CN107265502B - A kind of electric field regulation and control selective freezing synthesis double-perovskite kalium ion battery negative material and preparation method thereof - Google Patents
A kind of electric field regulation and control selective freezing synthesis double-perovskite kalium ion battery negative material and preparation method thereof Download PDFInfo
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Abstract
A kind of electric field regulation and control selective freezing synthesis double-perovskite kalium ion battery negative material and preparation method thereof, it is characterized in that：The group of the negative material becomes KSc0.8La0.1Ba0.1ZrNbO6, 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 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 and electromigration resistance；Accelerate the rate of electrolyte and potassium ion transfer ability and redox reaction in lattice；Such structure also has certain structural rigidity, changes to form buffering for the material volume in charge and discharge process；Further the K and Sc by A are occupied jointly and La, Ba of the positions Sc are adulterated by formed high performance kalium ion battery negative material.
Description
Technical field
The present invention relates to a kind of kalium 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 potassium 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 kalium ion battery negative material of alloy mechanism is it can also happen that following electrification
Learn reaction：
2K++MeO+2e-→K2O+Me0
Km+Me0 n→KmMe0 n
And larger specific capacity can be released, however generally since potassium 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 kalium 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 kalium ion battery negative material, may carry
For near or above 300mAh.g-1Specific capacity, potassium ion enter or abjection material volume variation it is also smaller；However the material
Research and development in kalium ion battery is substantially at blank.And its main problem is：1, ionic conductivity and electronic conductance
Rate is relatively low；2, the product potassium oxide after conversion reaction is electronic body and its potassium 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 potassium ion diffusion, shorten the diffusion time of potassium 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 potassium 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, to material
Expect the regulation and control of 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 kalium ion battery negative material.
Invention content
The present invention proposes a kind of electric field regulation and control selective freezing synthesis double-perovskite potassium 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 KSc0.8La0.1Ba0.1ZrNbO6, prepared
Change the crystallization property with lattice defect crystal using the electric field for applying specific direction in high temperature solid state reaction in journey, along electricity
Field direction grows to form cylindrical shape particle；The non-homogeneous crystallization of cylindrical shape particle surface simultaneously and it is big in surface curvature radius
Position unevenly adheres to sintering aid and part adhesive becomes continuous poriferous pattern；Such pattern advantageously reduces crystal boundary resistance
Power improves locomitivity of the potassium ion in lattice；Continuous electron transfer network is formed, electromigration resistance is reduced；Increase
With the contact area of electrolyte, accelerate the rate of electrolyte and potassium ion transfer ability and redox reaction in lattice；This
The structure of sample also has certain structural rigidity, changes to form buffering for the material volume in charge and discharge process；Further pass through A
The K and Sc of position are occupied jointly, are improved electronic conductivity and are adulterated by La, Ba of the positions Sc, improve potassium ion conductivity；Most
End form is at high performance kalium ion battery negative material.
This electric field regulation and control selective freezing synthesizes double-perovskite kalium ion battery negative material, and preparation method is：By nitre
Sour barium, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, scandium oxide, niobium pentaoxide are according to stoichiometric equation
KSc0.8La0.1Ba0.1ZrNbO6It is put into ball mill, the mass ratio of ball milling and material is 20: 1, with 200-400 revs/min
Speed ball milling 10-20 hours.Material after ball milling is warming up to 800-900 DEG C in tube furnace with 2-10 DEG C/min of speed
Apply a DC voltage, voltage 600-900V, after at this temperature and keeping the temperature 3-6 hours under electric field at the both ends of tube furnace afterwards
Cool to 30 DEG C with the furnace；Material after cooling is ground 5-15 minutes in mortar, in Teflon stir paddle with 900-
The speed of 1200rpm persistently stirs in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature, the quality of lithium metaborate saturated solution
Mass ratio with 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 minutes, and it filters thereafter, it is 5-10 hours dry in 120-160 DEG C of drying box.It then will be after drying
Material is warming up to 450-550 DEG C and is kept the temperature 3-5 hours at this temperature in tube furnace with 2-10 DEG C/min of speed is made this
Electric field regulates and controls selective freezing and synthesizes double-perovskite kalium 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 potassium 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 potassium 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 K and Sc, improves electronic conductivity and lead to
La, Ba doping for crossing the portion positions Sc, improve potassium ion conductivity；Ultimately form high performance kalium 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.
The scanning electron microscope (SEM) photograph of Fig. 2 materials.
Specific implementation mode
Below in conjunction with embodiment, present invention is further described in detail.
Embodiment 1：Barium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, scandium oxide, niobium pentaoxide are pressed
According to stoichiometric equation KSc0.8La0.1Ba0.1ZrNbO6It is put into ball mill, the mass ratio of ball milling and material is 20: 1, with 400
Rev/min speed ball milling 20 hours.Material after ball milling is warming up to 900 DEG C in tube furnace with 10 DEG C/min of speed
Apply a DC voltage, voltage 900V, with furnace cooling after at this temperature and keeping the temperature 5 hours under electric field at the both ends of tube furnace afterwards
But to 30 DEG C；Material after cooling is ground 12 minutes in mortar, is held with the speed of 1200rpm in Teflon stir paddle
Continuous stirring is lower to immerse in 30 DEG C of lithium metaborate saturated solutions of constant temperature, the quality of lithium metaborate saturated solution and immersion it is after cooling
The mass ratio of material is 10: 1, after persistently stirring 9 minutes, thermostat temperature is reduced to 22 DEG C and continues stirring 15 minutes, thereafter
Filtering, it is 10 hours dry in 160 DEG C of drying box.Then by the material after drying in tube furnace with 10 DEG C/min of speed
Degree, which is warming up to 550 DEG C and keeps the temperature 5 hours at this temperature, is made electric field regulation and control selective freezing synthesis double-perovskite potassium ion electricity
Pond negative material.
Embodiment 2：Barium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, scandium oxide, niobium pentaoxide are pressed
According to stoichiometric equation KSc0.8La0.1Ba0.1ZrNbO6It is put into ball mill, the mass ratio of ball milling and material is 20: 1, with 400
Rev/min speed ball milling 15 hours.After material after ball milling is warming up to 900 DEG C in tube furnace with 8 DEG C/min of speed
Apply a DC voltage, voltage 900V, furnace cooling after at this temperature and keeping the temperature 5 hours under electric field at the both ends of tube furnace
To 30 DEG C；Material after cooling is ground 12 minutes in mortar, is continued with the speed of 1000rpm in Teflon stir paddle
Stirring is lower to immerse in 30 DEG C of lithium metaborate saturated solutions of constant temperature, the quality of lithium metaborate saturated solution and the object after cooling of immersion
The mass ratio of material is 10: 1, after persistently stirring 7 minutes, thermostat temperature is reduced to 20 DEG C and continues stirring 10 minutes, thereafter mistake
Filter, it is 8 hours dry in 140 DEG C of drying box.Then by the material after drying in tube furnace with 7 DEG C/min of speed liter
Temperature keeps the temperature 4 hours to 500 DEG C and at this temperature electric field regulation and control selective freezing synthesis double-perovskite kalium ion battery is made negative
Pole material.Embodiment 3：Barium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, scandium oxide, niobium pentaoxide are pressed
According to stoichiometric equation KSc0.8La0.1Ba0.1ZrNbO6It is put into ball mill, the mass ratio of ball milling and material is 20: 1, with 200
Rev/min speed ball milling 10 hours.After material after ball milling is warming up to 800 DEG C in tube furnace with 2 DEG C/min of speed
Apply a DC voltage, voltage 600V, furnace cooling after at this temperature and keeping the temperature 3 hours under electric field at the both ends of tube furnace
To 30 DEG C；Material after cooling is ground 6 minutes in mortar, is persistently stirred with the speed of 900rpm in Teflon stir paddle
It mixes in lower 30 DEG C of lithium metaborate saturated solutions of immersion constant temperature, the quality of lithium metaborate saturated solution and the material after cooling of immersion
Mass ratio be 10: 1, thermostat temperature after five minutes, is reduced to 18 DEG C and continues stirring 5 minutes, filtered thereafter by lasting stirring,
It is 5 hours dry in 120 DEG C of drying box.Then the material after drying is warming up in tube furnace with 3 DEG C/min of speed
450 DEG C and at this temperature keep the temperature 3 hours be made the electric field regulation and control selective freezing synthesize double-perovskite kalium ion battery cathode material
Material.Embodiment 4：By barium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, scandium oxide, niobium pentaoxide according to change
Learn metering-type KSc0.8La0.1Ba0.1ZrNbO6It is put into ball mill, the mass ratio of ball milling and material is 20: 1, with 300 revs/min
The speed ball milling of clock 15 hours.Material after ball milling is warming up to after 850 DEG C with 8 DEG C/min of speed in pipe in tube furnace
The both ends of formula stove apply a DC voltage, and voltage 900V cools to 30 with the furnace at this temperature and after keeping the temperature 6 hours under electric field
℃；Material after cooling is ground 15 minutes in mortar, is persistently stirred with the speed of 1000rpm in Teflon stir paddle
In lower 30 DEG C of lithium metaborate saturated solutions of immersion constant temperature, the quality of lithium metaborate saturated solution and the material after cooling of immersion
Mass ratio is 10: 1, after persistently stirring 7 minutes, thermostat temperature is reduced to 18 DEG C and continues stirring 5 minutes, is filtered thereafter,
It is 5 hours dry in 120 DEG C of drying box.Then the material after drying is warming up in tube furnace with 8 DEG C/min of speed
520 DEG C and at this temperature keep the temperature 5 hours be made the electric field regulation and control selective freezing synthesize double-perovskite kalium ion battery cathode material
Material.Embodiment 5：By barium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, scandium oxide, niobium pentaoxide according to change
Learn metering-type KSc0.8La0.1Ba0.1ZrNbO6It is put into ball mill, the mass ratio of ball milling and material is 20: 1, with 400 revs/min
The speed ball milling of clock 20 hours.Material after ball milling is warming up to after 850 DEG C with 6 DEG C/min of speed in pipe in tube furnace
The both ends of formula stove apply a DC voltage, and voltage 800V cools to 30 with the furnace at this temperature and after keeping the temperature 5 hours under electric field
℃；Material after cooling is ground 12 minutes in mortar, is persistently stirred with the speed of 1100rpm in Teflon stir paddle
In lower 30 DEG C of lithium metaborate saturated solutions of immersion constant temperature, the quality of lithium metaborate saturated solution and the material after cooling of immersion
Mass ratio is 10: 1, after persistently stirring 7 minutes, thermostat temperature is reduced to 19 DEG C and continues stirring 12 minutes, is filtered thereafter,
It is 7 hours dry in 150 DEG C of drying box.Then the material after drying is warming up in tube furnace with 8 DEG C/min of speed
500 DEG C and at this temperature keep the temperature 5 hours be made the electric field regulation and control selective freezing synthesize double-perovskite kalium ion battery cathode material
Material.
Claims (1)
1. a kind of electric field regulation and control selective freezing synthesizes double-perovskite kalium ion battery negative material, it is characterized in that：Group becomes
KSc0.8La0.1Ba0.1ZrNbO6；Preparation method is by barium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, oxidation
Scandium, niobium pentaoxide are according to stoichiometric equation KSc0.8La0.1Ba0.1ZrNbO6It is put into ball mill, the quality of ball milling and material
Than being 20: 1, with 200-400 revs/min of speed ball milling 10-20 hours；By the material after ball milling with 2-10 in tube furnace
DEG C/min speed be warming up to after 800-900 DEG C the both ends in tube furnace apply a DC voltage, voltage 600-900V,
30 DEG C are cooled to the furnace after keeping the temperature 3-6 hours at a temperature of this and under electric field；Material after cooling is ground to 5-15 points in mortar
It is molten to immerse 30 DEG C of lithium metaborate saturations of constant temperature in the case where Teflon stir paddle is persistently stirred with the speed of 900-1200rpm for clock
In liquid, the mass ratio of the quality of lithium metaborate saturated solution and the material after cooling of immersion is 10: 1, persistently stirs 5-10 points
Thermostat temperature is reduced to 18-22 DEG C and continues stirring 5-15 minutes, filtered thereafter, in 120-160 DEG C of drying box by Zhong Hou
It is 5-10 hours dry；Then the material after drying is warming up to 450-550 DEG C simultaneously in tube furnace with 2-10 DEG C/min of speed
It keeps the temperature 3-5 hours at this temperature and electric field regulation and control selective freezing synthesis double-perovskite kalium ion battery negative material is made.
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