CN113410456A - O3 type sodium ion battery layered positive electrode material with low sodium content - Google Patents
O3 type sodium ion battery layered positive electrode material with low sodium content Download PDFInfo
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- CN113410456A CN113410456A CN202110726094.0A CN202110726094A CN113410456A CN 113410456 A CN113410456 A CN 113410456A CN 202110726094 A CN202110726094 A CN 202110726094A CN 113410456 A CN113410456 A CN 113410456A
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- 239000011734 sodium Substances 0.000 title claims abstract description 64
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 34
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 28
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 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 title claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 12
- 239000010405 anode material Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 5
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 5
- 229910019020 PtO2 Inorganic materials 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910000417 bismuth pentoxide Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 15
- 238000013461 design Methods 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract 4
- 238000000034 method Methods 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000004146 energy storage Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 239000013078 crystal Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 201000004569 Blindness Diseases 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the field of electrochemical power sources, and particularly relates to a layered positive electrode material of an O3 type sodium-ion battery with low sodium content. The chemical formula of the layered anode material is Na0.67AxByCzDrO2The transition metal layer comprises two or three kinds of transition metal elements, wherein A is selected from two or three kinds of divalent metal ions, B is selected from two or three kinds of trivalent metal ions, C is selected from two or three kinds of tetravalent metal ions, D is selected from one or two kinds of pentavalent metal ions, the number of the transition metal elements is 7-10, x + y + z + r =1, and 2.8-2 x +3y +4z +5 r-3.2. The invention successfully obtains the O3 type structural material with low sodium content based on the specific high-entropy transition metal layer component, so that the structural design of the material is more controllable, new insight is provided for the optimized design of the layered positive electrode material of the high-performance sodium-ion battery, and the invention has wide application prospect.
Description
Technical Field
The invention belongs to the field of electrochemical power sources, and particularly relates to a layered positive electrode material of an O3 type sodium-ion battery with low sodium content.
Background
As concerns about environmental problems and rapid consumption of fossil fuels continue to grow, the strong demand of modern society for the utilization of renewable energy and the popularization of smart grids have driven the development of advanced energy storage technologies, and the demand of large electrochemical energy storage systems has received great attention in the past decades. Among various electric energy storage systems, rechargeable batteries are considered as one of the most typical representatives of advanced energy storage technologies due to their high safety, high conversion efficiency, low cost, and environmental friendliness. The alkali metal ion battery occupies an extremely important position in the field of energy storage due to the advantages of high energy density, long cycle life and the like.
In recent years, the layered oxide positive electrode material in the alkali metal ion battery has a series of advantages of reversible lithium ion, sodium ion and other crystal structures, high specific capacity, simple preparation method, low price and the like, so that the intensive research of scientists in the field of energy storage becomes a focus of much attention.
Layered transition metal oxide NaxMO2(M is transition metal) is one of the most widely studied candidate materials at present, sodium ions in P2 type occupy the space positions of triangular prisms, the arrangement rule of oxygen layers is ABBA, and x is more than or equal to 0.45 and less than or equal to 0.8; the sodium ions of the O3 type material occupy octahedral positions, the arrangement rule of the oxygen layers is ABCABC, and x is more than or equal to 0.8 and less than or equal to 1. The difference of the crystal structure naturally has obvious influence on the electrochemical performance of the material.
The difference of the phase structure is closely related to the content of sodium ions contained in the material, generally speaking, the high Na content (0.8 is not less than x and not more than 1) is helpful for forming an O3 type structure, while the low Na content (0.45 is not less than x and not more than 0.8) is used for forming a P2 type structure, and the design and the control of the structure mainly depend on trial experiments with high flux, so that the method has obvious blindness.
Disclosure of Invention
The invention aims to provide a layered positive electrode material of an O3 type sodium-ion battery with low sodium content, which comprises the following components in percentage by weight: the chemical formula of the layered anode material is Na0.67AxByCzDrO2A is selected from two or three of divalent metal elements, B is selected from two or three of trivalent metal elements, C is selected from two or three of tetravalent metal elements, and D is selected from one or two of pentavalent metal elements.
Layered positive electrode material Na0.67AxByCzDrO2The kind of the medium transition metal layer element is between 7 and 10.
Layered positive electrode material Na0.67AxByCzDrO2Wherein x, y, z and r are respectively the mole fractions of the corresponding elements in the transition metal element component, and the relationship satisfies that x + y + z + r is 1, and 2.8 is less than or equal to 2x +3y +4z +5r is less than or equal to 3.2.
The A element is two or three of Ni, Cu, Mg or Zn;
the element B is two or three of Fe, Co, Al, Sc or In;
the C element is two or three of Mn, Ti, Sn, V, Cr, Zr or Hf;
the element D is one or two of Sb, Nb, Mo, Pt or Bi.
The material can be prepared by applying a traditional solid phase method, and the method comprises the following specific steps:
(3) feeding, grinding and uniformly mixing metal oxides of corresponding elements according to a proportion, grinding for 24-36 h, and pressing the uniformly ground powder into a wafer with the diameter of 10mm under the pressure of 10MPa by using a tablet machine;
(4) placing the wafer in a crucible, moving the wafer to a muffle furnace, and carrying out temperature programming calcination; the calcination temperature is 800-1000 ℃; the calcining time is 10-15 h, and the O3 type sodium-ion battery layered positive electrode material with low sodium content is obtained.
In the temperature programming calcination step, the temperature rise rate is 3-8 ℃ min-1。
The corresponding oxide is NiO, CuO, MgO, ZnO and Fe2O3,Co3O4,Al2O3,Sc2O3,In2O3,Mn2O3,TiO2,SnO2,VO2,Cr2O3,ZrO2,HfO2,Sb2O3,Nb2O5,MoO3,PtO2,Bi2O5。
Reagents and apparatus according to the present invention are commercially available unless otherwise specified.
By comparing diffraction patterns of XRD, the above materials all have a diffraction peak with a plane index of (003), and the standard diffraction pattern of O3 phase is satisfied, so that the material can be judged to be O3 type material.
Compared with the prior art, the invention has more targeting property on the structural design of the sodium ion layered cathode material, provides reference for designing a high-performance cathode material, and has certain regularity and universality.
The composite anode is prepared by mixing the materials with a conductive additive, a binder and a solvent according to a certain proportion and carrying out the processes of pulping, smearing, drying and the like. The obtained pole piece is assembled with the diaphragm, the organic electrolyte and the cathode metal sodium in the glove box, and the sodium ion battery can be obtained to store and release energy.
According to the invention, by constructing the components of the high-entropy transition metal layer, the charge disorder of the transition metal layer is promoted, the interaction between the transition metal layer and the oxygen layer is weakened, and further the coulomb interaction between the sodium layer and the oxygen layer is enhanced, so that sodium ions still occupy octahedral positions with narrower interlayer spacing under low sodium content, and an O3 type structure is presented.
Drawings
FIG. 1 shows Na0.67Ni0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2XRD pattern of
Detailed Description
The invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings.
In the figure, the three strong peaks of the P2 phase have (002), (012) and (104) plane indexes at diffraction angles of 15.79 °, 39.45 ° and 48.84 °, and the three strong peaks of the O3 phase have (003), (012) and (104) plane indexes at diffraction angles of 16.58 °, 36.89 ° and 41.91 °, respectively, and the comparison of diffraction patterns by XRD shows that all the materials have a diffraction peak with a plane index of (003) and meet the standard diffraction pattern of the O3 phase, so that the material can be judged to be the O3 type material.
Example 1
(A1)) Preparation of Na0.67Ni0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2Positive electrode material
Weighing Na with corresponding mass according to the amount of the substances in the target product2CO3、NiO、CuO、MgO、Fe2O3、Co3O4、Mn2O3、TiO2、Sb2O3、SnO2Ball-milling for 24h, mixing uniformly, pressing into a wafer with the diameter of 10mm under the pressure of 10MPa, placing in a muffle furnace, heating at 900 ℃ and calcining for 15h to obtain sample powder, wherein the heating rate is 8 ℃ for min-1。
(II) para Na0.67Ni0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2XRD (X-ray diffraction) test is carried out on the anode material sample powder
Obtaining Na by using X-ray diffractometer by utilizing diffraction effect of X-rays in crystalline substance0.67Ni0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2The XRD patterns of the sample powders were analyzed for the structure of the material with reference to a standard PDF card, as shown in the figure.
(III) application:
Na0.67Ni0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2preparation of composite cathode
The prepared anode material prepared in the embodiment is uniformly mixed with a conductive additive Super-P and a binder polyvinylidene fluoride (PVDF) according to the mass ratio of 8: 1, and a solvent N-methyl pyrrolidone is added to obtain a composite anode through the processes of pulping, smearing, drying and the like.
Assembling the prepared composite anode and a sodium cathode into a sodium ion battery in a glove box, and selecting electrolyteCarbonate electrolyte (1M NaClO)4The EC/PC (volume ratio 1:1) solution) of (a), the above sodium ion battery was subjected to a charge-discharge test at a constant rate of 0.2C using a blue charge-discharge tester, and the results were good.
Example 2
(one) preparation of Na0.67Ni0.12Cu0.12Zn0.12Fe0.1Co0.1Al0.1Mn0.1V0.1Sb0.14O2And (3) a positive electrode material. (raw material is Na)2CO3、NiO、CuO、ZnO、Fe2O3、Co3O4、Al2O3、Mn2O3、VO2、Sb2O3The other steps are the same as those in example 1)
(II) para Na0.67Ni0.12Cu0.12Zn0.12Fe0.1Co0.1Al0.1Mn0.1V0.1 Sb0.14O2XRD testing of the sample powder (same procedure as in example 1)
(III) application (the concrete steps are the same as those in example 1)
Example 3
(one) preparation of Na0.67Ni0.18Zn0.18Fe0.1Sc0.1Al0.1Mn0.1V0.1Ti0.1Nb0.04O2And (3) a positive electrode material. (raw material is Na)2CO3、NiO、ZnO、Fe2O3、Sc2O3、Al2O3、Mn2O3、VO2、TiO2、Nb2O5The rest steps are the same as
Example 1)
(II) para Na0.67Ni0.18Zn0.18Fe0.1Sc0.1Al0.1Mn0.1V0.1Ti0.1Nb0.04O2XRD testing of the sample powder (same procedure as in example 1)
(III) application (the concrete steps are the same as those in example 1)
Example 4
(one) preparation of Na0.67Mg0.18Zn0.18Fe0.1Sc0.1In0.1Mn0.16Ti0.16Pt0.02O2And (3) a positive electrode material. (raw material is Na)2CO3、MgO、ZnO、Fe2O3、Sc2O3、In2O3、Mn2O3、TiO2、PtO2The other steps are the same as those in example 1)
(II) para Na0.67Mg0.18Zn0.18Fe0.1Sc0.1In0.1Mn0.16Ti0.16Pt0.02O2XRD testing of the sample powder (same procedure as in example 1)
(III) application (the concrete steps are the same as those in example 1)
Example 5
(one) preparation of Na0.67Ni0.12Zn0.12Mg0.12Sc0.15Al0.15Sn0.11V0.11Hf0.11Pt0.01O2And (3) a positive electrode material. (raw material is Na)2CO3、NiO、ZnO、MgO、Sc2O3、Al2O3、SnO2、VO2、HfO2、PtO2The other steps are the same as those in example 1)
(II) para Na0.67Ni0.12Zn0.12Mg0.12Sc0.15Al0.15Sn0.11V0.11Hf0.11Pt0.01O2XRD testing of the sample powder (same procedure as in example 1)
(III) application (the concrete steps are the same as those in example 1)
Comparative example 1
(one) preparation of Na0.67Ni0.18Mg0.18Co0.3Mn0.23Sn0.2O2And (3) a positive electrode material. (raw material is Na)2CO3、NiO、MgO、Co3O4、Mn2O3、SnO2The other steps are performed in the same wayEXAMPLE 1)
(II) para Na0.67Ni0.18Mg0.18Co0.3Mn0.23Sn0.2O2XRD testing of the sample powder (same procedure as in example 1)
(III) application (the concrete steps are the same as those in example 1)
Comparative example 2
(one) preparation of Na0.67Ni0.12Cu0.12Mg0.12Al0.15Co0.15Mn0.43O2And (3) a positive electrode material. (raw material is Na)2CO3、NiO、CuO、MgO、Al2O3、Co3O4、Mn2O3The other steps are the same as those in example 1)
(II) para Na0.67Ni0.12Cu0.12Mg0.12Al0.15Co0.15Mn0.43O2XRD testing of the sample powder (same procedure as in example 1)
(III) application (the concrete steps are the same as those in example 1)
Comparative example 3
(one) preparation of Na0.67Ni0.18Mg0.18Co0.3Sn0.2Mn0.14O2And (3) a positive electrode material. (raw material is Na)2CO3、NiO、MgO、Co3O4、SnO2、Mn2O3The other steps are the same as those in example 1)
(II) para Na0.67Ni0.18Mg0.18Co0.3Sn0.2Mn0.14O2XRD testing of the sample powder (same procedure as in example 1)
(III) application (the concrete steps are the same as those in example 1)
Comparative example 4
(one) preparation of Na0.67Ni0.12Cu0.12Mg0.12Co0.3Mn0.34O2And (3) a positive electrode material. (raw material is Na)2CO3、NiO、CuO、MgO、Co3O4、Mn2O3The rest steps are the same as the embodiment1)
(II) para Na0.67Ni0.12Cu0.12Mg0.12Co0.3Mn0.34O2XRD testing of the sample powder (same procedure as in example 1)
(III) application (the concrete steps are the same as those in example 1)
Comparative example 5
(one) preparation of Na0.67Ni0.36Al0.1Fe0.1Co0.1Ti0.1Mn0.24O2And (3) a positive electrode material. (raw material is Na)2CO3、NiO、Al2O3、Co3O4、Fe2O3、TiO2、Mn2O3The other steps are the same as those in example 1)
(II) para Na0.67Ni0.36Al0.1Fe0.1Co0.1Ti0.1Mn0.24O2XRD testing of the sample powder (same procedure as in example 1)
(III) application (the concrete steps are the same as those in example 1)
As can be seen from the comparison of the above examples with comparative examples, examples 1, 2, 3, 4, 5 obtained the O3 phase in the case where the kinds of transition metal layer elements were not less than 7 and not more than 10, while the transition metal layer compositions of comparative examples 1, 2, 3, 4, 5 did not satisfy this requirement and no O3 phase was obtained under the conditions of the same temperature and reaction time by the high-temperature solid phase method, so that the method of designing the O3-type layered cathode material with low sodium content based on the high-entropy transition metal layer composition was effectively feasible.
In conclusion, the layered positive electrode material of the O3 type sodium-ion battery with low sodium content, which is obtained based on the construction of the high-entropy transition metal layer component, has the advantages of simple corresponding preparation method, easily obtained raw materials and low price, so the invention can provide new insight for the optimization design of the structure of the layered positive electrode material of the high-performance sodium-ion battery, and has wide application prospect.
The above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the embodiments of the present invention, and those skilled in the art can easily make various changes or modifications according to the main concept and spirit of the present invention, so the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (8)
1. A low-sodium-content O3 type sodium ion layered positive electrode material is characterized in that: the chemical formula of the layered anode material is Na0.67AxByCzDrO2A is selected from two or three of divalent metal elements, B is selected from two or three of trivalent metal elements, C is selected from two or three of tetravalent metal elements, and D is selected from one or two of pentavalent metal elements;
layered positive electrode material Na0.67AxByCzDrO2The types of the elements of the middle transition metal layer are between 7 and 10;
layered positive electrode material Na0.67AxByCzDrO2Wherein x, y, z and r are respectively the mole fractions of the corresponding elements in the transition metal element component, and the relationship satisfies that x + y + z + r is 1, and 2.8 is less than or equal to 2x +3y +4z +5r is less than or equal to 3.2.
2. The layered positive electrode material of O3 type Na ion with low Na content of claim 1, wherein A is two or three of Ni, Cu, Mg and Zn.
3. The layered positive electrode material of O3 type Na ion with low Na content of claim 1, wherein B is two or three of Fe, Co, Al, Sc and In.
4. The layered positive electrode material of O3 type Na ion with low Na content of claim 1, wherein the C element is two or three of Mn, Ti, Sn, V, Cr, Zr and Hf.
5. The O3 type Na-ion layered positive electrode material with low Na content according to claim 1, wherein the D element is one or two of Sb, Nb, Mo, Pt and Bi.
6. The O3 type sodium ion layered positive electrode material with low sodium content of claim 1, wherein the preparation method of the O3 type sodium ion layered positive electrode material with low sodium content comprises the following steps:
(1) feeding, grinding and uniformly mixing metal oxides of corresponding elements according to a proportion, grinding for 24-36 h, and pressing the uniformly ground powder into a wafer with the diameter of 10mm under the pressure of 10MPa by using a tablet machine;
(2) placing the wafer in a crucible, moving the wafer to a muffle furnace, and carrying out temperature programming calcination; the calcination temperature is 800-1000 ℃; the calcining time is 10-15 h, and the O3 type sodium-ion battery layered positive electrode material with low sodium content is obtained.
7. The O3 type sodium ion layered positive electrode material with low sodium content according to claim 6, wherein in the temperature programming calcination step, the temperature rise rate is 3-8 ℃ for min-1。
8. The layered positive electrode material of O3 type Na-ion with low Na-content as claimed in claim 6, wherein the corresponding oxide is NiO, CuO, MgO, ZnO, Fe2O3,Co3O4,Al2O3,Sc2O3,In2O3,Mn2O3,TiO2,SnO2,VO2,Cr2O3,ZrO2,HfO2,Sb2O3,Nb2O5,MoO3,PtO2,Bi2O5。
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