CN107352583B - A kind of double-perovskite Magnesium ion battery negative material of electric field regulation and control selective freezing synthesis - Google Patents
A kind of double-perovskite Magnesium ion battery negative material of electric field regulation and control selective freezing synthesis Download PDFInfo
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- CN107352583B CN107352583B CN201710550411.1A CN201710550411A CN107352583B CN 107352583 B CN107352583 B CN 107352583B CN 201710550411 A CN201710550411 A CN 201710550411A CN 107352583 B CN107352583 B CN 107352583B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
- C01G33/006—Compounds containing, besides niobium, two or more other elements, with the exception of oxygen or hydrogen
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- H—ELECTRICITY
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02E60/10—Energy storage using batteries
Abstract
A kind of electric field regulation and control selective freezing synthesis double-perovskite Magnesium ion battery negative material and preparation method thereof, it is characterized in that：The group of the negative material becomes MgY0.7Li0.3Zr0.8Cu0.1Zn0.1NbO6, change the crystallization property with lattice defect crystal using the electric field for applying specific direction in high temperature solid state reaction in preparation process, grow to form cylindrical shape particle along direction of an electric field；The non-homogeneous crystallization of cylindrical shape particle surface simultaneously unevenly adheres to sintering aid at the big position of surface curvature radius and part adhesive becomes continuous poriferous pattern；The pattern advantageously reduces crystal boundary resistance and electromigration resistance；Accelerate magnesium ion transfer ability and redox reaction rate；Also there is certain structural rigidity, be that the volume change in charge and discharge process forms buffering；It is further occupied jointly by A Mg and Y, the Li of Y location doping and B Cu, Zn doping improve the stability of perovskite structure to form high performance Magnesium ion battery negative material.
Description
Technical field
The present invention relates to a kind of Magnesium ion battery negative material manufacturing method technical fields.
Background technology
Lithium rechargeable battery has volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, cycle
The absolute advantages such as long lifespan, power density height, at present global mobile power 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 has intermittence, for the electricity for meeting lasting
Power in requisition for simultaneously use a large amount of energy-storage battery；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 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 power 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, low have become of positive electrode specific capacity promotes bottleneck of the lithium ion battery than energy.It compares
It is also very big in the room for promotion of anode, negative material capacity, such as tin and tin alloy material, silicon and silicon alloy material, all kinds of transition
Jin Shuyanghuawu [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]Deng.But high rate performance, cycle 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 material has higher lithium ion diffusion coefficient, however is electronic body, and the negative 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
Ion has larger volume change during being embedded in deintercalation, to cause the broken and active electrode material of electrode material granules
Expect that the loss in cyclic process, big volume change also bring 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 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 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 be released more than 1000mAh.g during the two-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 materials of compound, sulfide, phosphide, carbonate, chloride obtain more research, these conversion alloys
Type negative 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.Seeking a kind of electrochemical energy storing device of alternative low cost becomes 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 replace 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 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 larger 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
His same valence state or the atomic component of aliovalent state substitute all there may be different types of lattice defect, 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 material, may carry
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 is：1, ionic conductivity and electronic conductance
Rate is relatively low；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, these problems can be extenuated to a certain extent by changing the pattern of material, 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；Ion doping
It is also a kind of effective microstructure for adjusting lattice, changes 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 double calcium are used
Perovskite like structure A and B can be occupied by two kinds of metals, also can partly be replaced by aliovalent or iso-valence metal, therefore, right
The regulation and control of material structure, the flexible adjustment of electronics and ion motion property.
Therefore it is that structure of double perovskite aoxidizes to develop a kind of structure of double perovskite oxide with excellent electrochemical performance
The key that object is applied as secondary Magnesium ion battery negative material.
Invention content
The present invention proposes a kind of electric field regulation and control selective freezing synthesis double-perovskite magnesium ion electricity for existing background technology
Pond negative material and preparation method thereof, it is characterized in that：The group of the negative material becomes MgY0.7Li0.3Zr0.8Cu0.1Zn0.1NbO6,
Change the crystallization spy with lattice defect crystal in preparation process using the electric field for applying specific direction in high temperature solid state reaction
Property, it grows to form cylindrical shape particle along direction of an electric field；Simultaneously cylindrical shape particle surface non-homogeneous crystallization and surface song
The big position of rate radius unevenly adheres to sintering aid and part adhesive becomes continuous poriferous pattern；Such pattern is conducive to drop
Low crystal boundary resistance improves locomitivity of the magnesium ion in lattice；Continuous electron transfer network is formed, electron transfer resistance is reduced
Power；Increase the contact area with electrolyte, the magnesium ion transfer ability and redox reaction in quickening electrolyte and lattice
Rate；Such structure also has certain structural rigidity, changes to form buffering for the material volume in charge and discharge process；Into one
Step is occupied jointly by A Mg and Y, is improved electronic conductivity and is adulterated by the Li of part Y location, improves magnesium ion
Conductivity；By B Cu, Zn doping improves the stability of perovskite structure, and it is negative to ultimately form high performance Magnesium ion battery
Pole material.
This electric field regulation and control selective freezing synthesizes double-perovskite Magnesium ion battery negative material, and preparation method is：By nitre
Sour lithium, magnesium nitrate hexahydrate, six nitric hydrate yttriums, Gerhardite, five nitric hydrate zirconiums, zinc nitrate hexahydrate, five oxidations
Two niobiums are according to stoichiometric equation MgY0.7Li0.3Zr0.8Cu0.1Zn0.1NbO6It is put into ball mill, the mass ratio of ball milling and material is
20: 1, with 200-400 revs/min of speed ball milling 10-20 hours.By the material after ball milling with 2-10 DEG C/minute in tube furnace
The speed of clock is warming up to after 800-900 DEG C the both ends in tube furnace and applies a DC voltage, voltage 600-900V, in this temperature
30 DEG C are cooled to the furnace after keeping the temperature 3-6 hours under lower and electric field；Material after cooling is ground 5-15 minutes in mortar, poly-
Tetrafluoroethene agitating paddle is persistently stirred with the speed of 900-1200rpm in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature, partially
The mass ratio of the quality of lithium borate saturated solution and the material after cooling of immersion is 10: 1, will after persistently stirring 5-10 minutes
Thermostat temperature is reduced to 18-22 DEG C and continues stirring 5-15 minutes, filters thereafter, the dry 5- in 120-160 DEG C of drying box
10 hours.Then the material after drying is warming up to 450-550 DEG C and herein temperature in tube furnace with 2-10 DEG C/min of speed
Degree lower heat preservation is made electric field regulation and control selective freezing for 3-5 hours and synthesizes double-perovskite Magnesium ion battery negative material.
Compared with the prior art, the advantages of the present invention are as follows：Utilize the electricity for applying specific direction in high temperature solid state reaction
Field changes the crystallization property with lattice defect crystal, grows to form cylindrical shape particle along direction of an electric field；Cylindrical shape simultaneously
The non-homogeneous crystallization of particle surface and unevenly adhere to sintering aid at the big position of surface curvature radius and part adhesive becomes
Continuous poriferous pattern；Such pattern advantageously reduces crystal boundary resistance, improves locomitivity of the magnesium ion in lattice；The company of being formed
Continuous electron transfer network reduces electromigration resistance；Increase the contact area with electrolyte, accelerates in electrolyte and lattice
The rate of magnesium ion transfer ability and redox reaction；Such structure also has certain structural rigidity, is charge and discharge
Material volume in journey changes to form buffering；It is further occupied jointly by A Mg and Y, improves electronic conductivity and lead to
The Li doping for crossing part Y location, improves magnesium ion conductivity；By B Cu, Zn doping improves the stabilization of perovskite structure
Property, ultimately form high performance Magnesium ion battery negative material.
Description of the drawings
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 cycles of Fig. 1 materials, voltage range 0.1V-
3.0V, charging and discharging currents 0.5C.
Specific implementation mode
Below in conjunction with embodiment, present invention is further described in detail.
Embodiment 1：By lithium nitrate, magnesium nitrate hexahydrate, six nitric hydrate yttriums, Gerhardite, five nitric hydrate zirconiums,
Zinc nitrate hexahydrate, niobium pentaoxide are according to stoichiometric equation MgY0.7Li0.3Zr0.8Cu0.1Zn0.1NbO6It is put into ball mill, ball
The mass ratio of mill and material is 20: 1, with 400 revs/min of speed ball milling 20 hours.By the material after ball milling in tube furnace
In with 10 DEG C/min of speed be warming up to after 900 DEG C the both ends in tube furnace apply a DC voltage, voltage 900V, herein
At a temperature of and electric field under keep the temperature 5 hours after cool to 30 DEG C with the furnace；Material after cooling is ground 12 minutes in mortar, poly-
Tetrafluoroethene agitating paddle is persistently stirred with the speed of 1200rpm in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature, metaboric acid
The mass ratio of the quality of lithium saturated solution and the material after cooling of immersion is 10: 1, after persistently stirring 9 minutes, by thermostat temperature
It is reduced to 22 DEG C and continues stirring 15 minutes, filter thereafter, it is 10 hours dry in 160 DEG C of drying box.Then after will be dry
Material in tube furnace with 10 DEG C/min of speed be warming up to 550 DEG C and at this temperature keep the temperature 5 hours be made the electric field tune
It controls selective freezing and synthesizes double-perovskite Magnesium ion battery negative material.
Embodiment 2：By lithium nitrate, magnesium nitrate hexahydrate, six nitric hydrate yttriums, Gerhardite, five nitric hydrate zirconiums,
Zinc nitrate hexahydrate, niobium pentaoxide are according to stoichiometric equation MgY0.7Li0.3Zr0.8Cu0.1Zn0.1NbO6It is put into ball mill, ball
The mass ratio of mill and material is 20: 1, with 400 revs/min of speed ball milling 15 hours.By the material after ball milling in tube furnace
In with 8 DEG C/min of speed be warming up to after 900 DEG C the both ends in tube furnace apply a DC voltage, voltage 900V, herein
At a temperature of and electric field under keep the temperature 5 hours after cool to 30 DEG C with the furnace；Material after cooling is ground 12 minutes in mortar, poly-
Tetrafluoroethene agitating paddle is persistently stirred with the speed of 1000rpm in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature, metaboric acid
The mass ratio of the quality of lithium saturated solution and the material after cooling of immersion is 10: 1, after persistently stirring 7 minutes, by thermostat temperature
It is reduced to 18 DEG C and continues stirring 10 minutes, filter thereafter, it is 8 hours dry in 140 DEG C of drying box.It then will be after drying
Material, which is warming up to 500 DEG C with 7 DEG C/min of speed in tube furnace and keeps the temperature 4 hours at this temperature, is made electric field regulation and control
Selective freezing synthesizes double-perovskite Magnesium ion battery negative material.
Embodiment 3：By lithium nitrate, magnesium nitrate hexahydrate, six nitric hydrate yttriums, Gerhardite, five nitric hydrate zirconiums,
Zinc nitrate hexahydrate, niobium pentaoxide are according to stoichiometric equation MgY0.7Li0.3Zr0.8Cu0.1Zn0.1NbO6It is put into ball mill, ball
The mass ratio of mill and material is 20: 1, with 200 revs/min of speed ball milling 10 hours.By the material after ball milling in tube furnace
In with 2 DEG C/min of speed be warming up to after 800 DEG C the both ends in tube furnace apply a DC voltage, voltage 600V, herein
At a temperature of and electric field under keep the temperature 3 hours after cool to 30 DEG C with the furnace；Material after cooling is ground 6 minutes in mortar, poly-
Tetrafluoroethene agitating paddle is persistently stirred with the speed of 900rpm in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature, lithium metaborate
The mass ratio of the quality of saturated solution and the material after cooling of immersion is 10: 1, and after five minutes, thermostat temperature is dropped for lasting stirring
Down to 20 DEG C and continue stirring 5 minutes, to filter thereafter, it is 5 hours dry in 120 DEG C of drying box.Then by the object after drying
Material, which is warming up to 450 DEG C with 3 DEG C/min of speed in tube furnace and keeps the temperature 3 hours at this temperature, is made electric field regulation and control choosing
Select crystallization synthesis double-perovskite Magnesium ion battery negative material.
Embodiment 4：By lithium nitrate, magnesium nitrate hexahydrate, six nitric hydrate yttriums, Gerhardite, five nitric hydrate zirconiums,
Zinc nitrate hexahydrate, niobium pentaoxide are according to stoichiometric equation MgY0.7Li0.3Zr0.8Cu0.1Zn0.1NbO6It is put into ball mill, ball
The mass ratio of mill and material is 20: 1, with 300 revs/min of speed ball milling 15 hours.By the material after ball milling in tube furnace
In with 8 DEG C/min of speed be warming up to after 850 DEG C the both ends in tube furnace apply a DC voltage, voltage 900V, herein
At a temperature of and electric field under keep the temperature 6 hours after cool to 30 DEG C with the furnace；Material after cooling is ground 15 minutes in mortar, poly-
Tetrafluoroethene agitating paddle is persistently stirred with the speed of 1000rpm in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature, metaboric acid
The mass ratio of the quality of lithium saturated solution and the material after cooling of immersion is 10: 1, after persistently stirring 7 minutes, by thermostat temperature
It is reduced to 20 DEG C and continues stirring 5 minutes, filter thereafter, it is 5 hours dry in 120 DEG C of drying box.It then will be after drying
Material, which is warming up to 520 DEG C with 8 DEG C/min of speed in tube furnace and keeps the temperature 5 hours at this temperature, is made electric field regulation and control
Selective freezing synthesizes double-perovskite Magnesium ion battery negative material.
Embodiment 5：By lithium nitrate, magnesium nitrate hexahydrate, six nitric hydrate yttriums, Gerhardite, five nitric hydrate zirconiums,
Zinc nitrate hexahydrate, niobium pentaoxide are according to stoichiometric equation MgY0.7Li0.3Zr0.8Cu0.1Zn0.1NbO6It is put into ball mill, ball
The mass ratio of mill and material is 20: 1, with 400 revs/min of speed ball milling 20 hours.By the material after ball milling in tube furnace
In with 6 DEG C/min of speed be warming up to after 850 DEG C the both ends in tube furnace apply a DC voltage, voltage 800V, herein
At a temperature of and electric field under keep the temperature 5 hours after cool to 30 DEG C with the furnace；Material after cooling is ground 12 minutes in mortar, poly-
Tetrafluoroethene agitating paddle is persistently stirred with the speed of 1100rpm in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature, metaboric acid
The mass ratio of the quality of lithium saturated solution and the material after cooling of immersion is 10: 1, after persistently stirring 7 minutes, by thermostat temperature
It is reduced to 18 DEG C and continues stirring 12 minutes, filter thereafter, it is 7 hours dry in 150 DEG C of drying box.It then will be after drying
Material, which is warming up to 500 DEG C with 8 DEG C/min of speed in tube furnace and keeps the temperature 5 hours at this temperature, is made electric field regulation and control
Selective freezing synthesizes double-perovskite Magnesium ion battery negative material.
Claims (1)
1. a kind of electric field regulation and control selective freezing synthesizes double-perovskite Magnesium ion battery negative material, it is characterized in that：Group becomes
MgY0.7Li0.3Zr0.8Cu0.1Zn0.1NbO6, preparation process is by lithium nitrate, magnesium nitrate hexahydrate, six nitric hydrate yttriums, three hydrations
Copper nitrate, five nitric hydrate zirconiums, zinc nitrate hexahydrate, niobium pentaoxide are according to stoichiometric equation
MgY0.7Li0.3Zr0.8Cu0.1Zn0.1NbO6It being put into ball mill, the mass ratio of ball milling and material is 20: 1, turned with 200-400/
The speed ball milling of minute 10-20 hours；Material after ball milling is warming up to 800- in tube furnace with 2-10 DEG C/min of speed
Apply a DC voltage at the both ends of tube furnace after 900 DEG C, voltage 600-900V keeps the temperature 3-6 at this temperature and under electric field
30 DEG C are cooled to the furnace after hour；Material after cooling is ground 5-15 minutes in mortar, Teflon stir paddle with
The speed of 900-1200rpm persistently stirs in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature, lithium metaborate saturated solution
The mass ratio of quality and the material after cooling of immersion is 10: 1, and after persistently stirring 5-10 minutes, thermostat temperature is reduced to 18-
22 DEG C and continue stirring 5-15 minute, filter thereafter, in 120-160 DEG C of drying box dry 5-10 hours；Then it will dry
Material afterwards is warming up to 450-550 DEG C and is kept the temperature 3-5 hours at this temperature and made in tube furnace with 2-10 DEG C/min of speed
It obtains electric field regulation and control selective freezing and synthesizes double-perovskite Magnesium ion battery negative material.
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