CN109585795A - Mixed phase structure layered oxide material and its preparation method and application - Google Patents
Mixed phase structure layered oxide material and its preparation method and application Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical group 0.000 claims abstract description 5
- 239000012071 phase Substances 0.000 claims description 67
- 239000002243 precursor Substances 0.000 claims description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 31
- 239000011572 manganese Substances 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 18
- 229910001415 sodium ion Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 13
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000975 co-precipitation Methods 0.000 claims description 7
- 238000004146 energy storage Methods 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 238000010248 power generation Methods 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 5
- 239000002738 chelating agent Substances 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 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 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000002482 conductive additive Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 229910014211 My O Inorganic materials 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 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 15
- 229910052708 sodium Inorganic materials 0.000 description 15
- 230000005611 electricity Effects 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- -1 Co2 + Chemical compound 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 235000015424 sodium Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001232464 Delma Species 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910013410 LiNixCoyAlzO2 Inorganic materials 0.000 description 1
- 229910013467 LiNixCoyMnzO2 Inorganic materials 0.000 description 1
- 229910018337 Mn(C2 H3 O2)2 Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present embodiments relate to a kind of mixed phase structure layered oxide material and its preparation method and application, the mixed phase structure layered oxide material, chemical general formula are as follows: NaxNiiFejMnkMyO2+β；Wherein, M is that substituted element is doped to transition metal position, and the x, y, i, j, k, β are respectively molar percentage shared by corresponding element；Wherein y+i+j+k=1, and x+my+2i+3j+4k=2 (2+ β)；Wherein 0.6≤x≤0.9；0 i≤0.3 <；0 j≤0.5 <；0 k≤0.5 <；-0.02≤β≤0.02；M is the valent state of the M；The structure of the mixed phase layered oxide is the mixed phase of P2 and O3, and space group is respectively as follows: P63/mmc and R-3m；In the oxygen arrangement of mixed phase, a part forms p-type arrangement, and a part forms O-shaped arrangement, and two kinds of structures are staggeredly compatible on an atomic scale.
Description
Technical field
The present invention relates to field of material technology more particularly to a kind of mixed phase structure layered oxide material and its preparation sides
Method and purposes.
Background technique
With the development of society, fossil energy consumption increasingly sharpens and has been approached exhaustion.Reproducible clean energy resource is as too
Utilizing on a large scale for positive energy wind energy is very urgent.But this kind of energy is because the properties such as discontinuity, relatively difficult when grid-connected, it is electric
Chemical energy storage is just particularly important.Lithium ion battery has been commercialized and has been obtained with its high-energy density and power density
Immense success.But because lithium resource is limited and extraction cost is high, so that lithium ion battery cost increases, it is unable to satisfy big
The inexpensive demand of sizable application；And the elements of Na and lithium for being in same main group with it are with closely similar physics and chemically
Matter, and the abundance of sodium on earth is higher than lithium, and cost is relatively low, so developing sodium ion secondary battery as extensive energy storage
Equipment becomes a relatively good selection.
As lithium ion battery, layered oxide is the hot spot of sodium-ion battery research field.Sodium-ion battery anode
Layered oxide structural formula is NaxMO2, according to the definition that Delmas is taught, stratified material can be divided into P2, P3, O2, O3 type etc.
[Solid State Ionics,1985,3/4,165-169].In general, the sodium content of 03 phase material is higher, 0.8≤x≤
1, reversible specific capacity is also higher, but its high rate performance is poor.The sodium content of P2 phase material is lower, x < 0.8, initial capacity
It is low, but good rate capability.[Part.Part.Syst.Charact.2016,33,538–544,J.Mater.Chem.A,
2016,4,11103-11109] two kinds of structures respectively have advantage and disadvantage, and respective disadvantage has all influenced the application of material.
In addition, being LiCoO because of lithium battery applications material the most extensive or best growth momentum2、NCM
(LiNixCoyMnzO2, x+y+z=1) and NCA (LiNixCoyAlzO2, x+y+z=1), wherein metal Co is all contained, and Co
Price is abnormal expensive.With the prosperity of electric car industry, the price of Co will be promoted further.This also directly results in electricity
The raising of pond cost.
Summary of the invention
The object of the present invention is to provide a kind of mixed phase structure layered oxide materials and its preparation method and application.It is described
The preparation of mixed phase structure layered oxide material is simple, and contained transition metal is cooperated excellent with a small amount of nickel based on iron, manganese
Change performance, abundance of the raw material in the earth's crust is high, therefore manufacturing cost is cheap.Using mixed phase layered oxide material of the invention
The sodium ion secondary battery of material, first week is high-efficient, and cycle performance is excellent, and high rate performance is excellent, has a safety feature, and combines two kinds
The advantages of structure, has very big practical value, can be used for solar power generation, wind-power electricity generation, smart grid peak regulation, distribution electricity
It stands, the extensive energy storage device of backup power supply or communication base station.
To achieve the above object, in a first aspect, the present invention provides a kind of mixed phase structure layered oxide material, chemistry
General formula are as follows: NaxNiiFejMnkMyO2+β；
Wherein, M is that substituted element, specially Li are doped to transition metal position+, Cu2+, Mg2+, Mn2+, Zn2+, Co2 +, Ca2+, Ba2+, Sr2+, Mn3+, Al3+, B3+, Cr3+, Co3+, V3+, Zr4+, Ti4+, Sn4+, V4+, Mo4+, Mo5+, Ru4+, Nb5+, Si4+,
Sb5+, Nb5+, Mo6+, Te6+One of or it is a variety of；
The x, y, i, j, k, β are respectively molar percentage shared by corresponding element；Pass between wherein x, y, i, j, k, β
System meets y+i+j+k=1, and x+my+2i+3j+4k=2 (2+ β)；Wherein 0.6≤x≤0.9；0 i≤0.3 <；0 j≤0.5 <；
0 k≤0.5 <；-0.02≤β≤0.02；M is the valent state of the M；
The structure of the mixed phase layered oxide is the mixed phase of P2 and O3, and space group is respectively as follows: P63/mmc and R-
3m；In the oxygen arrangement of mixed phase, a part forms p-type arrangement, and a part forms O-shaped arrangement, and two kinds of structures are in atom
Scale submits misphase appearance.
Preferably, 0.76≤x≤0.8；0.1 i≤0.3 <；0 j≤0.5 <；0 k≤0.5 <；-0.02≤β≤0.02.
Second aspect, the embodiment of the invention provides a kind of preparation methods of mixed phase structure layered oxide material, are
Solid phase method, comprising:
By the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and the nickel oxide of required stoichiometry, oxidation
The oxide of iron, manganese oxide and M is mixed into presoma in proportion；The M is specially Li+, Cu2+, Mg2+, Mn2+, Zn2+, Co2+,
Ca2+, Ba2+, Sr2+, Mn3+, Al3+, B3+, Cr3+, Co3+, V3+, Zr4+, Ti4+, Sn4+, V4+, Mo4+, Mo5+, Ru4+, Nb5+, Si4+,
Sb5+, Nb5+, Mo6+, Te6+One of or it is a variety of；
The presoma is uniformly mixed to get by precursor powder using the method for ball milling；
The precursor powder is placed in Muffle furnace, it is small that 2~24 are heat-treated in 700 DEG C~1000 DEG C of air atmosphere
When；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
The third aspect, the embodiment of the invention provides a kind of preparation methods of mixed phase structure layered oxide material, are
Spray drying process, comprising:
By the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and the nickel oxide of required stoichiometry, oxidation
The oxide of iron, manganese oxide and M is mixed into presoma in proportion；The M is specially Li+, Cu2+, Mg2+, Mn2+, Zn2+, Co2+,
Ca2+, Ba2+, Sr2+, Mn3+, Al3+, B3+, Cr3+, Co3+, V3+, Zr4+, Ti4+, Sn4+, V4+, Mo4+, Mo5+, Ru4+, Nb5+, Si4+,
Sb5+, Nb5+, Mo6+, Te6+One of or it is a variety of；
It stirs evenly to form slurry after the presoma is added ethyl alcohol or water；
Precursor powder is obtained after being spray-dried to the slurry；
The precursor powder is placed in Muffle furnace, it is small that 2~24 are heat-treated in 650 DEG C~1000 DEG C of air atmosphere
When；
Precursor powder after heat treatment is ground, the mixed phase structure layered oxide material is obtained.
Fourth aspect, the embodiment of the invention provides a kind of preparation methods of mixed phase structure layered oxide material, are
Spray drying process, comprising:
By nickel nitrate, the nitric acid of the sodium nitrate of stoichiometry 100wt%~108wt% of required sodium and required stoichiometry
The nitrate of iron, manganese acetate and M is mixed into presoma in proportion；The M is specially Li+, Cu2+, Mg2+, Mn2+, Zn2+, Co2+,
Ca2+, Ba2+, Sr2+, Mn3+, Al3+, B3+, Cr3+, Co3+, V3+, Zr4+, Ti4+, Sn4+, V4+, Mo4+, Mo5+, Ru4+, Nb5+, Si4+,
Sb5+, Nb5+, Mo6+, Te6+One of or it is a variety of；
It stirs evenly to form slurry after the presoma is added ethyl alcohol or water；
Precursor powder is obtained after being spray-dried to the slurry；
The precursor powder is placed in Muffle furnace, it is small that 2~24 are heat-treated in 650 DEG C -1000 DEG C of air atmosphere
When；
Precursor powder after heat treatment is ground, layered oxide material is obtained.
5th aspect, the embodiment of the invention provides a kind of preparation methods of mixed phase structure layered oxide material, are
Sol-gel method, comprising:
By the sodium acetate of stoichiometry 100wt%~108wt% of required sodium or sodium nitrate or sodium carbonate or sodium sulphate, contain
There are nickel, iron, manganese, the nitrate of doped chemical M or sulfate to be stoichiometrically dissolved in water or be dissolved in ethyl alcohol and is mixed into forerunner
Liquid solution；The M is specially Li+, Cu2+, Mg2+, Mn2+, Zn2+, Co2+, Ca2+, Ba2+, Sr2+, Mn3+, Al3+, B3+, Cr3+, Co3+,
V3+, Zr4+, Ti4+, Sn4+, V4+, Mo4+, Mo5+, Ru4+, Nb5+, Si4+, Sb5+, Nb5+, Mo6+, Te6+One of or it is a variety of；
It is stirred at 50 DEG C~100 DEG C, and appropriate chelating agent is added, be evaporated to form aqueous precursor gel；
The aqueous precursor gel is placed in crucible, under 200~500 DEG C of air atmosphere, 2 hours of pre-burning；
It is heat-treated 2~24 hours at 600 DEG C~1000 DEG C again；
Precursor powder after heat treatment is ground, the mixed phase structure layered oxide material is obtained.
6th aspect, the embodiment of the invention provides a kind of preparation methods of mixed phase structure layered oxide material, are
Coprecipitation, comprising:
By the nitrate containing nickel, iron, manganese and M or sulfate or carbonate or hydroxide of required stoichiometric ratio
It is dissolved in the deionized water of certain volume respectively, and is respectively formed solution；The M is specially Li+, Cu2+, Mg2+, Mn2+, Zn2+,
Co2+, Ca2+, Ba2+, Sr2+, Mn3+, Al3+, B3+, Cr3+, Co3+, V3+, Zr4+, Ti4+, Sn4+, V4+, Mo4+, Mo5+, Ru4+, Nb5+,
Si4+, Sb5+, Nb5+, Mo6+, Te6+One of or it is a variety of；
The solution is slowly added dropwise in a certain concentration and the ammonia spirit of pH value with peristaltic pump, generates sediment；
Obtained sediment is cleaned up with deionized water, is uniformly mixed with sodium carbonate according to stoichiometric ratio after drying
Obtained predecessor；
The predecessor is placed in crucible, under 600 DEG C~1000 DEG C of air atmosphere, is heat-treated 6~24 hours,
Obtain precursor powder；
Precursor powder after heat treatment is ground, the mixed phase structure layered oxide material is obtained.
7th aspect, the embodiment of the invention provides a kind of anode pole pieces of sodium ion secondary battery, comprising:
Collector, coated on the collector conductive additive and binder and above-mentioned first aspect described in layer
Shape oxide material.
Eighth aspect, the embodiment of the invention provides the secondary electricity of sodium ion of anode pole piece described in the 7th aspect of one kind
Pond.
9th aspect, the embodiment of the invention provides a kind of purposes of sodium ion secondary battery described in eighth aspect, institutes
Sodium ion secondary battery is stated for solar power generation, wind-power electricity generation, smart grid peak regulation, distribution power station, backup power supply or communication
The extensive energy storage device of base station.
Mixed phase structure layered oxide material preparation provided in an embodiment of the present invention is simple, contained major shift gold
Category iron, manganese are all the elements of non-toxic and safe, and the abundance in the earth's crust is high.And it without the common cobalt element of lithium electricity, therefore manufactures
It is low in cost.And the advantage that phase structure has two kinds of layer structures is mixed, O3 can be modulated by the structural stability of P2
Phase phase transformation bring volume change, and higher sodium content is brought by O3 phase, i.e., higher capacity.Using layer of the invention
The sodium ion secondary battery of shape oxide material possesses all charging capacitys of relatively high head, and cycle performance is excellent, and high rate performance is excellent
It is different, it has a safety feature, there is very big practical value, can be used for solar power generation, wind-power electricity generation, smart grid peak regulation, distribution
The extensive energy storage device such as power station, backup power supply or communication base station.
Detailed description of the invention
Fig. 1 is the multiple mixed phase structure layered oxides for the different element molar percentages that the embodiment of the present invention 1 provides
The XRD spectrum of material；
Fig. 2 is the preparation method that the solid phase method that the embodiment of the present invention 2 provides prepares mixed phase structure layered oxide material
Flow chart；
Fig. 3 is the preparation that the spray drying process that the embodiment of the present invention 3 provides prepares mixed phase structure layered oxide material
Method flow diagram；
Fig. 4 is the preparation that the sol-gel method that the embodiment of the present invention 4 provides prepares mixed phase structure layered oxide material
Method flow diagram；
Fig. 5 is the preparation method that the present invention implements that the coprecipitation that 5 provide prepares mixed phase structure layered oxide material
Flow chart；
Fig. 6 is that the stereoscan photograph that material is made is spray-dried in the embodiment of the present invention 7；
Fig. 7 is to be spray-dried that the last fortnight charging and discharging curve that material is assembled into battery is made in the embodiment of the present invention 7；
Fig. 8 is to be spray-dried that the cycle performance that material is assembled into battery is made in the embodiment of the present invention 7；
Fig. 9 is to be spray-dried that the high rate performance that material is assembled into battery is made in the embodiment of the present invention 7；
Figure 10 is the stereoscan photograph that material is made in sol-gal process in the embodiment of the present invention 8；
Figure 11 is that the last fortnight charging and discharging curve that material is assembled into battery is made in sol-gal process in the embodiment of the present invention 8；
Figure 12 is to be spray-dried that the cycle performance that material is assembled into battery is made in the embodiment of the present invention 8；
Figure 13 is to be spray-dried that the high rate performance that material is assembled into battery is made in the embodiment of the present invention 8；
Figure 14 is the stereoscan photograph that material is made in coprecipitation in the embodiment of the present invention 9；
Figure 15 is that the last fortnight charging and discharging curve that material is assembled into battery is made in coprecipitation in the embodiment of the present invention 9；
Figure 16 is to be spray-dried that the cycle performance that material is assembled into battery is made in the embodiment of the present invention 9；
Figure 17 is to be spray-dried that the high rate performance that material is assembled into battery is made in the embodiment of the present invention 9.
Specific embodiment
Below by drawings and examples, technical scheme of the present invention will be described in further detail.
Embodiment 1
The embodiment of the present invention 1 provides a kind of mixed phase structure layered oxide material, chemical general formula are as follows:
NaxNiiFejMnkMyO2+β。
Wherein, M is that substituted element, specially Li are doped to transition metal position+, Cu2+, Mg2+, Mn2+, Zn2+, Co2 +, Ca2+, Ba2+, Sr2+, Mn3+, Al3+, B3+, Cr3+, Co3+, V3+, Zr4+, Ti4+, Sn4+, V4+, Mo4+, Mo5+, Ru4+, Nb5+, Si4+,
Sb5+, Nb5+, Mo6+, Te6+One of or it is a variety of；
X, y, i, j, k, β are respectively molar percentage shared by corresponding element；Relationship between wherein x, y, i, j, k, β is full
Sufficient y+i+j+k=1, and x+my+2i+3j+4k=2 (2+ β)；Wherein 0.6≤x≤0.9；0 i≤0.3 <；0 j≤0.5 <；0 < k
≤0.5；-0.02≤β≤0.02；；M is the valent state of the M；In a preferred embodiment, 0.76≤x≤0.8；0.1 < i
≤0.3；0 j≤0.5 <；0 k≤0.5 <；-0.02≤β≤0.02.
The structure of mixed phase layered oxide is the mixed phase of P2 and O3, and space group is respectively as follows: P63/mmc and R-3m；?
In the oxygen arrangement of mixed phase, a part forms p-type arrangement, and a part forms O-shaped arrangement, and two kinds of structures are on an atomic scale
It is staggeredly compatible.Mixing phase structure has the advantage of two kinds of layer structures, can modulate O3 phase phase by the structural stability of P2
Become bring volume change, and higher sodium content is brought by O3 phase, i.e., higher capacity.
It has been presented in Fig. 1 the X ray diffracting spectrum of multiple layered oxide materials of different element molar percentages, by
XRD spectrum can be seen that Na provided in this embodimentxNiiFejMnkMyO2+βCrystal structure be P2/O3 mixed phase structure stratiform
Oxide material.
Embodiment 2
The embodiment of the present invention 2 provides a kind of preparation method of mixed phase structure layered oxide material, is solid phase method, such as
Shown in Fig. 2, comprising:
Step 210, by the oxygen of the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and required stoichiometry
The oxide for changing nickel, iron oxide, manganese oxide and M is mixed into presoma in proportion；
M is specially Li+, Cu2+, Mg2+, Mn2+, Zn2+, Co2+, Ca2+, Ba2+, Sr2+, Mn3+, Al3+, B3+, Cr3+, Co3+, V3+,
Zr4+, Ti4+, Sn4+, V4+, Mo4+, Mo5+, Ru4+, Nb5+, Si4+, Sb5+, Nb5+, Mo6+, Te6+One of or it is a variety of；
Step 220, presoma is uniformly mixed to get by precursor powder using the method for ball milling；
Step 230, precursor powder is placed in Muffle furnace, in 700 DEG C~1000 DEG C of air atmosphere be heat-treated 2~
24 hours；
Step 240, the precursor powder after heat treatment is ground, obtains the layered oxide material.
Embodiment 3
The embodiment of the present invention 3 provides a kind of preparation method of mixed phase structure layered oxide material, spray drying process,
As shown in Figure 3, comprising:
Step 310, by the oxygen of the sodium carbonate of stoichiometry 100wt%~108wt% of required sodium and required stoichiometry
The oxide for changing nickel, iron oxide, manganese oxide and M is mixed into presoma in proportion；Or the nitric acid using corresponding chemical metering ratio
Sodium, nickel nitrate, ferric nitrate, manganese acetate and M nitrate be presoma；
The M is specially Li+, Cu2+, Mg2+, Mn2+, Zn2+, Co2+, Ca2+, Ba2+, Sr2+, Mn3+, Al3+, B3+, Cr3+, Co3 +, V3+, Zr4+, Ti4+, Sn4+, V4+, Mo4+, Mo5+, Ru4+, Nb5+, Si4+, Sb5+, Nb5+, Mo6+, Te6+One of or it is a variety of；
Step 320, it will stir evenly to form slurry after presoma plus ethyl alcohol or water；
Step 330, precursor powder is obtained after being spray-dried to slurry；
Step 340, precursor powder is placed in Muffle furnace, in 650 DEG C~1000 DEG C of air atmosphere be heat-treated 2~
24 hours；
Step 350, the precursor powder after heat treatment is ground, obtains the mixed phase structure layered oxide material
Material.
Embodiment 4
The embodiment of the present invention 4 provides a kind of preparation method of layered oxide material, is sol-gel method, such as Fig. 4 institute
Show, comprising:
Step 410, by the sodium acetate of stoichiometry 100wt%~108wt% of required sodium or sodium nitrate or sodium carbonate or
Sodium sulphate is stoichiometrically dissolved in water containing nickel, iron, manganese, the nitrate of doped chemical M or sulfate or is dissolved in ethyl alcohol and mixes
Synthesize precursor solution；
M is specially Li+, Cu2+, Mg2+, Mn2+, Zn2+, Co2+, Ca2+, Ba2+, Sr2+, Mn3+, Al3+, B3+, Cr3+, Co3+, V3+,
Zr4+, Ti4+, Sn4+, V4+, Mo4+, Mo5+, Ru4+, Nb5+, Si4+, Sb5+, Nb5+, Mo6+, Te6+One of or it is a variety of；
Step 420, it is stirred at 50 DEG C~100 DEG C, and appropriate chelating agent is added, be evaporated to form aqueous precursor gel；
Step 430, aqueous precursor gel is placed in crucible, under 200~500 DEG C of air atmosphere, 2 hours of pre-burning；
Step 440, it then at 600 DEG C~1000 DEG C is heat-treated 2~24 hours；
Step 450, the precursor powder after heat treatment is ground, obtains mixed phase structure layered oxide material.
Embodiment 5
The embodiment of the present invention 5 provides a kind of preparation method of layered oxide material, is coprecipitation, as shown in figure 5,
Include:
Step 510, by the nitrate containing nickel, iron, manganese and M or sulfate or carbonate of required stoichiometric ratio or
Hydroxide is dissolved in respectively in the deionized water of certain volume, and is respectively formed solution；
M is specially Li+, Cu2+, Mg2+, Mn2+, Zn2+, Co2+, Ca2+, Ba2+, Sr2+, Mn3+, Al3+, B3+, Cr3+, Co3+, V3+,
Zr4+, Ti4+, Sn4+, V4+, Mo4+, Mo5+, Ru4+, Nb5+, Si4+, Sb5+, Nb5+, Mo6+, Te6+One of or it is a variety of；
Step 520, the solution is slowly added dropwise in a certain concentration and the ammonia spirit of pH value with peristaltic pump, it is heavy to generate
Starch；
Step 530, obtained sediment is cleaned up with deionized water, with sodium carbonate according to stoichiometric ratio after drying
The predecessor being uniformly mixed to get；
Step 540, predecessor is placed in crucible, under 600 DEG C~1000 DEG C of air atmosphere, is heat-treated 6~24
Hour, obtain precursor powder；
Step 550, the precursor powder after heat treatment is ground, obtains mixed phase structure layered oxide material.
The technical solution provided for a better understanding of the present invention, it is following to be illustrated respectively with multiple specific examples using the present invention
Several method provided by the above embodiment prepares the detailed process of layered oxide material, and is applied to secondary cell
Method and battery behavior.
Embodiment 6
Mixed phase structure layered oxide material is prepared using solid phase method method described in previous embodiment 2 in the present embodiment
Material, specific method is as previously mentioned, be specifically detailed in following list 1, comprising:
Table 1
It is used the above-mentioned mixed phase structure layered oxide material being prepared as the active material of cell positive material
In the preparation of sodium-ion battery, specific steps are as follows: by the material powder prepared and acetylene black, binder Kynoar
(PVDF) it is mixed according to the mass ratio of 80:10:10, suitable N-Methyl pyrrolidone (NMP) solution is added, in air drying
Grinding forms slurry in environment, and then slurry is evenly applied in current collector aluminum foil, after drying, is cut into the entelechy that diameter is 12
Piece.Pole piece under vacuum conditions, 120 DEG C drying 12 hours, it is spare to be transferred to glove box immediately.
It is carried out in the glove box for being assemblied in Ar atmosphere of simulated battery, using metallic sodium as to electrode, with NaPF6/ carbonic acid
Acrylic ester (PC) solution is assembled into CR2032 button cell as electrolyte.It is close in C/10 electric current using constant current charge-discharge mode
Degree is lower to carry out charge-discharge test.Test condition are as follows: electric discharge by voltage be 2.5V, charging by voltage be 4V, battery number with
Respective material number corresponds.The XRD of each material of synthesis is as a result, SEM result and the chemical property result of battery are equal
It is listed in the following table 2:
Table 2
Embodiment 7
Mixed phase structure layered oxide material is prepared using spray drying process described in previous embodiment 3 in the present embodiment
Material.
The sodium nitrate of stoichiometric ratio, nickel nitrate, ferric nitrate, manganese acetate predecessor, by predecessor are weighed in the present embodiment
It is dissolved in the water to obtain clear solution；Solution is placed in spray dryer, is spray-dried at 130 DEG C；Collect spray
Presoma out is transferred in aluminum oxide crucible, and 750 DEG C heat treatment 6 hours under air atmosphere, obtain depth in Muffle furnace
Color powder layered oxide material is Na0.78Ni0.2Fe0.38Mn0.42O2, XRD is similar with Fig. 1, shows it for mixed phase stratiform
Oxide.Fig. 6 is Na0.78Ni0.2Fe0.38Mn0.42O2SEM figure, it can be seen from the figure that the particle size average out to of the material
1 micron.
Sodium ion electricity is used for using the above-mentioned layered oxide material being prepared as the active material of cell positive material
The preparation in pond, and carry out charge discharge test.Its preparation process and test method are the same as embodiment 6.Test voltage range is
2.5V~4V, test result are shown in Fig. 7.First week and second week charging and discharging curve are shown in Fig. 7.It can be seen that head Zhou Fang electricity
For specific capacity up to 91.4mAh/g, first week coulombic efficiency is about 93.8%.Fig. 8 and Fig. 9 shows the cycle performance of material respectively
And high rate performance, it can be seen that have excellent performance.
Embodiment 8
Layered oxide material is prepared using sol-gel method described in previous embodiment 4 in the present embodiment.
The specific preparation step of the present embodiment is stoichiometrically to weigh precursor compound NaNO first3、Fe
(NO3)3、Ni(NO3)2、Mn(C2H3O2)2It is successively dissolved in deionized water respectively, adds suitable citric acid as chelating agent,
It is put into 80 DEG C of oil bath pan and stirs；The xerogel being evaporated is transferred in aluminum oxide crucible, at 200 DEG C, in advance
Burn 2 hours；750 DEG C heat treatment 10 hours, the stratiform for obtaining reddish brown black powder aoxidize under air atmosphere in Muffle furnace again
Object material is Na0.78Ni0.2Fe0.38Mn0.42O2, XRD spectrum is similar with Fig. 1.Figure 10 is Na0.78Ni0.2Fe0.38Mn0.42O2's
Scanning electron microscope (SEM) figure, it can be seen from the figure that the particle size distribution of the material is mainly micro- from 500 nanometers to 1
Rice.
Sodium ion electricity is used for using the above-mentioned layered oxide material being prepared as the active material of cell positive material
The preparation in pond, and carry out charge discharge test.Its preparation process and test method are the same as embodiment 6.Test voltage range is
2.5V~4V, test result are shown in Figure 11.First week and second week charging and discharging curve are shown in Figure 11.As can be seen that first put in week
Electric specific capacity is up to 96.4mAh/g, and first week coulombic efficiency is about 96.7%, Figure 12 and Figure 13 shows the circulation of material respectively
Performance and high rate performance, it can be seen that have excellent performance.
Embodiment 9
Mixed phase structure layered oxide material is prepared using coprecipitation described in previous embodiment 5 in the present embodiment.
It specifically includes:
Predecessor nickel nitrate, ferric nitrate and manganese acetate is weighed according to stoichiometric ratio to dissolve respectively in deionized water；With
The aqueous solution of pre-arranged nickel nitrate, ferric nitrate and manganese acetate is slowly added drop-wise to a certain concentration and pH value by peristaltic pump tube
In ammonia spirit；The precipitating taking-up of generation is washed with deionized water completely after the reaction was completed, is dried in being put into 80 DEG C of vacuum drying ovens
It is dry；The powder of drying and sodium carbonate are uniformly mixed to get predecessor according to stoichiometric ratio；Predecessor is transferred to Muffle again
800 DEG C of 12 hours of heat treatment in furnace.Powder mull after heat treatment, which is obtained black layered oxide material, is
Na0.78Ni0.2Fe0.38Mn0.42O2.Its XRD is similar to Figure 1.Figure 14 is Na0.78Ni0.2Fe0.38Mn0.42O2Scanning electron microscopy
Mirror (SEM) figure, it can be seen from the figure that the particle size distribution of the material is mainly from 1 to 10 micron.It is prepared above-mentioned
Layered oxide material is used for the preparation of sodium-ion battery as the active material of cell positive material, and carries out electrochemistry charge and discharge
Electrical testing.Its preparation process and test method are the same as embodiment 6.The electrochemical profiles of its last fortnight are as shown in figure 15, test voltage
Range is 2.5V~4V, and for first week specific discharge capacity up to 93.8mAh/g, first week coulombic efficiency is about 95.0%, Figure 16 and Figure 17
Show the cycle performance and high rate performance of material respectively, it can be seen that have excellent performance.
Mixed phase structure layered oxide material preparation provided in an embodiment of the present invention is simple, contained major shift gold
Category iron, manganese are all the elements of non-toxic and safe, and the abundance in the earth's crust is high.And it without the common cobalt element of lithium electricity, therefore manufactures
It is low in cost.And the advantage that phase structure has two kinds of layer structures is mixed, O3 can be modulated by the structural stability of P2
Phase phase transformation bring volume change, and higher sodium content is brought by O3 phase, i.e., higher capacity.Using layer of the invention
The sodium ion secondary battery of shape oxide material possesses all charging capacitys of relatively high head, and cycle performance is excellent, and high rate performance is excellent
It is different, it has a safety feature, there is very big practical value, can be used for solar power generation, wind-power electricity generation, smart grid peak regulation, distribution
The extensive energy storage device such as power station, backup power supply or communication base station.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (10)
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| CN112670497A (en) * | 2019-09-27 | 2021-04-16 | 宁德时代新能源科技股份有限公司 | Positive electrode active material for sodium ion battery, battery module, battery pack, and device each made of the active material |
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| CN112103483B (en) * | 2020-08-27 | 2024-10-18 | 上海大学 | Two-phase manganese-based P2-phase sodium ion battery positive electrode material for low-temperature operation and preparation method thereof |
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| CN112279309A (en) * | 2020-10-24 | 2021-01-29 | 江苏理工学院 | NaNixMnyM1-x-yO2Preparation method and application of material |
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| CN114551848A (en) * | 2021-12-16 | 2022-05-27 | 南京大学深圳研究院 | Li-doped sodium-ion battery cathode material and preparation method thereof |
| WO2023123049A1 (en) * | 2021-12-29 | 2023-07-06 | 宁德时代新能源科技股份有限公司 | Layered oxide positive electrode active material, and positive electrode plate containing same, sodium ion battery, and electrical apparatus |
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| WO2024131048A1 (en) * | 2022-12-22 | 2024-06-27 | 深圳市贝特瑞新能源技术研究院有限公司 | Positive electrode material and sodium ion battery |
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