CN107293741A - A kind of continuous electronic ion Quick conductive double-perovskite Magnesium ion battery negative material and preparation method thereof - Google Patents
A kind of continuous electronic ion Quick conductive double-perovskite Magnesium ion battery negative material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- Y02E60/10—Energy storage using batteries
Abstract
A kind of continuous electronic ion Quick conductive double-perovskite Magnesium ion battery negative material and preparation method thereof, it is characterized in that：The composition of the negative material is Mg0.8Sr0.2La0.5Y0.2Li0.3Ti0.8Cu0.1Zn0.1NbO6, by the use of the continuous pore passage structure of gel as template in preparation process, form the continuous poriferous pattern structure of double perovskite product that particle part is bonded mutually；The continuous high conductivity carbon film for sticking to surface of active material is formed by the cracking under protective gas simultaneously；Such pattern advantageously reduces crystal boundary resistance and electromigration resistance；The contact area of increase and electrolyte simultaneously has certain structural rigidity；Further occupied jointly by the Mg and La of A and part Y, Li of the part Sr replacements by Mg positions and La positions are substituted, improve electronic conductivity；By the Cu of B, Zn doping improves the stability of perovskite structure, ultimately forms high performance Magnesium ion battery negative material.
Description
Technical field
The present invention relates to a kind of Magnesium ion battery negative material manufacture method technical field.
Background technology
Lithium rechargeable battery has volume, weight energy higher than high, voltage, low self-discharge rate, memory-less effect, circulation
Long lifespan, power density height etc. definitely advantage, 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 that vehicle exhaust is brought is increasingly serious, electronic
Very urgent stage has been arrived in vigorously advocating and developing for car (EV) or hybrid electric vehicle (HEV)；These demands are provided
Lithium ion battery explosive growth point, while also the performance to lithium ion battery proposes higher requirement.
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 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 commercialization in 1991, the actual specific capacity of positive electrode is hesitated all the time
Wander between 100-180mAh/g, the low bottleneck for having become lifting lithium ion battery specific energy of positive electrode specific capacity.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 occurring redox reaction
Conducted with quick Lithium-ion embeding deintercalation and electronics, i.e., while there is good electron conduction and ionic conductivity, 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 is increased 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 there is multielectron transfer 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 used 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, traditional lithium ion cell positive and negative pole all exist lithium ion can be embedded in or deintercalation space, it is 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 can occur the alloy process of diversified forms, such as：
Lim+Me0 n→LimMe0 n
It can be discharged more than 1000mAh.g during the two-1Specific capacity, thus it is high to obtain investigation of materials personnel
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, be it is following be expected to replace lithium ion battery most have 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, study it also very inadequate at present.
Perovskite structure ABO3Type oxide obtains important application in solar cells recently.Its structure is A
The larger cation of radius, in 12 coordination structures, positioned in the hole that octahedron is constituted；B are transition metal class
Compared with small cation, with six oxonium ion formation octahedral coordinations.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
Research and development in Magnesium ion battery is substantially at blank.And its subject matter is：1st, ionic conductivity and electronic conductance
Rate is relatively low；2nd, 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；3rd, synthesis temperature is higher, easily causes 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
Particle size reduction can reduce the approach of magnesium ion diffusion to the yardstick of nanometer, 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 infiltration of electrolyte between particles difficult, the problems such as magnesium ion migration velocity is slow；Ion doping
It is also a kind of microstructure of effective regulation 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 using double calcium
Perovskite like structure A and B can be occupied by two kinds of metals, partly can also be replaced by aliovalent or iso-valence metal, therefore, to material
Expect the flexible adjustment of regulation and control, electronics and the ion motion property of structure.
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 proposes a kind of continuous electronic ion Quick conductive double-perovskite magnesium ion electricity for existing background technology
Pond negative material and preparation method thereof, it is characterized in that：The composition of the negative material is
Mg0.8Sr0.2La0.5Y0.2Li0.3Ti0.8Cu0.1Zn0.1NbO6, the continuous pore passage structure in preparation process by the use of gel as template,
Form the continuous poriferous pattern structure of double perovskite product that particle part is bonded mutually；Pass through the cracking shape under protective gas simultaneously
Into the continuous high conductivity carbon film for sticking to surface of active material；Such pattern advantageously reduces crystal boundary resistance, improve magnesium from
Locomitivity of the son in lattice；Continuous electron transfer network is formed, electromigration resistance is reduced；Increase connects with electrolyte
Contacting surface is accumulated, and accelerates electrolyte and the magnesium ion transfer ability and the speed of redox reaction in lattice；Such structure also has
There is certain structural rigidity, be that the material volume in charge and discharge process changes to form buffering；Further it is total to by the Mg and La of A
Part Sr replacements and part Y, Li of La positions with occupying and by Mg positions are substituted, and improve electronic conductivity；Pass through B
Cu, Zn doping improve perovskite structure stability, ultimately form high performance Magnesium ion battery negative material.
This continuous electronic ion Quick conductive double-perovskite Magnesium ion battery negative material, its preparation method is：By six
Nitric hydrate magnesium, lithium nitrate, butyl titanate, strontium nitrate, lanthanum nitrate hexahydrate, six nitric hydrate yttriums, Gerhardite, six
Nitric hydrate zinc, niobium oxalate are according to stoichiometric equation Mg0.8Sr0.2La0.5Y0.2Li0.3Ti0.8Cu0.1Zn0.1NbO6Mixing, admixture
The amount of matter for 5.0-10.0 times of the amount of total metal ion species citric acid and add water and stir to form total concentration of metal ions
For 1.0-2.5molL-1Initial aqueous solution；By the acrylamide and 1gN, N of 6g acrylamides/100mL waters '-methylene
The material of acrylamide in the N of bisacrylamide/100mL waters, N '-methylene-bisacrylamide and water mixed dissolution, solution
Amount be 0.5-1.2 times of the amount of total metal ion species in initial aqueous solution；Using Teflon stir oar with
It is risen to 75-85 DEG C with 5-10 DEG C/min of speed after stirring 5-15 minutes and kept by 1500rpm-2000rpm speed
The temperature is until it becomes gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying process
Using finished product freeze drier in the market, gel is put into freeze drier sample disc and starts refrigeration machine, sample is treated
Gelling temp is reduced to subzero 50 DEG C of subzero 45- on disk, opens vavuum pump and improves vacuum, treats that gas pressure is reduced in system
Below 25-35Pa, opens baffle temperature control and starts to dehydrate, other operating parameters take machine preset value, treat in system
Stable gas pressure dry terminate after, dried gel is put into initial aqueous solution, stand 10-20 minutes, then with 5-10 DEG C/
The speed of minute rises to 75-90 DEG C and at this temperature constant temperature 1-3 hours, then puts it into 80 DEG C of -120 DEG C of drying boxes
It is put into after drying 10-20 hours in tube furnace, 300-400 DEG C is warming up to simultaneously with 2-10 DEG C/min of speed in air atmosphere
Kept for 0.5-1 hours at this temperature, be then warming up to 400-550 DEG C simultaneously in argon gas atmosphere with 2-10 DEG C/min of speed
At this temperature keep 2-4 hours after continue in argon gas atmosphere with 2-10 DEG C/min of speed be warming up to 800-950 DEG C and
Kept for 4-10 hours at a temperature of this, the continuous electronic ion Quick conductive double-perovskite Magnesium ion battery negative material is made.
Compared with prior art, the advantage of the invention is that：Template, formation are used as by the use of the continuous pore passage structure of gel
The continuous poriferous pattern structure of double perovskite product that grain part is bonded mutually；Formed and adhered to by the cracking under protective gas simultaneously
In the continuous high conductivity carbon film of surface of active material；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 and the contact surface of electrolyte
Product, accelerates electrolyte and the magnesium ion transfer ability and the speed of redox reaction in lattice；Such structure also has one
Fixed structural rigidity, is that the material volume in charge and discharge process changes to form buffering；Further accounted for jointly by the Mg and La of A
Substituted according to and by the part Sr replacements of Mg positions and part Y, Li of La positions, improve electronic conductivity；Pass through B
Cu, Zn doping improve the stability of perovskite structure, ultimately form high performance Magnesium ion battery negative material.
Brief description of the drawings
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of preceding 10 circulations of Fig. 1 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, lithium nitrate, butyl titanate, strontium nitrate, lanthanum nitrate hexahydrate, six hydration nitre
Sour yttrium, Gerhardite, zinc nitrate hexahydrate, niobium oxalate are according to stoichiometric equation
Mg0.8Sr0.2La0.5Y0.2Li0.3Ti0.8Cu0.1Zn0.1NbO6Mixing, the amount for adding material is 5.0 times of the amount of total metal ion species
Citric acid and adding water stir to form total concentration of metal ions for 1.0molL-1Initial aqueous solution；By 6g acryloyls
The acrylamide and 1gN, N of amine/100mL waters '-methylene-bisacrylamide/100mL waters N, N '-methylene bisacrylamide
The amount of the material of acrylamide is the amount of total metal ion species in initial aqueous solution in acid amides and water mixed dissolution, solution
0.5 times；It is risen with 5 DEG C/min of speed after being stirred 5 minutes with 1500rpm speed using Teflon stir oar
To 75 DEG C and the temperature is kept until it becomes gelatin gel.The gel of formation is done in the environment of low-temperature high-vacuum degree
Dry, gel is put into freeze drier sample disc and started using finished product freeze drier in the market by the drying process
Refrigeration machine, treats that gelling temp is reduced to subzero 45 DEG C in sample disc, opens vavuum pump and improve vacuum, treat gas pressure in system
Below 25Pa is reduced to, baffle temperature control is opened and starts to dehydrate, other operating parameters take machine preset value, treat system
After interior stable gas pressure drying terminates, dried gel is put into initial aqueous solution, 10 minutes are stood, then with 5 DEG C/min
Speed rise to 75 DEG C and at this temperature constant temperature 1 hour, then put it into 80 DEG C of drying boxes dry 11 hours after put
Enter in tube furnace, be warming up to 320 DEG C with 3 DEG C/min of speed in air atmosphere and kept for 0.6 hour at this temperature, and
420 DEG C are warming up in argon gas atmosphere with 3 DEG C/min of speed and continue after being kept for 2 hours at this temperature in argon gas gas afterwards
800 DEG C being warming up to 2 DEG C/min of speed in atmosphere and being kept for 4 hours at this temperature, the continuous electronic ion is made and quickly leads
Electric double-perovskite Magnesium ion battery negative material.
Embodiment 2：By magnesium nitrate hexahydrate, lithium nitrate, butyl titanate, strontium nitrate, lanthanum nitrate hexahydrate, six hydration nitre
Sour yttrium, Gerhardite, zinc nitrate hexahydrate, niobium oxalate are according to stoichiometric equation
Mg0.8Sr0.2La0.5Y0.2Li0.3Ti0.8Cu0.1Zn0.1NbO6Mixing, it is 7 times of the amount of total metal ion species to add the amount of material
Citric acid and adding water stirs to form total concentration of metal ions for 1.5molL-1Initial aqueous solution；By 6g acrylamides/
The acrylamide and 1gN, N of 100mL waters '-methylene-bisacrylamide/100mL waters N, N '-methylene-bisacrylamide
With water mixed dissolution, the amount of the material of acrylamide is 0.7 times of the amount of total metal ion species in initial aqueous solution in solution；
It is risen to 80 DEG C with 8 DEG C/min of speed after being stirred 10 minutes with 1700rpm speed using Teflon stir oar
And the temperature is kept until it becomes gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, this is done
Gel is put into freeze drier sample disc using finished product freeze drier in the market and is started refrigeration machine by dry process,
Treat that gelling temp is reduced to subzero 47 DEG C in sample disc, open vavuum pump and improve vacuum, treat that gas pressure is reduced in system
Below 30Pa, opens baffle temperature control and starts to dehydrate, other operating parameters take machine preset value, treat air pressure in system
Stablize after dry terminate, dried gel is put into initial aqueous solution, 15 minutes are stood, then with 8 DEG C/min of speed
85 DEG C and at this temperature constant temperature 2 hours are risen to, then puts it into after being dried 15 hours in 100 DEG C of drying boxes and is put into tubular type
In stove, it is warming up to 350 DEG C with 8 DEG C/min of speed in air atmosphere and is kept for 0.7 hour at this temperature, then in argon
450 DEG C are warming up to 8 DEG C/min of speed and continue after being kept for 3 hours at this temperature in argon gas atmosphere with 8 in gas atmosphere
DEG C/min speed be warming up to 900 DEG C and kept for 8 hours at this temperature, the double calcium of continuous electronic ion Quick conductive are made
Titanium ore Magnesium ion battery negative material.
Embodiment 3：By magnesium nitrate hexahydrate, lithium nitrate, butyl titanate, strontium nitrate, lanthanum nitrate hexahydrate, six hydration nitre
Sour yttrium, Gerhardite, zinc nitrate hexahydrate, niobium oxalate are according to stoichiometric equation
Mg0.8Sr0.2La0.5Y0.2Li0.3Ti0.8Cu0.1Zn0.1NbO6Mixing, the amount for adding material is the amount 10.0 of total metal ion species
Times citric acid and adding water stir to form total concentration of metal ions for 2.5molL-1Initial aqueous solution；By 6g acryloyls
The acrylamide and 1gN, N of amine/100mL waters '-methylene-bisacrylamide/100mL waters N, N '-methylene bisacrylamide
The amount of the material of acrylamide is the amount of total metal ion species in initial aqueous solution in acid amides and water mixed dissolution, solution
1.2 again；It is risen with 9 DEG C/min of speed after being stirred 15 minutes with 2000rpm speed using Teflon stir oar
To 85 DEG C and the temperature is kept until it becomes gelatin gel.The gel of formation is done in the environment of low-temperature high-vacuum degree
Dry, gel is put into freeze drier sample disc and started using finished product freeze drier in the market by the drying process
Refrigeration machine, treats that gelling temp is reduced to subzero 50 DEG C in sample disc, opens vavuum pump and improve vacuum, treat gas pressure in system
Below 33Pa is reduced to, baffle temperature control is opened and starts to dehydrate, other operating parameters take machine preset value, treat system
After interior stable gas pressure drying terminates, dried gel is put into initial aqueous solution, 18 minutes are stood, then with 8 DEG C/min
Speed rise to 89 DEG C and at this temperature constant temperature 3 hours, then put it into 118 DEG C of drying boxes dry 20 hours after put
Enter in tube furnace, 400 DEG C and at this temperature holding 1 hour are warming up to 10 DEG C/min of speed in air atmosphere, then
530 DEG C are warming up to 8 DEG C/min of speed and continue after being kept for 4 hours at this temperature in argon gas atmosphere in argon gas atmosphere
In with 10 DEG C/min of speed be warming up to 950 DEG C and at this temperature keep 10 hours, be made the continuous electronic ion quickly lead
Electric double-perovskite Magnesium ion battery negative material.
Embodiment 4：By magnesium nitrate hexahydrate, lithium nitrate, butyl titanate, strontium nitrate, lanthanum nitrate hexahydrate, six hydration nitre
Sour yttrium, Gerhardite, zinc nitrate hexahydrate, niobium oxalate are according to stoichiometric equation
Mg0.8Sr0.2La0.5Y0.2Li0.3Ti0.8Cu0.1Zn0.1NbO6Mixing, it is 9 times of the amount of total metal ion species to add the amount of material
Citric acid and adding water stirs to form total concentration of metal ions for 2.0molL-1Initial aqueous solution；By 6g acrylamides/
The acrylamide and 1gN, N of 100mL waters '-methylene-bisacrylamide/100mL waters N, N '-methylene-bisacrylamide
With water mixed dissolution, the amount of the material of acrylamide is 1.1 times of the amount of total metal ion species in initial aqueous solution in solution；
It is risen to 80 DEG C with 8 DEG C/min of speed after being stirred 10 minutes with 1700rpm speed using Teflon stir oar
And the temperature is kept until it becomes gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, this is done
Gel is put into freeze drier sample disc using finished product freeze drier in the market and is started refrigeration machine by dry process,
Treat that gelling temp is reduced to subzero 45 DEG C in sample disc, open vavuum pump and improve vacuum, treat that gas pressure is reduced in system
Below 30Pa, opens baffle temperature control and starts to dehydrate, other operating parameters take machine preset value, treat air pressure in system
Stablize after dry terminate, dried gel is put into initial aqueous solution, 15 minutes are stood, then with 8 DEG C/min of speed
88 DEG C and at this temperature constant temperature 3 hours are risen to, then puts it into after being dried 15 hours in 110 DEG C of drying boxes and is put into tubular type
In stove, it is warming up to 400 DEG C with 8 DEG C/min of speed in air atmosphere and is kept for 0.8 hour at this temperature, then in argon
In gas atmosphere with 8 DEG C/min of speed be warming up to 500 DEG C and at this temperature keep 4 hours after continue in argon gas atmosphere with
10 DEG C/min of speed is warming up to 950 DEG C and kept for 10 hours at this temperature, the continuous electronic ion Quick conductive is made double
Perovskite Magnesium ion battery negative material.
Embodiment 5：By magnesium nitrate hexahydrate, lithium nitrate, butyl titanate, strontium nitrate, lanthanum nitrate hexahydrate, six hydration nitre
Sour yttrium, Gerhardite, zinc nitrate hexahydrate, niobium oxalate are according to stoichiometric equation
Mg0.8Sr0.2La0.5Y0.2Li0.3Ti0.8Cu0.1Zn0.1NbO6Mixing, the amount for adding material is 10 times of the amount of total metal ion species
Citric acid and adding water stir to form total concentration of metal ions for 1.5molL-1Initial aqueous solution；By 6g acryloyls
The acrylamide and 1gN, N of amine/100mL waters '-methylene-bisacrylamide/100mL waters N, N '-methylene bisacrylamide
The amount of the material of acrylamide is the amount of total metal ion species in initial aqueous solution in acid amides and water mixed dissolution, solution
1.2 again；By it with 10 DEG C/min of speed after being stirred 10 minutes with 2000rpm speed using Teflon stir oar
It is raised to 85 DEG C and keeps the temperature until it becomes gelatin gel.The gel of formation is done in the environment of low-temperature high-vacuum degree
Dry, gel is put into freeze drier sample disc and started using finished product freeze drier in the market by the drying process
Refrigeration machine, treats that gelling temp is reduced to subzero 45 DEG C in sample disc, opens vavuum pump and improve vacuum, treat gas pressure in system
Below 35Pa is reduced to, baffle temperature control is opened and starts to dehydrate, other operating parameters take machine preset value, treat system
After interior stable gas pressure drying terminates, dried gel is put into initial aqueous solution, 15 minutes are stood, then with 10 DEG C/minute
The speed of clock rises to 90 DEG C and at this temperature constant temperature 3 hours, then puts it into after being dried 20 hours in 110 DEG C of drying boxes
It is put into tube furnace, is warming up to 400 DEG C with 8 DEG C/min of speed in air atmosphere and is kept for 0.8 hour at this temperature,
Then 550 DEG C are warming up in argon gas atmosphere with 10 DEG C/min of speed and continue after being kept for 3 hours at this temperature in argon gas
950 DEG C are warming up to 10 DEG C/min of speed in atmosphere and are kept for 10 hours at this temperature, the continuous electronic ion is made fast
Fast conduction double-perovskite Magnesium ion battery negative material.
Claims (1)
1. a kind of continuous electronic ion Quick conductive double-perovskite Magnesium ion battery negative material, it is characterized in that：Constitute and be
Mg0.8Sr0.2La0.5Y0.2Li0.3Ti0.8Cu0.1Zn0.1NbO6, preparation process is by magnesium nitrate hexahydrate, lithium nitrate, the fourth of metatitanic acid four
Ester, strontium nitrate, lanthanum nitrate hexahydrate, six nitric hydrate yttriums, Gerhardite, zinc nitrate hexahydrate, niobium oxalate are according to chemistry
Metering-type Mg0.8Sr0.2La0.5Y0.2Li0.3Ti0.8Cu0.1Zn0.1NbO6Mixing, it is total metal ion species to add the amount of material
Measure 5.0-10.0 times of citric acid and add water and stir to form total concentration of metal ions for 1.0-2.5molL-1Initial water
Solution；By the acrylamide and 1gN, N of 6g acrylamides/100mL waters ' N of-methylene-bisacrylamide/100mL waters,
The amount of the material of acrylamide is total metal in initial aqueous solution in N '-methylene-bisacrylamide and water mixed dissolution, solution
0.5-1.2 times of the amount of ionic species；Using Teflon stir oar with 1500rpm-2000rpm 5-15 points of speed stirring
It is risen to 75-85 DEG C with 5-10 DEG C/min of speed after clock and the temperature is kept until it becomes gelatin gel；By shape
Into gel dried in the environment of low-temperature high-vacuum degree, the drying process using finished product freeze drier in the market,
Gel is put into freeze drier sample disc and starts refrigeration machine, treats that gelling temp is reduced to subzero 45- subzero 50 in sample disc
DEG C, open vavuum pump and improve vacuum, treat that gas pressure is reduced to below 25-35Pa in system, open baffle temperature control and open
Beginning dehydrates, and other operating parameters take machine preset value, after stable gas pressure drying terminates in system, will be dried solidifying
Glue is put into initial aqueous solution, stands 10-20 minutes, then rises to 75-90 DEG C and warm herein with 5-10 DEG C/min of speed
Degree lower constant temperature 1-3 hours, then puts it into after being dried 10-20 hours in 80 DEG C of -120 DEG C of drying boxes and is put into tube furnace,
300-400 DEG C is warming up to 2-10 DEG C/min of speed in air atmosphere and is kept for 0.5-1 hours at this temperature, then exist
400-550 DEG C is warming up to 2-10 DEG C/min of speed and continue after being kept for 2-4 hours at this temperature in argon in argon gas atmosphere
800-950 DEG C is warming up to 2-10 DEG C/min of speed in gas atmosphere and is kept for 4-10 hours at this temperature, this is made continuous
Electronic and ionic Quick conductive double-perovskite Magnesium ion battery negative material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110109293A (en) * | 2019-04-04 | 2019-08-09 | 深圳市华星光电技术有限公司 | The manufacturing method of the inorganic orientation film of liquid crystal |
| CN112321298A (en) * | 2020-11-06 | 2021-02-05 | 中国科学院新疆理化技术研究所 | Perovskite-like thermistor material and preparation method thereof |
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| CN106848259A (en) * | 2017-03-25 | 2017-06-13 | 宁波吉电鑫新材料科技有限公司 | A kind of continuous conduction original position C/Ag, Zr/ZrF4Compound zirconium fluoride anode material for lithium-ion batteries and preparation method thereof |
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| JPH05330827A (en) * | 1991-12-06 | 1993-12-14 | Rhone Poulenc Chim | Perovskite wherein tantalum or niobium is base material and preparation thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110109293A (en) * | 2019-04-04 | 2019-08-09 | 深圳市华星光电技术有限公司 | The manufacturing method of the inorganic orientation film of liquid crystal |
| CN112321298A (en) * | 2020-11-06 | 2021-02-05 | 中国科学院新疆理化技术研究所 | Perovskite-like thermistor material and preparation method thereof |
| CN112321298B (en) * | 2020-11-06 | 2022-03-11 | 中国科学院新疆理化技术研究所 | Perovskite-like thermistor material and preparation method thereof |
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