CN107352587A - A kind of electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery and preparation method thereof - Google Patents
A kind of electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery and preparation method thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 230000005684 electric field Effects 0.000 title claims abstract description 24
- 239000010405 anode material Substances 0.000 title claims abstract description 19
- 230000033228 biological regulation Effects 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 14
- 238000007710 freezing Methods 0.000 title claims abstract description 13
- 230000008014 freezing Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 67
- 238000000498 ball milling Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 13
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012047 saturated solution Substances 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 11
- 239000004809 Teflon Substances 0.000 claims description 7
- 229920006362 Teflon® Polymers 0.000 claims description 7
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 7
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 7
- 239000004323 potassium nitrate Substances 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 2
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 16
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 10
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- 239000011734 sodium Substances 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 238000006479 redox reaction Methods 0.000 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 230000003139 buffering effect Effects 0.000 abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000003746 solid phase reaction Methods 0.000 abstract description 3
- 238000010671 solid-state reaction Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 150000004677 hydrates Chemical class 0.000 description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000004087 circulation Effects 0.000 description 4
- 238000009831 deintercalation Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 oxonium ions Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01M4/48—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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery and preparation method thereof, it is characterized in that：The composition of the negative material is NaBa0.3La0.3K0.4Zr0.8Ni0.1Mn0.1MoO6, 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 turns into continuous poriferous pattern；The pattern advantageously reduces crystal boundary resistance, electromigration resistance；Accelerate the speed of sodium ion transfer ability and redox reaction；Also there is certain structural rigidity, buffering is formed for Volume Changes；Further occupied jointly by the Na and La of A positions, Ba, K of La positions are adulterated and the Ni of B positions, Mn adulterate so as to form high performance anode material of lithium-ion battery.
Description
Technical field
The present invention relates to a kind of anode material of lithium-ion battery 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 sodium 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 anode material of lithium-ion battery of alloy mechanism is it can also happen that following electrification
Learn reaction：
2Na++MeO+2e-→Na2O+Me0
Nam+Me0 n→NamMe0 n
And larger specific capacity can be discharged, but generally because sodium 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 sodium-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 compound can carry out alloy reaction, it can when carrying out alloy reaction with two kinds of metals
The Alloy solid solution of a variety of phases can be produced, 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 anode material of lithium-ion battery, and it may be provided
Near or above 500mAh.g-1Specific capacity, sodium ion enter or abjection material volume change it is also smaller；But the material exists
Research and development in sodium-ion battery is substantially at blank.And its subject matter is：1st, ionic conductivity and electronic conductivity
It is relatively low；2nd, the product sodium oxide molybdena after conversion reaction is electronic body and its sodium ion Diffusion Activation Energy is also higher, is caused larger
Activation polarization；3rd, synthesis temperature is higher, easily causes growing up and reuniting for crystal grain.
For these problems, these problems, such as by material can be extenuated to a certain extent by changing the pattern of material
Particle size reduction can reduce the approach of sodium ion diffusion to the yardstick of nanometer, shorten diffusion time of sodium 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 sodium 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 anode material of lithium-ion battery.
The content of the invention
The present invention proposes a kind of electric field regulation and control selective freezing synthesis double-perovskite sodium 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
NaBa0.3La0.3K0.4Zr0.8Ni0.1Mn0.1MoO6, the electricity for applying specific direction in high temperature solid state reaction is utilized in preparation process
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 turns into
Continuous poriferous pattern；Such pattern advantageously reduces crystal boundary resistance, improves locomitivity of the sodium ion in lattice；The company of being formed
Continuous electron transfer network, reduce electromigration resistance；Increase and the contact area of electrolyte, accelerate in electrolyte and lattice
The speed of sodium ion transfer ability and redox reaction；Such structure also has certain structural rigidity, is discharge and recharge
Material volume in journey changes to form buffering；Further occupied jointly by the Na and La of A positions, improve electronic conductivity and lead to
Ba, K doping of La positions are crossed, improves sodium ion electrical conductivity；By the Ni of B positions, Mn doping improves the stability of perovskite structure,
Ultimately form high performance anode material of lithium-ion battery.
This electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery, its preparation method are：By nitre
Sour barium, sodium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, four nitric hydrate manganese, Ammonium Molybdate Tetrahydrate, six hydrations
Nickel nitrate is according to stoichiometric equation NaBa0.3La0.3K0.4Zr0.8Ni0.1Mn0.1MoO6It is put into ball mill, ball milling and material
Mass ratio is 20: 1, with 200-400 revs/min of speed ball milling 10-20 hours.By the material after ball milling in tube furnace with 2-
10 DEG C/min of speed, which is warming up to after 800-900 DEG C, applies a DC voltage at the both ends of tube furnace, voltage 600-900V,
Cool to 30 DEG C with the furnace at this temperature and after being incubated 3-6 hours under electric field；Material after cooling is ground into 5-15 in mortar
Minute, 30 DEG C of lithium metaborate saturations of constant temperature are immersed in the case where Teflon stir oar is persistently stirred with 900-1200rpm speed
In solution, the quality of lithium metaborate saturated solution and the mass ratio of the material after the cooling immersed are 10: 1, persistently stir 5-10
After minute, thermostat temperature is reduced to 18-22 DEG C and continues to stir 5-15 minutes, is filtered thereafter, in 120-160 DEG C of drying box
Middle dry 5-10 hours.Then dried material is warming up to 450-550 DEG C in tube furnace with 2-10 DEG C/min of speed
And electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery is made in insulation 3-5 hours at this temperature.
Compared with prior art, the advantage of the invention is that：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 turns into
Continuous poriferous pattern；Such pattern advantageously reduces crystal boundary resistance, improves locomitivity of the sodium ion in lattice；The company of being formed
Continuous electron transfer network, reduce electromigration resistance；Increase and the contact area of electrolyte, accelerate in electrolyte and lattice
The speed of sodium ion transfer ability and redox reaction；Such structure also has certain structural rigidity, is discharge and recharge
Material volume in journey changes to form buffering；Further occupied jointly by the Na and La of A positions, improve electronic conductivity and lead to
Ba, K doping of La positions are crossed, improves sodium ion electrical conductivity；By the Ni of B positions, Mn doping improves the stability of perovskite structure,
Ultimately form high performance anode material of lithium-ion battery.
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 barium nitrate, sodium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, four nitric hydrates
Manganese, Ammonium Molybdate Tetrahydrate, Nickelous nitrate hexahydrate are according to stoichiometric equation NaBa0.3La0.3K0.4Zr0.8Ni0.1Mn0.1MoO6It is put into ball
In grinding machine, ball milling is 20: 1 with the mass ratio of material, with 400 revs/min of speed ball milling 20 hours.By the material after ball milling
It is warming up in tube furnace with 10 DEG C/min of speed after 900 DEG C and applies a DC voltage at the both ends of tube furnace, voltage is
900V, cool to 30 DEG C with the furnace at this temperature and after being incubated 5 hours under electric field；Material after cooling is ground 12 in mortar
Minute, 30 DEG C of lithium metaborate saturated solutions of constant temperature are immersed in the case where Teflon stir oar is persistently stirred with 1200rpm speed
In, the mass ratio of the quality of lithium metaborate saturated solution and the material after the cooling immersed is 10: 1, after persistently stirring 9 minutes,
Thermostat temperature is reduced to 22 DEG C and continues stirring 15 minutes, filters thereafter, is dried 10 hours in 160 DEG C of drying box.So
Dried material is warming up to 550 DEG C and is incubated 5 hours at this temperature in tube furnace with 10 DEG C/min of speed afterwards and is made
Obtain electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery.
Embodiment 2：By barium nitrate, sodium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, four nitric hydrates
Manganese, Ammonium Molybdate Tetrahydrate, Nickelous nitrate hexahydrate are according to stoichiometric equation NaBa0.3La0.3K0.4Zr0.8Ni0.1Mn0.1MoO6It is put into ball
In grinding machine, ball milling is 20: 1 with the mass ratio of material, with 400 revs/min of speed ball milling 15 hours.By the material after ball milling
It is warming up in tube furnace with 8 DEG C/min of speed after 900 DEG C and applies a DC voltage at the both ends of tube furnace, voltage is
900V, cool to 30 DEG C with the furnace at this temperature and after being incubated 5 hours under electric field；Material after cooling is ground 12 in mortar
Minute, 30 DEG C of lithium metaborate saturated solutions of constant temperature are immersed in the case where Teflon stir oar is persistently stirred with 1000rpm speed
In, the mass ratio of the quality of lithium metaborate saturated solution and the material after the cooling immersed is 10: 1, after persistently stirring 7 minutes,
Thermostat temperature is reduced to 18 DEG C and continues stirring 10 minutes, filters thereafter, is dried 8 hours in 140 DEG C of drying box.Then
Dried material is warming up to 500 DEG C and is incubated 4 hours at this temperature in tube furnace with 7 DEG C/min of speed and is made
Electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery.
Embodiment 3：By barium nitrate, sodium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, four nitric hydrates
Manganese, Ammonium Molybdate Tetrahydrate, Nickelous nitrate hexahydrate are according to stoichiometric equation NaBa0.3La0.3K0.4Zr0.8Ni0.1Mn0.1MoO6It is put into ball
In grinding machine, ball milling is 20: 1 with the mass ratio of material, with 200 revs/min of speed ball milling 10 hours.By the material after ball milling
It is warming up in tube furnace with 2 DEG C/min of speed after 800 DEG C and applies a DC voltage at the both ends of tube furnace, voltage is
600V, cool to 30 DEG C with the furnace at this temperature and after being incubated 3 hours under electric field；Material after cooling is ground 6 in mortar
Minute, 30 DEG C of lithium metaborate saturated solutions of constant temperature are immersed in the case where Teflon stir oar is persistently stirred with 900rpm speed
In, the mass ratio of the quality of lithium metaborate saturated solution and the material after the cooling immersed is 10: 1, after persistently stirring 5 minutes,
Thermostat temperature is reduced to 20 DEG C and continues stirring 5 minutes, filters thereafter, is dried 5 hours in 120 DEG C of drying box.Then
Dried material is warming up to 450 DEG C and is incubated 3 hours at this temperature in tube furnace with 3 DEG C/min of speed and is made
Electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery.
Embodiment 4：By barium nitrate, sodium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, four nitric hydrates
Manganese, Ammonium Molybdate Tetrahydrate, Nickelous nitrate hexahydrate are according to stoichiometric equation NaBa0.3La0.3K0.4Zr0.8Ni0.1Mn0.1MoO6It is put into ball
In grinding machine, ball milling is 20: 1 with the mass ratio of material, with 300 revs/min of speed ball milling 15 hours.By the material after ball milling
It is warming up in tube furnace with 8 DEG C/min of speed after 850 DEG C and applies a DC voltage at the both ends of tube furnace, voltage is
900V, cool to 30 DEG C with the furnace at this temperature and after being incubated 6 hours under electric field；Material after cooling is ground 15 in mortar
Minute, 30 DEG C of lithium metaborate saturated solutions of constant temperature are immersed in the case where Teflon stir oar is persistently stirred with 1000rpm speed
In, the mass ratio of the quality of lithium metaborate saturated solution and the material after the cooling immersed is 10: 1, after persistently stirring 7 minutes,
Thermostat temperature is reduced to 20 DEG C and continues stirring 5 minutes, filters thereafter, is dried 5 hours in 120 DEG C of drying box.Then
Dried material is warming up to 520 DEG C and is incubated 5 hours at this temperature in tube furnace with 8 DEG C/min of speed and is made
Electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery.
Embodiment 5：By barium nitrate, sodium nitrate, potassium nitrate, lanthanum nitrate hexahydrate, five nitric hydrate zirconiums, four nitric hydrates
Manganese, Ammonium Molybdate Tetrahydrate, Nickelous nitrate hexahydrate are according to stoichiometric equation NaBa0.3La0.3K0.4Zr0.8Ni0.1Mn0.1MoO6It is put into ball
In grinding machine, ball milling is 20: 1 with the mass ratio of material, with 400 revs/min of speed ball milling 20 hours.By the material after ball milling
It is warming up in tube furnace with 6 DEG C/min of speed after 850 DEG C and applies a DC voltage at the both ends of tube furnace, voltage is
800V, cool to 30 DEG C with the furnace at this temperature and after being incubated 5 hours under electric field；Material after cooling is ground 12 in mortar
Minute, 30 DEG C of lithium metaborate saturated solutions of constant temperature are immersed in the case where Teflon stir oar is persistently stirred with 1100rpm speed
In, the mass ratio of the quality of lithium metaborate saturated solution and the material after the cooling immersed is 10: 1, after persistently stirring 7 minutes,
Thermostat temperature is reduced to 19 DEG C and continues stirring 12 minutes, filters thereafter, is dried 7 hours in 150 DEG C of drying box.Then
Dried material is warming up to 500 DEG C and is incubated 5 hours at this temperature in tube furnace with 8 DEG C/min of speed and is made
Electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery.
Claims (1)
1. a kind of electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery, it is characterized in that：Form and be
NaBa0.3La0.3K0.4Zr0.8Ni0.1Mn0.1MoO6, preparation process be by barium nitrate, sodium nitrate, potassium nitrate, lanthanum nitrate hexahydrate,
Five nitric hydrate zirconiums, four nitric hydrate manganese, Ammonium Molybdate Tetrahydrate, Nickelous nitrate hexahydrate are according to stoichiometric equation
NaBa0.3La0.3K0.4Zr0.8Ni0.1Mn0.1MoO6It is put into ball mill, the mass ratio of ball milling and material is 20: 1, with 200-
400 revs/min of speed ball milling 10-20 hours；Material after ball milling is heated up in tube furnace with 2-10 DEG C/min of speed
Apply a DC voltage at the both ends of tube furnace after to 800-900 DEG C, voltage 600-900V, protect at this temperature and under electric field
30 DEG C are cooled to the furnace after warm 3-6 hours；Material after cooling is ground into 5-15 minutes in mortar, in Teflon stir
Oar is persistently stirred in lower immersion 30 DEG C of lithium metaborate saturated solutions of constant temperature with 900-1200rpm speed, and lithium metaborate saturation is molten
The mass ratio of the quality of liquid and the material after the cooling immersed is 10: 1, and after persistently stirring 5-10 minutes, thermostat temperature is reduced
To 18-22 DEG C and continue to stir 5-15 minutes, filter thereafter, 5-10 hours are dried in 120-160 DEG C of drying box；Then will
Dried material is warming up to 450-550 DEG C in tube furnace with 2-10 DEG C/min of speed and insulation 3-5 is small at this temperature
When be made the electric field regulation and control selective freezing synthesis double-perovskite anode material of lithium-ion battery.
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