CN107359332A - A kind of continuous electronic ion Quick conductive double-perovskite kalium ion battery negative material and preparation method thereof - Google Patents

A kind of continuous electronic ion Quick conductive double-perovskite kalium ion battery negative material and preparation method thereof Download PDF

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CN107359332A
CN107359332A CN201710550970.2A CN201710550970A CN107359332A CN 107359332 A CN107359332 A CN 107359332A CN 201710550970 A CN201710550970 A CN 201710550970A CN 107359332 A CN107359332 A CN 107359332A
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ion battery
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姘存芳
水淼
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Ningbo Kyrgyzstan Xin New Mstar Technology Ltd
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A kind of continuous electronic ion Quick conductive double-perovskite kalium ion battery negative material and preparation method thereof, it is characterized in that：The composition of the negative material is KTb0.5Ba0.2Y0.2Li0.1Zr0.8Fe0.1Zn0.1NbO6, 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 being adhered to surface of active material is formed by the cracking under protective gas simultaneously；Such pattern advantageously reduces crystal boundary resistance；Continuous electron transfer network is formed, reduces electromigration resistance；The contact area of increase and electrolyte simultaneously has certain structural rigidity；Further occupied by the K and Tb of A positions and substituted by part Ba, Y, Li of Tb positions jointly, improve electronic conductivity；By the Fe of B positions, Zn doping improves the stability of perovskite structure, ultimately forms high performance kalium ion battery negative material.

Description

A kind of continuous electronic ion Quick conductive double-perovskite kalium ion battery negative material and Its preparation method
Technical field
The present invention relates to a kind of kalium 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 potassium 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 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 discharged, but generally because potassium 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 kalium 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 kalium ion battery negative material, and it may be carried For near or above 300mAh.g-1Specific capacity, potassium ion enter or abjection material volume change it is also smaller；But the material Research and development in kalium ion battery is substantially at blank.And its subject matter is：1st, ionic conductivity and electronic conductance Rate is relatively low；2nd, 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；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 potassium ion diffusion to the yardstick of nanometer, shorten diffusion time of potassium 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 potassium 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 kalium ion battery negative material.
The content of the invention
The present invention proposes a kind of continuous electronic ion Quick conductive double-perovskite potassium 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 KTb0.5Ba0.2Y0.2Li0.1Zr0.8Fe0.1Zn0.1NbO6, template, shape are used as by the use of the continuous pore passage structure of gel in preparation process The continuous poriferous pattern structure of double perovskite product being bonded mutually into particle part；Formed simultaneously by the cracking under protective gas It is adhered to the continuous high conductivity carbon film of surface of active material；Such pattern advantageously reduces crystal boundary resistance, improves potassium ion Locomitivity in lattice；Continuous electron transfer network is formed, reduces electromigration resistance；Increase the contact with electrolyte Area, accelerate electrolyte and the potassium ion transfer ability and the speed of redox reaction in lattice；Such structure also has Certain structural rigidity, it is that the material volume in charge and discharge process changes to form buffering；It is further common by the K and Tb of A positions Occupy and substituted by part Ba, Y, Li of Tb positions, improve electronic conductivity；By the Fe of B positions, Zn doping improves calcium titanium The stability of ore deposit structure, ultimately form high performance kalium ion battery negative material.
This continuous electronic ion Quick conductive double-perovskite potassium ion cell negative pole material, its preparation method are：By nitric acid Potassium, six nitric hydrate terbiums, lithium nitrate, barium nitrate, five nitric hydrate zirconiums, six nitric hydrate yttriums, Fe(NO3)39H2O, six hydration nitre Sour zinc, niobium oxalate are according to stoichiometric equation KTb0.5Ba0.2Y0.2Li0.1Zr0.8Fe0.1Zn0.1NbO6Mixing, the amount for adding material are The citric acid of 5-10 times of the amount of total metal ion species and plus water stir that to form total concentration of metal ions be 1.0- 2.5mol·L-1Initial aqueous solution；By the acrylamide and 1gN, N of 6g acrylamides/100mL waters '-methylene bisacrylamide The N of acid amides/100mL waters, N '-methylene-bisacrylamide and water mixed dissolution, the amount of the material of acrylamide is in solution 0.5-1.2 times of the amount of total metal ion species in initial aqueous solution；Using Teflon stir oar with 1500rpm- It is risen to 75-85 DEG C with 5-10 DEG C/min of speed after 2000rpm speed stirring 5-15 minutes and keeps the temperature straight To as gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, the drying process is using current The finished product freeze drier of in the market, gel is put into freeze drier sample disc and starts refrigeration machine, treats gel in sample disc Temperature is reduced to subzero 50 DEG C of subzero 45-, opens vavuum pump and improves vacuum, treats that gas pressure is reduced to 25-35Pa in system Hereinafter, open baffle temperature control to start to dehydrate, other operating parameters take machine preset value, treat stable gas pressure in system Dry after terminating, dried gel is put into initial aqueous solution, 10-20 minutes are stood, then with 5-10 DEG C/min of speed Degree rises to 75-90 DEG C and at this temperature constant temperature 1-3 hours, then puts it into and 10- is dried in 80 DEG C of -120 DEG C of drying boxes It is put into after 20 hours in tube furnace, 300-400 DEG C is warming up to and in this temperature with 2-10 DEG C/min of speed in air atmosphere Lower holding 0.5-1 hours, then it is warming up to 400-550 DEG C and in this temperature in argon gas atmosphere with 2-10 DEG C/min of speed Continue to be warming up to 800-950 DEG C and at this temperature in argon gas atmosphere with 2-10 DEG C/min of speed after lower holding 2-4 hours Kept for 4-10 hours, the continuous electronic ion Quick conductive double-perovskite kalium 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；Adhesion is formed 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 potassium ion in crystalline substance Locomitivity in lattice；Continuous electron transfer network is formed, reduces electromigration resistance；Increase and the contact surface of electrolyte Product, accelerate electrolyte and the potassium ion transfer ability and the speed of redox reaction in lattice；Such structure also has one Fixed structural rigidity, it is that the material volume in charge and discharge process changes to form buffering；Further accounted for jointly by the K and Tb of A positions Substituted according to and by part Ba, Y, Li of Tb positions, improve electronic conductivity；By the Fe of B positions, Zn doping improves perovskite The stability of structure, ultimately form high performance kalium 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.
The scanning electron microscope (SEM) photograph of Fig. 2 materials.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1：By potassium nitrate, six nitric hydrate terbiums, lithium nitrate, barium nitrate, five nitric hydrate zirconiums, six nitric hydrates Yttrium, Fe(NO3)39H2O, zinc nitrate hexahydrate, niobium oxalate are according to stoichiometric equation KTb0.5Ba0.2Y0.2Li0.1Zr0.8Fe0.1Zn0.1NbO6Mixing, the amount for adding material are the lemon of 5 times of the amount of total metal ion species Lemon acid and add water to stir to form total concentration of metal ions be 1.0molL-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 0.5 times of the amount of total metal ion species in initial aqueous solution in solution； It is risen to 75 DEG C with 5 DEG C/min of speed after being stirred 5 minutes with 1500rpm 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 dry Dry process uses finished product freeze drier in the market, and gel is put into freeze drier sample disc and starts refrigeration machine, 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 25Pa, open baffle temperature control and start to dehydrate, other operating parameters take machine preset value, treat air pressure in system After stablizing dry terminate, dried gel is put into initial aqueous solution, 10 minutes are stood, then with 5 DEG C/min of speed 75 DEG C and at this temperature constant temperature 1 hour are risen to, then puts it into 80 DEG C of drying boxes after drying 11 hours and is put into tubular type In stove, it is warming up to 320 DEG C with 3 DEG C/min of speed in air atmosphere and is kept for 0.6 hour at this temperature, then in argon 420 DEG C are warming up to 3 DEG C/min of speed and continue after being kept for 2 hours at this temperature in argon gas atmosphere with 2 in gas atmosphere DEG C/min speed be warming up to 800 DEG C and kept for 4 hours at this temperature, the double calcium of continuous electronic ion Quick conductive are made Titanium ore kalium ion battery negative material.
Embodiment 2：By potassium nitrate, six nitric hydrate terbiums, lithium nitrate, barium nitrate, five nitric hydrate zirconiums, six nitric hydrates Yttrium, Fe(NO3)39H2O, zinc nitrate hexahydrate, niobium oxalate are according to stoichiometric equation KTb0.5Ba0.2Y0.2Li0.1Zr0.8Fe0.1Zn0.1NbO6Mixing, the amount for adding material are the lemon of 8 times of the amount of total metal ion species Lemon acid and add water to stir to form total concentration of metal ions be 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 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 dry Dry process uses finished product freeze drier in the market, and gel is put into freeze drier sample disc and starts refrigeration machine, 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, open baffle temperature control and start to dehydrate, other operating parameters take machine preset value, treat air pressure in system After stablizing 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 100 DEG C of drying boxes after drying 15 hours 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 kalium ion battery negative material.
Embodiment 3：By potassium nitrate, six nitric hydrate terbiums, lithium nitrate, barium nitrate, five nitric hydrate zirconiums, six nitric hydrates Yttrium, Fe(NO3)39H2O, zinc nitrate hexahydrate, niobium oxalate are according to stoichiometric equation KTb0.5Ba0.2Y0.2Li0.1Zr0.8Fe0.1Zn0.1NbO6Mixing, the amount for adding material are the lemon of 10 times of the amount of total metal ion species Lemon acid and add water to stir to form total concentration of metal ions be 2.5molL-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 1.2 times of the amount of total metal ion species in initial aqueous solution in solution； It is risen to 85 DEG C with 9 DEG C/min of speed after being stirred 15 minutes with 2000rpm 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 dry Dry process uses finished product freeze drier in the market, and gel is put into freeze drier sample disc and starts refrigeration machine, Treat that gelling temp is reduced to subzero 50 DEG C in sample disc, open vavuum pump and improve vacuum, treat that gas pressure is reduced in system Below 33Pa, open baffle temperature control and start to dehydrate, other operating parameters take machine preset value, treat air pressure in system After stablizing dry terminate, dried gel is put into initial aqueous solution, 18 minutes are stood, then with 8 DEG C/min of speed 89 DEG C and at this temperature constant temperature 3 hours are risen to, then puts it into 118 DEG C of drying boxes after drying 20 hours and is put into tubular type In stove, it is warming up to 400 DEG C with 10 DEG C/min of speed in air atmosphere and is kept for 1 hour at this temperature, then in argon gas 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 with 10 in atmosphere DEG C/min speed be warming up to 950 DEG C and kept for 10 hours at this temperature, the double calcium of continuous electronic ion Quick conductive are made Titanium ore kalium ion battery negative material.
Embodiment 4：By potassium nitrate, six nitric hydrate terbiums, lithium nitrate, barium nitrate, five nitric hydrate zirconiums, six nitric hydrates Yttrium, Fe(NO3)39H2O, zinc nitrate hexahydrate, niobium oxalate are according to stoichiometric equation KTb0.5Ba0.2Y0.2Li0.1Zr0.8Fe0.1Zn0.1NbO6Mixing, the amount for adding material are the lemon of 9 times of the amount of total metal ion species Lemon acid and add water to stir to form total concentration of metal ions be 1.8molL-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 dry Dry process uses finished product freeze drier in the market, and gel is put into freeze drier sample disc and starts refrigeration machine, 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, open baffle temperature control and start to dehydrate, other operating parameters take machine preset value, treat air pressure in system After stablizing 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 110 DEG C of drying boxes after drying 15 hours 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, and it is double that the continuous electronic ion Quick conductive is made Perovskite kalium ion battery negative material.
Embodiment 5：By potassium nitrate, six nitric hydrate terbiums, lithium nitrate, barium nitrate, five nitric hydrate zirconiums, six nitric hydrates Yttrium, Fe(NO3)39H2O, zinc nitrate hexahydrate, niobium oxalate are according to stoichiometric equation KTb0.5Ba0.2Y0.2Li0.1Zr0.8Fe0.1Zn0.1NbO6Mixing, the amount for adding material are the lemon of 8 times of the amount of total metal ion species Lemon acid and add water to stir to form total concentration of metal ions be 2.3molL-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 1.2 times of the amount of total metal ion species in initial aqueous solution in solution； It is risen to 85 with 10 DEG C/min of speed after being stirred 10 minutes with 2000rpm speed using Teflon stir oar DEG C and keep the temperature until it becomes gelatin gel.The gel of formation is dried in the environment of low-temperature high-vacuum degree, should Gel is put into start in freeze drier sample disc and freezed by drying process using finished product freeze drier in the market Machine, treat that gelling temp is reduced to subzero 45 DEG C in sample disc, open vavuum pump and improve vacuum, treat that gas pressure reduces in system To below 35Pa, open baffle temperature control and start to dehydrate, other operating parameters take machine preset value, treat gas in system After pressure stablizes dry terminate, dried gel is put into initial aqueous solution, 15 minutes are stood, then with 10 DEG C/min Speed rises to 90 DEG C and at this temperature constant temperature 3 hours, then puts it into 110 DEG C of drying boxes after drying 20 hours and is put into In tube furnace, 400 DEG C and at this temperature holding 0.8 hour are warming up to 8 DEG C/min of speed in air atmosphere, then 550 DEG C are warming up to 10 DEG C/min of speed and continue after being kept for 3 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 kalium ion battery negative material.

Claims (1)

1. a kind of continuous electronic ion Quick conductive double-perovskite kalium ion battery negative material, it is characterized in that：Form and be KTb0.5Ba0.2Y0.2Li0.1Zr0.8Fe0.1Zn0.1NbO6, preparation process is by potassium nitrate, six nitric hydrate terbiums, lithium nitrate, nitric acid Barium, five nitric hydrate zirconiums, six nitric hydrate yttriums, Fe(NO3)39H2O, zinc nitrate hexahydrate, niobium oxalate are according to stoichiometric equation KTb0.5Ba0.2Y0.2Li0.1Zr0.8Fe0.1Zn0.1NbO6Mixing, the amount for adding material are 5-10 times of the amount of total metal ion species Citric acid and add water to stir to form total concentration of metal ions be 1.0-2.5molL-1Initial aqueous solution；By 6g acryloyls The acrylamide and 1gN, N of amine/100mL waters '-methylene-bisacrylamide/100mL waters N, N '-methylene bisacrylamide Acid amides and water mixed dissolution, the amount of the material of acrylamide is the amount of total metal ion species in initial aqueous solution in solution 0.5-1.2 times；Using Teflon stir oar with after 1500rpm-2000rpm speed stirring 5-15 minutes by it with 5-10 DEG C/min speed rise to 75-85 DEG C and keep the temperature until it becomes gelatin gel；By the gel of formation in low temperature Dried in the environment of condition of high vacuum degree, gel is put into freezing by the drying process using finished product freeze drier in the market Start refrigeration machine in drying machine sample disc, treat that gelling temp is reduced to subzero 50 DEG C of subzero 45- in sample disc, open vavuum pump and carry Condition of high vacuum degree, treat that gas pressure is reduced to below 25-35Pa in system, open baffle temperature control and start to dehydrate, other Operating parameter takes machine preset value, after stable gas pressure drying terminates in system, dried gel is put into initial water-soluble In liquid, 10-20 minutes are stood, then 75-90 DEG C is risen to 5-10 DEG C/min of speed and constant temperature 1-3 is small at this temperature When, then put it into 80 DEG C of -120 DEG C of drying boxes after drying 10-20 hours and be put into tube furnace, with 2- in air atmosphere 10 DEG C/min of speed is warming up to 300-400 DEG C and kept for 0.5-1 hours at this temperature, then with 2- in argon gas atmosphere 10 DEG C/min of speed is warming up to 400-550 DEG C and continued after keeping 2-4 hours at this temperature in argon gas atmosphere with 2-10 DEG C/min speed be warming up to 800-950 DEG C and at this temperature keep 4-10 hours, be made the continuous electronic ion quickly lead Electric double-perovskite kalium ion battery negative material.
CN201710550970.2A 2017-06-29 2017-06-29 A kind of continuous electronic ion Quick conductive double-perovskite kalium ion battery negative material and preparation method thereof Pending CN107359332A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05330827A (en) * 1991-12-06 1993-12-14 Rhone Poulenc Chim Perovskite wherein tantalum or niobium is base material and preparation thereof
CN102534546A (en) * 2012-01-16 2012-07-04 燕山大学 Preparation method of perovskite type nanocrystalline thin film on glass substrate
CN104078647A (en) * 2013-03-27 2014-10-01 比亚迪股份有限公司 Lithium ion battery negative electrode, preparing method of lithium ion battery negative electrode and lithium ion battery
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05330827A (en) * 1991-12-06 1993-12-14 Rhone Poulenc Chim Perovskite wherein tantalum or niobium is base material and preparation thereof
CN102534546A (en) * 2012-01-16 2012-07-04 燕山大学 Preparation method of perovskite type nanocrystalline thin film on glass substrate
CN104078647A (en) * 2013-03-27 2014-10-01 比亚迪股份有限公司 Lithium ion battery negative electrode, preparing method of lithium ion battery negative electrode and lithium ion battery
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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