nd, the product magnesia after conversion reaction is electronic body and its magnesium ion Diffusion Activation Energy is also higher, is caused Larger activation polarization；3rd, synthesis temperature is higher, easily causes growing up and reuniting for crystal grain.
For these problems, these problems, such as by material can be extenuated to a certain extent by changing the pattern of material Particle size reduction can reduce the approach of magnesium ion diffusion to the yardstick of nanometer, shorten diffusion time of magnesium ion so as 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；Ion doping And a kind of microstructure of effective regulation lattice, change the means of lattice electron and ionic transport properties, however, ion is mixed Miscellaneous even polyion collaboration doping is extremely complex to the mechanism of action of parent, and effect is often difficult to expect.In addition using double calcium Perovskite like structure A positions and B positions can be occupied by two kinds of metals, partly can also be substituted by aliovalent or iso-valence metal, therefore, to material Expect the flexible adjustment of the regulation and control of structure, electronics and ion motion property.
Therefore it is structure of double perovskite oxidation to develop a kind of structure of double perovskite oxide with excellent electrochemical performance The key that thing is applied as secondary Magnesium ion battery negative material.
The content of the invention
The present invention for existing background technology propose a kind of one-step synthesis double-perovskite Magnesium ion battery negative material and Preparation method, it is characterized in that：The composition of the negative material is MgNd0.8Li0.2Fe0.9Cu0.1Nb0.9Zn0.1O6, profit in preparation process Reaction raw materials are carried with air-flow and unevenly adhere to sintering aid quickly through the sintering aid region of atomization, then in high temperature pipe A step continuously obtains product and product grain part adhesive is turned into continuous more by unevenly adhering to sintering aid in formula stove Hole pattern；Such pattern advantageously reduces crystal boundary resistance, improves locomitivity of the magnesium ion in lattice；Form continuous electricity Son migration network, reduces electromigration resistance；Increase and the contact area of electrolyte, accelerate electrolyte and the magnesium ion in lattice The speed of transfer ability and redox reaction；Such structure also has certain structural rigidity, is in charge and discharge process Material volume changes to form buffering；Further occupied jointly by the Mg and Nd of A positions, improve electronic conductivity；Pass through B positions Zn, Cu doping improve the stability of perovskite structure, ultimately form high performance Magnesium ion battery negative material.
This one-step synthesis double-perovskite Magnesium ion battery negative material, its preparation method are：By magnesium nitrate hexahydrate, oxygen Change neodymium, lithium nitrate, zinc nitrate hexahydrate, Fe(NO3)39H2O, niobium pentaoxide, Gerhardite according to stoichiometric equation MgNd0.8Li0.2Fe0.9Cu0.1Nb0.9Zn0.1O6It is put into ball mill, the mass ratio of ball milling and material is 20: 1, with 200-400 Rev/min speed ball milling 10-20 hours.Material carrier gas 1 after ball milling is sent into synthesizer as shown in Figure 1, carried The flow velocity of gas 1 is 0.5-3.5m3·min-1；The synthesizer is by ultrasonic atomizer, droplet region, tube furnace and cyclone separator Four parts form；At the same time, start in ultrasonic atomizer and be immersed in 1.0-1.5molL-1Power is in Alkitrate 250W immersed ultrasonic transducer, produces a large amount of droplets and is 0.5-3.5Lmin by flow velocity-1Carrier gas 2 carry from below To droplet region；Carrier gas 1 with the material after ball milling by through a length being 2-5 rice behind droplet region, temperature it is constant In 900-1200 DEG C of tube furnace and enter in cyclone separator and collection material from below；It is collected into from cyclone separator Material is warming up to 800-900 DEG C and herein in the oxygen and argon gas atmosphere that volume ratio is 45: 55 with 2-10 DEG C/min of speed At a temperature of keep 2-5 hours the one-step synthesis double-perovskite Magnesium ion battery negative material is made.
Above-mentioned carrier gas 1 is one kind in air, nitrogen；Carrier gas 2 is the oxygen that volume ratio is 20: 80 and argon gas gaseous mixture Body.
Compared with prior art, the advantage of the invention is that：Reaction raw materials are carried in preparation process using air-flow quickly to lead to The sintering aid region for crossing atomization unevenly adheres to sintering aid, and then a step continuously obtains product simultaneously in high temperature process furnances Product part adhesive is turned into continuous poriferous pattern by unevenly adhering to sintering aid；Such pattern advantageously reduces Crystal boundary resistance, improve locomitivity of the magnesium ion in lattice；Continuous electron transfer network is formed, reduces electron transfer resistance Power；Increase and the contact area of electrolyte, accelerate electrolyte and the magnesium ion transfer ability in lattice and redox reaction Speed；Such structure also has certain structural rigidity, is that the material volume in charge and discharge process changes to form buffering；Enter one Step is occupied jointly by the Mg and Nd of A positions, improves electronic conductivity；By the Zn of B positions, Cu doping improves perovskite structure Stability, ultimately form high performance Magnesium ion battery negative material.
Brief description of the drawings
Fig. 1 synthesizer schematic diagrames.
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of Fig. 2 materials, voltage range 0.1V- 3.0V, charging and discharging currents 0.5C.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：By magnesium nitrate hexahydrate, neodymia, lithium nitrate, zinc nitrate hexahydrate, Fe(NO3)39H2O, five oxidations Two niobiums, Gerhardite are according to stoichiometric equation MgNd0.8Li0.2Fe0.9Cu0.1Nb0.9Zn0.1O6It is put into ball mill, ball milling Son is 20: 1 with the mass ratio of material, with 200 revs/min of speed ball milling 11 hours.Material after ball milling is sent into air In synthesizer as shown in Figure 1, the flow velocity of air is 0.5m3·min-1；The synthesizer is by ultrasonic atomizer, droplet area Domain, tube furnace and the part of cyclone separator four composition；At the same time, start in ultrasonic atomizer and be immersed in 1.0molL-1Nitric acid Power is 250W immersed ultrasonic transducer in aqueous solutions of potassium, produces a large amount of droplets and is 0.5Lmin by flow velocity-1Volume Carried from below to droplet region than the oxygen for 20: 80 and argon gas mixed gas；Air passes through mist with the material after ball milling Drip region after through a length be 3 meters, temperature it is constant in 900 DEG C of tube furnace and enter cyclone separator in and receive from below Collect material；The material being collected into from cyclone separator is in the oxygen and argon gas atmosphere that volume ratio is 45: 55 with 2 DEG C/min Speed be warming up to 800 DEG C and at this temperature keep 2 hours be made the one-step synthesis double-perovskite Magnesium ion battery negative pole material Material.
Embodiment 2：By magnesium nitrate hexahydrate, neodymia, lithium nitrate, zinc nitrate hexahydrate, Fe(NO3)39H2O, five oxidations Two niobiums, Gerhardite are according to stoichiometric equation MgNd0.8Li0.2Fe0.9Cu0.1Nb0.9Zn0.1O6It is put into ball mill, ball milling Son is 20: 1 with the mass ratio of material, with 400 revs/min of speed ball milling 19 hours.Material after ball milling is sent into air In synthesizer as shown in Figure 1, the flow velocity of air is 3.5m3·min-1；The synthesizer is by ultrasonic atomizer, droplet area Domain, tube furnace and the part of cyclone separator four composition；At the same time, start in ultrasonic atomizer and be immersed in 1.5molL-1Nitric acid Power is 250W immersed ultrasonic transducer in aqueous solutions of potassium, produces a large amount of droplets and is 3.5Lmin by flow velocity-1Volume Carried from below to droplet region than the oxygen for 20: 80 and argon gas mixed gas；Air passes through mist with the material after ball milling It is 5 meters that a length is passed through behind drop region, and temperature is constant in 1200 DEG C of tube furnace and in entrance cyclone separator and from below Collection material；The material being collected into from cyclone separator is in the oxygen and argon gas atmosphere that volume ratio is 45: 55 with 10 DEG C/minute The speed of clock is warming up to 900 DEG C and keeps the one-step synthesis double-perovskite Magnesium ion battery negative pole being made in 5 hours at this temperature Material.
Embodiment 3：By magnesium nitrate hexahydrate, neodymia, lithium nitrate, zinc nitrate hexahydrate, Fe(NO3)39H2O, five oxidations Two niobiums, Gerhardite are according to stoichiometric equation MgNd0.8Li0.2Fe0.9Cu0.1Nb0.9Zn0.1O6It is put into ball mill, ball milling Son is 20: 1 with the mass ratio of material, with 300 revs/min of speed ball milling 15 hours.Material after ball milling is sent into nitrogen In synthesizer as shown in Figure 1, the flow velocity of nitrogen is 3.0m3·min-1；The synthesizer is by ultrasonic atomizer, droplet area Domain, tube furnace and the part of cyclone separator four composition；At the same time, start in ultrasonic atomizer and be immersed in 1.2molL-1Nitric acid Power is 250W immersed ultrasonic transducer in aqueous solutions of potassium, produces a large amount of droplets and is 2.5Lmin by flow velocity-1Volume Carried from below to droplet region than the oxygen for 20: 80 and argon gas mixed gas；Nitrogen passes through mist with the material after ball milling It is 4 meters that a length is passed through behind drop region, and temperature is constant in 1100 DEG C of tube furnace and in entrance cyclone separator and from below Collection material；The material being collected into from cyclone separator is in the oxygen and argon gas atmosphere that volume ratio is 45: 55 with 8 DEG C/minute The speed of clock is warming up to 850 DEG C and keeps the one-step synthesis double-perovskite Magnesium ion battery negative pole being made in 4 hours at this temperature Material.
Embodiment 4：By magnesium nitrate hexahydrate, neodymia, lithium nitrate, zinc nitrate hexahydrate, Fe(NO3)39H2O, five oxidations Two niobiums, Gerhardite are according to stoichiometric equation MgNd0.8Li0.2Fe0.9Cu0.1Nb0.9Zn0.1O6It is put into ball mill, ball milling Son is 20: 1 with the mass ratio of material, with 400 revs/min of speed ball milling 15 hours.Material after ball milling is sent into nitrogen In synthesizer as shown in Figure 1, the flow velocity of nitrogen is 3.5m3·min-1；The synthesizer is by ultrasonic atomizer, droplet area Domain, tube furnace and the part of cyclone separator four composition；At the same time, start in ultrasonic atomizer and be immersed in 1.2molL-1Nitric acid Power is 250W immersed ultrasonic transducer in aqueous solutions of potassium, produces a large amount of droplets and is 3.0Lmin by flow velocity-1Volume Carried from below to droplet region than the oxygen for 20: 80 and argon gas mixed gas；Nitrogen passes through mist with the material after ball milling It is 5 meters that a length is passed through behind drop region, and temperature is constant in 1200 DEG C of tube furnace and in entrance cyclone separator and from below Collection material；The material being collected into from cyclone separator is in the oxygen and argon gas atmosphere that volume ratio is 45: 55 with 10 DEG C/minute The speed of clock is warming up to 900 DEG C and keeps the one-step synthesis double-perovskite Magnesium ion battery negative pole being made in 5 hours at this temperature Material.
Embodiment 5：By magnesium nitrate hexahydrate, neodymia, lithium nitrate, zinc nitrate hexahydrate, Fe(NO3)39H2O, five oxidations Two niobiums, Gerhardite are according to stoichiometric equation MgNd0.8Li0.2Fe0.9Cu0.1Nb0.9Zn0.1O6It is put into ball mill, ball milling Son is 20: 1 with the mass ratio of material, with 300 revs/min of speed ball milling 10 hours.Material after ball milling is sent into air In synthesizer as shown in Figure 1, the flow velocity of air is 2.5m3·min-1；The synthesizer is by ultrasonic atomizer, droplet area Domain, tube furnace and the part of cyclone separator four composition；At the same time, start in ultrasonic atomizer and be immersed in 1.1molL-1Nitric acid Power is 250W immersed ultrasonic transducer in aqueous solutions of potassium, produces a large amount of droplets and is 0.5Lmin by flow velocity-1Volume Carried from below to droplet region than the oxygen for 20: 80 and argon gas mixed gas；Air passes through mist with the material after ball milling Drip region after through a length be 2 meters, temperature it is constant in 900 DEG C of tube furnace and enter cyclone separator in and receive from below Collect material；The material being collected into from cyclone separator is in the oxygen and argon gas atmosphere that volume ratio is 45: 55 with 10 DEG C/min Speed be warming up to 800 DEG C and at this temperature keep 2 hours be made the one-step synthesis double-perovskite Magnesium ion battery negative pole material Material.

Claims (2)

1. a kind of one-step synthesis double-perovskite Magnesium ion battery negative material, it is characterized in that：Form and be MgNd0.8Li0.2Fe0.9Cu0.1Nb0.9Zn0.1O6, preparation process is by magnesium nitrate hexahydrate, neodymia, lithium nitrate, six hydration nitre Sour zinc, Fe(NO3)39H2O, niobium pentaoxide, Gerhardite are according to stoichiometric equation MgNd0.8Li0.2Fe0.9Cu0.1Nb0.9Zn0.1O6It is put into ball mill, the mass ratio of ball milling and material is 20: 1, with 200-400 Rev/min speed ball milling 10-20 hours；By the material after ball milling with carrier gas 1 with 0.5-3.5m3·min-1Flow velocity be sent into close Into in device, the synthesizer is made up of ultrasonic atomizer, droplet region, tube furnace and the part of cyclone separator four；It is same with this When, start in ultrasonic atomizer and be immersed in 1.0-1.5molL-1Power is that 250W immersed ultrasonic changes in Alkitrate Can device, produce droplet and be 0.5-3.5Lmin by flow velocity-1Carrier gas 2 carry from below to droplet region；Carrier gas 1 is with ball By through a length being 2-5 rice behind droplet region, temperature is constant to go forward side by side in 900-1200 DEG C of tube furnace for material after mill Enter in cyclone separator and collection material from below；The material being collected into from cyclone separator is in the oxygen that volume ratio is 45: 55 Being warming up to 800-900 DEG C with 2-10 DEG C/min of speed in gas and argon gas atmosphere and keep 2-5 hours to be made at this temperature should One-step synthesis double-perovskite Magnesium ion battery negative material.
2. a kind of one-step synthesis double-perovskite Magnesium ion battery negative material as claimed in claim, it is characterized in that：Above-mentioned Carrier gas 1 is one kind in air, nitrogen；Carrier gas 2 is the oxygen that volume ratio is 20: 80 and argon gas mixed gas.
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