CN116864651A - O3-type nickel-iron-manganese-based low-nickel monocrystal positive electrode material and preparation method and application thereof - Google Patents
O3-type nickel-iron-manganese-based low-nickel monocrystal positive electrode material and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 25
- URQWOSCGQKPJCM-UHFFFAOYSA-N [Mn].[Fe].[Ni] Chemical compound [Mn].[Fe].[Ni] URQWOSCGQKPJCM-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 108
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010405 anode material Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000011572 manganese Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000011162 core material Substances 0.000 claims abstract description 9
- 229910002059 quaternary alloy Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000011247 coating layer Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 46
- 238000005245 sintering Methods 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000007873 sieving Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 229910001415 sodium ion Inorganic materials 0.000 claims description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 13
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 9
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 9
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 abstract description 4
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 8
- 235000012255 calcium oxide Nutrition 0.000 description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002671 adjuvant Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical group [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 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
- 239000011888 foil Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- 238000001000 micrograph Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an O3 type nickel-iron-manganese based low-nickel monocrystal anode material, and a preparation method and application thereof. The O3 type quaternary single crystal positive electrode material comprises a core material and a carbon coating layer coating the outer surface of the core material; the core material consists of a quaternary system main material and auxiliary materials doped in the quaternary system main material; the chemical formula of the quaternary system main material is NaNi x M y Fe 1/3 Mn 1/3 O 2 Wherein M is Ca 2+ 、Zr 4+ 、Zn 2+ 、Mg 2+ And Ti is 4+ One of the following; x is more than 0 and less than or equal to 1/3, and x+y=1/3; the auxiliary materials are two or more of transition metal ions except M. The invention is doped by ionsThe method improves and improves the material performance together with carbon coating, can reduce collapse of material structure in repeated charge and discharge processes, optimizes the cycle performance of the material and improves gram capacity of the material, simultaneously utilizes doped transition metal elements to replace part of nickel, reduces raw material cost, and utilizes low-cost carbon source to carry out secondary coating.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery anode materials, and particularly relates to an O3-type nickel-iron-manganese-based low-nickel monocrystal anode material doped with transition metal oxide and coated with carbon, and a preparation method and application thereof.
Background
Sodium ion batteries are expected to benefit from new energy storage developments as new electrochemical energy storage technologies. Sodium batteries have similar discharge times, efficiencies, and cycle lives as lithium batteries and have lower manufacturing costs and are also considered potential candidates due to the abundance of sodium ion resources distributed in the crust and ocean. With the continuous maturity and industrialization promotion of sodium battery technology in the future, sodium batteries are expected to benefit from the novel energy storage development opportunity.
Since the radius of sodium ions is larger than that of lithium ions, na is caused + The layer and the transition metal layer are obviously separated, na + The structure taken together with the various transition metals belongs to NaMeO 2 alpha-NaFeO 2 . But the mixing of the various metal cations is such that in NaMeO 2 Is inhibited in order to optimize NaMeO suitable for the positive electrode of sodium-ion batteries 2 The composition can improve the structural stability of the layered oxide and improve the electrochemical performance by doping inactive elements and active elements. For example, the iron-based layered oxide has low cost and large-scale application prospect; cobalt-based materials having a high energy density; copper-based materials and the like that provide structural stability.
At present, the research of the layered structure is more that O3 type, P2 type and O3/P2 mixed phase type are adopted, compared with P2 type, O3 type has better first week charging capacity and higher energy density due to high sodium ion content, but the ionic conductivity is relatively poor, thereby influencing the cycle performance and the multiplying power performance.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide an O3 type nickel-iron-manganese based low-nickel monocrystal anode material, which is doped with transition metal oxide and carbon for coating, so that the nickel element content is reduced, and the cycle performance and the multiplying power performance of the O3 type nickel-iron-manganese based monocrystal material are improved.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in a first aspect, the invention provides an O3-type quaternary single crystal positive electrode material comprising the following components: a core material and a carbon coating layer coating the outer surface of the core material;
the core material consists of a quaternary system main material and auxiliary materials doped in the quaternary system main material;
the chemical formula of the quaternary system main material is NaNi x M y Fe 1/3 Mn 1/3 O 2 Wherein M is Ca 2+ 、Zr 4+ 、Zn 2+ 、Mg 2+ And Ti is 4+ One of the following; x is more than 0 and less than or equal to 1/3, and x+y=1/3; preferably, 0.26.ltoreq.x.ltoreq.1/3.
The auxiliary materials are Ca except M 2+ 、Zr 4+ 、Zn 2+ 、Mg 2+ And Ti is 4+ Two or more of (3) are provided.
The O3 type quaternary monocrystal anode material is a nickel-iron-manganese 111 system.
The mass of the auxiliary material accounts for 0.8% -1% of the mass of the O3-type quaternary single crystal positive electrode material, and is preferably 1%.
In a second aspect, the invention further provides a preparation method of the O3 type quaternary single crystal positive electrode material, which comprises the following steps:
s1, mixing a sodium source, a nickel source, an iron source, a manganese source, an M source and auxiliary materials, and performing 3D ball milling to obtain a mixed material;
s2, sintering and crushing the mixed material for the first time to obtain an initial product of the anode material;
and S3, mixing the primary product of the anode material with a carbon source, ball milling, performing secondary sintering under an inert atmosphere, and sieving to obtain the O3 type quaternary monocrystal anode material.
In step S1, the sodium source is light anhydrous sodium carbonate or sodium nitrate.
The nickel source is nickel oxide and/or nickel sesquioxide.
The iron source is one or more of ferric oxide, ferric oxide and ferric oxide.
The manganese source is one or more of manganous oxide, manganese dioxide and manganese oxide.
The M source is an oxide of the M.
The auxiliary materials are Ca except M 2+ 、Zr 4+ 、Zn 2+ 、Mg 2+ And Ti is 4+ An oxide of two or more of the above.
In the step S1, the total concentration of metal ions in the total material of the 3D ball mill is 0.8-1.2mol/L, preferably 1.2mol/L.
In step S1, the 3D ball milling time is as follows: 2.5 to 3.5 hours, preferably 3 hours.
In step S2, the conditions of the primary sintering are as follows: the temperature is 1000-1050 ℃, preferably 1000 ℃, and the time is 10-15h, preferably 15h.
The primary sintering process comprises the following steps: heating to 450-500 deg.C, preferably 500 deg.C, holding for 5-6 hr, preferably 5 hr, heating to 1000-1050 deg.C, holding for 10-15 hr, preferably 15 hr, cooling to 600-650 deg.C, holding for 2-3 hr, and cooling to normal temperature. Wherein the heating rate is 2-5 ℃/min, and the cooling rate is 2-5 ℃/min.
In step S3, the carbon source is one or more of sucrose, citric acid, glucose, oxalic acid, formic acid and ascorbic acid.
In the step S3, the carbon source is used in an amount of 10-15%, preferably 10%, of the mass of the primary product of the cathode material.
In step S3, the conditions of the secondary sintering are as follows: the temperature is 600-650 ℃, preferably 600 ℃, and the heat preservation time is 2-3h, preferably 3h.
In a third aspect, a sodium ion battery comprises a positive electrode and a negative electrode; the material of the positive electrode is the O3 type quaternary monocrystal positive electrode material.
The sodium ion battery is a button cell battery.
The positive pole piece of the button cell is prepared according to the following steps: crushing the O3 type quaternary monocrystal positive electrode material into powder, mixing the powder with a conductive agent and a binder to prepare slurry, coating the slurry on a current collector, and drying, rolling and drying to prepare the positive electrode plate of the button cell.
The conductive agent is one or more of carbon black, acetylene black, carbon nanotubes and graphene.
The binder is a conventional binder such as PVDF and the like.
In the slurry, the mass fraction of the O3-type quaternary single crystal positive electrode material is 90%.
The solids content of the slurry was 38.8%.
The beneficial effects obtained by the invention are as follows:
1. the invention adopts Ca 2+ 、Zr 4+ 、Zn 2+ 、Mg 2+ 、Ti 4+ The nickel in the elements is reduced to form a quaternary positive electrode composition, the grain diameter of monocrystal morphology grains of the original nickel-iron-manganese 111 system is increased, collapse of a material structure of a positive electrode material of the traditional nickel-iron-manganese 111 system in the repeated charge and discharge process is reduced, interface side reaction of the material and electrolyte is effectively relieved, the material structure is stabilized, the monocrystal fluxing effect is realized, the problems of poor air stability and the like are improved, and the 0.2C initial charge capacity and the circulation stability of a button cell prepared by the button cell are improved.
2. The invention replaces partial nickel by the doped transition metal element, reduces the cost of raw materials, utilizes low-cost carbon source to carry out secondary coating, has simple preparation method and is easy for large-scale production of the layered anode material of the sodium ion battery.
Drawings
Fig. 1 is a scanning electron microscope image of the positive electrode material provided in comparative example and example 1, example 2.
Fig. 2 is a charge-discharge curve of the positive electrode sheet of the sodium ion battery prepared by the positive electrode materials provided in comparative example and example 1 and example 2 at 0.2C.
Fig. 3 shows the cycle performance of the positive electrode sheet of the sodium ion battery prepared by the positive electrode materials provided in comparative example and example 1 and example 2 at 1C magnification.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Reagents, materials, instruments and the like used in the examples described below are commercially available unless otherwise specified.
Example 1 (M is zinc + adjuvant is zirconia and calcia + carbon coated)
The specific operation steps are as follows:
(1) The mass of sodium carbonate is 38.16g according to the total material concentration of 0.8 mol; the M source takes a zinc source as an example, so that the molar ratio of the nickel source is reduced; the molar ratio of the nickel source to the zinc source to the iron source to the manganese source is 0.3:0.03:0.33:0.33, respectively calculating the mass of each nickel oxide, zinc oxide, ferric oxide and manganous oxide; the auxiliary materials FG are selected to be zirconium oxide and calcium oxide, the materials are weighed according to 1% of the total mass of the materials, and then transferred to a ball milling tank to be placed into a 3D mixer for 3h mixing.
(2) Taking out the uniformly mixed materials, transferring the materials to a muffle furnace, heating to 500 ℃, keeping the temperature for 5 hours at a heating rate of 2 ℃/min, continuously heating to 1000 ℃ for primary sintering, and keeping the temperature for 15 hours at a heating rate of 2 ℃/min;
after the primary sintering is completed, cooling to 650 ℃, wherein the cooling rate is 2 ℃/min, and preserving heat for 2 hours; cooling to room temperature, taking out the sintered material, crushing and sieving;
(3) Adding 10% citric acid into the sieved material, then putting into a tube furnace, introducing nitrogen, heating to 600 ℃ for secondary sintering, wherein the heating rate is 2 ℃/min, and preserving heat for 3 hours;
and after the secondary sintering is finished, cooling to room temperature, taking out the sintered material, crushing, and sieving under a 250-mesh screen to obtain the anode material.
Example 2 (M is zinc + adjuvant is magnesia and titania + carbon coated)
The specific operation steps are as follows:
(1) The mass of sodium carbonate is 38.16g according to the total material concentration of 0.8 mol; the M source takes a zinc source as an example, so that the molar ratio of the nickel source is reduced; the molar ratio of the nickel source to the zinc source to the iron source to the manganese source is 0.26:0.07:0.33:0.33, respectively calculating the mass of nickel oxide, zinc oxide, ferric oxide and manganous oxide; the auxiliary materials are magnesium oxide and titanium dioxide, which are calculated according to 1%, respectively, the raw materials are weighed and transferred to a ball milling tank to be put into a 3D mixer for mixing for 3 hours.
(2) Taking out the uniformly mixed materials, transferring the materials to a muffle furnace, heating to 500 ℃, keeping the temperature for 5 hours at a heating rate of 2 ℃/min, continuously heating to 1000 ℃ for primary sintering, and keeping the temperature for 15 hours at a heating rate of 2 ℃/min;
after the primary sintering is completed, cooling to 650 ℃, wherein the cooling rate is 2 ℃/min, and preserving heat for 2 hours; cooling to room temperature, taking out the sintered material, crushing and sieving;
(3) Adding 10% of ascorbic acid into the sieved material, then putting the material into a tube furnace, introducing nitrogen, heating to 600 ℃ for secondary sintering, wherein the heating rate is 2 ℃/min, and preserving the heat for 3 hours;
and after the secondary sintering is finished, cooling to room temperature, taking out the sintered material, crushing, and sieving under a 250-mesh screen to obtain the anode material.
Example 3 (M element is titanium + adjuvant is calcium oxide and zirconium dioxide + carbon coating)
The specific operation steps are as follows:
(1) The mass of sodium carbonate is 38.16g according to the total material concentration of 0.8 mol; the M source takes a titanium source as an example, so that the molar ratio of the nickel source is reduced; the molar ratio of the nickel source to the titanium source to the iron source to the manganese source is 0.26:0.07:0.33:0.33, respectively calculating the mass of nickel oxide, titanium oxide, ferric oxide and manganous oxide; the auxiliary materials are calcium oxide and zirconium dioxide, respectively calculated according to 1%, and after weighing all the raw materials, the raw materials are transferred to a ball milling tank and put into a 3D mixer for mixing for 3 hours.
(2) Taking out the uniformly mixed materials, transferring the materials to a muffle furnace, heating to 500 ℃, keeping the temperature for 5 hours at a heating rate of 2 ℃/min, continuously heating to 1000 ℃ for primary sintering, and keeping the temperature for 15 hours at a heating rate of 2 ℃/min;
after the primary sintering is completed, cooling to 650 ℃, wherein the cooling rate is 2 ℃/min, and preserving heat for 2 hours; cooling to room temperature, taking out the sintered material, crushing and sieving;
(3) Adding 10% citric acid into the sieved material, then putting into a tube furnace, introducing nitrogen, heating to 600 ℃ for secondary sintering, wherein the heating rate is 2 ℃/min, and preserving heat for 3 hours;
and after the secondary sintering is finished, cooling to room temperature, taking out the sintered material, crushing, and sieving under a 250-mesh screen to obtain the anode material.
Example 4 (M is zinc + adjuvant is calcium oxide and titanium dioxide + carbon coating)
The specific operation steps are as follows:
(1) The mass of sodium carbonate is 38.16g according to the total material concentration of 0.8 mol; the M source takes a zinc source as an example, so that the molar ratio of the nickel source is reduced; the molar ratio of the nickel source to the zinc source to the iron source to the manganese source is 0.26:0.07:0.33:0.33, respectively calculating the mass of nickel oxide, zinc oxide, ferric oxide and manganous oxide; the auxiliary materials are calcium oxide and titanium dioxide, respectively calculated according to 1%, and after weighing the raw materials, the raw materials are transferred to a ball milling tank and put into a 3D mixer for mixing for 3 hours.
(2) Taking out the uniformly mixed materials, transferring the materials to a muffle furnace, heating to 500 ℃, keeping the temperature for 5 hours at a heating rate of 2 ℃/min, continuously heating to 1000 ℃ for primary sintering, and keeping the temperature for 15 hours at a heating rate of 2 ℃/min;
after the primary sintering is completed, cooling to 650 ℃, wherein the cooling rate is 2 ℃/min, and preserving heat for 2 hours; cooling to room temperature, taking out the sintered material, crushing and sieving;
(3) Adding 10% citric acid into the sieved material, then putting into a tube furnace, introducing nitrogen, heating to 600 ℃ for secondary sintering, wherein the heating rate is 2 ℃/min, and preserving heat for 3 hours;
and after the secondary sintering is finished, cooling to room temperature, taking out the sintered material, crushing, and sieving under a 250-mesh screen to obtain the anode material.
Comparative example 1 (without doping M element, without auxiliary material, without carbon coating)
The specific operation steps are as follows:
(1) The mass of sodium carbonate is 38.16g according to the total material concentration of 0.8 mol; the molar ratio of the nickel source to the iron source to the manganese source is 1:1:1 respectively calculating the mass of each nickel oxide, ferric oxide and manganous oxide, weighing each raw material, transferring the raw materials to a ball milling tank, and putting the raw materials into a 3D mixer for mixing for 3 hours.
(2) Taking out the uniformly mixed materials, transferring the materials to a muffle furnace, heating the materials at a temperature program of 0-500 ℃, heating the materials at a heating rate of 2 ℃/min, and preserving the heat for 5h; the set temperature program is 500-1000 ℃, the heating rate is 2 ℃/min, and the temperature is kept for 15h; the set temperature program is 1000-650 ℃, the cooling rate is 2 ℃/min, and the temperature is kept for 2 hours; and (3) calcining at high temperature in air, cooling to room temperature, taking out the sintered material, crushing, and sieving under a 250-mesh screen to obtain the anode material.
Comparative example 2 (M is zinc, without adjuvant, carbon coated)
The specific operation steps are as follows:
(1) The mass of sodium carbonate is 38.16g according to the total material concentration of 0.8 mol; the M source takes a zinc source as an example, so that the molar ratio of the nickel source is reduced; the molar ratio of the nickel source to the zinc source to the iron source to the manganese source is 0.26:0.07:0.33:0.33, respectively calculating the mass of nickel oxide, zinc oxide, ferric oxide and manganous oxide; weighing all the raw materials, transferring to a ball milling tank, and putting into a 3D mixer for mixing for 3 hours.
(2) Taking out the uniformly mixed materials, transferring the materials to a muffle furnace, heating to 500 ℃, keeping the temperature for 5 hours at a heating rate of 2 ℃/min, continuously heating to 1000 ℃ for primary sintering, and keeping the temperature for 15 hours at a heating rate of 2 ℃/min;
after the primary sintering is completed, cooling to 650 ℃, wherein the cooling rate is 2 ℃/min, and preserving heat for 2 hours; cooling to room temperature, taking out the sintered material, crushing and sieving;
(3) Adding 10% of ascorbic acid into the sieved material, then putting the material into a tube furnace, introducing nitrogen, heating to 600 ℃ for secondary sintering, wherein the heating rate is 2 ℃/min, and preserving the heat for 3 hours;
and after the secondary sintering is finished, cooling to room temperature, taking out the sintered material, crushing, and sieving under a 250-mesh screen to obtain the anode material.
Comparative example 3 (undoped M element, auxiliary materials were calcium oxide and titanium dioxide, carbon-coated)
The specific operation steps are as follows:
(1) The mass of sodium carbonate is 38.16g according to the total material concentration of 0.8 mol; the molar ratio of the nickel source to the iron source to the manganese source is 1:1:1 respectively calculating the mass of each nickel oxide, ferric oxide and manganous oxide, selecting calcium oxide and titanium dioxide as auxiliary materials, respectively calculating according to 1 percent, weighing each raw material, transferring the raw materials to a ball milling tank, and putting the raw materials into a 3D mixer for 3h mixing.
(2) Taking out the uniformly mixed materials, transferring the materials to a muffle furnace, heating to 500 ℃, keeping the temperature for 5 hours at a heating rate of 2 ℃/min, continuously heating to 1000 ℃ for primary sintering, and keeping the temperature for 15 hours at a heating rate of 2 ℃/min;
after the primary sintering is completed, cooling to 650 ℃, wherein the cooling rate is 2 ℃/min, and preserving heat for 2 hours; cooling to room temperature, taking out the sintered material, crushing and sieving;
(3) Adding 10% of ascorbic acid into the sieved material, then putting the material into a tube furnace, introducing nitrogen, heating to 600 ℃ for secondary sintering, wherein the heating rate is 2 ℃/min, and preserving the heat for 3 hours;
and after the secondary sintering is finished, cooling to room temperature, taking out the sintered material, crushing, and sieving under a 250-mesh screen to obtain the anode material.
And (3) effect verification:
1. structural morphology
As can be seen from fig. 1, the average particle size of the material obtained in comparative example 1 was 1.42 μm, the average particle size of the material obtained in example 1 was 3.02 μm, the average particle size of the material obtained in example 2 was 4.92 μm, it was found that the average particle sizes of the materials obtained in examples 1 and 2 were significantly larger than the average particle size of the material obtained in comparative example 1, the particle size of the material obtained in example 2 was significantly larger than the average particle size of the material obtained in example 1, and the single crystal morphology of the material obtained in example 2 was clearer. Therefore, the quaternary positive electrode material doped with the transition metal ions keeps the layered structure of the O3 type nickel-iron-manganese-based single crystal material unchanged, and increases the particle size of the single crystal morphology particles of the original nickel-iron-manganese 111 system.
2 electrochemical Properties
Preparing a positive plate of the sodium ion battery: the positive electrode materials obtained in example 1, example 2 and comparative example 1, conductive agent carbon black and binder PVDF were mixed in mass ratioIs 9:0.5:0.5, mixing to prepare slurry, controlling the solid content of the slurry to be 38.8%, coating the slurry on an aluminum foil current collector, drying, rolling, and vacuum drying at 80 ℃ for 12 hours to obtain a positive plate of the sodium ion battery, wherein the compacted density of the plate is controlled to be 2.5g/cm 3 。
As can be seen from fig. 2, the materials obtained in example 1 and example 2 were first higher in 0.2C than in comparative example 1 at a voltage range of 2.0-4.0V.
As can be seen from fig. 3, the capacity retention of the materials obtained in example 1 and example 2 at 1C magnification is significantly higher than that of comparative example 1.
It can be derived from this that the doping of the main element M and the auxiliary material FG contributes to the formation of single crystal grains and improves their initial charge capacity and cycle performance, and the molar ratio of zinc has more room for investigation on the electrochemical performance impact of the single crystal cathode material.
Button cells prepared from the positive electrode materials obtained in examples 1 to 4 and comparative examples 1 to 3 were tested for performance as follows.
Table 1 the electrical properties of the positive electrode materials of examples and comparative examples
As can be seen from the test results in Table 1, compared with the comparative examples, examples 1-4 can remarkably improve the initial charge, the rate capability and the 50-week capacity retention rate of the 0.2C button cell prepared from the materials by doping M element, auxiliary materials and carbon coating, and greatly improve the initial charge capacity and the cycle stability of the cell.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. An O3 type quaternary single crystal positive electrode material comprises the following components: a core material and a carbon coating layer coating the outer surface of the core material;
the core material consists of a quaternary system main material and auxiliary materials doped in the quaternary system main material;
the chemical formula of the quaternary system main material is NaNi x M y Fe 1/3 Mn 1/3 O 2 Wherein M is Ca 2+ 、Zr 4+ 、Zn 2+ 、Mg 2+ And Ti is 4+ One of the following; x is more than 0 and less than or equal to 1/3, and x+y=1/3;
the auxiliary materials are Ca except M 2+ 、Zr 4+ 、Zn 2+ 、Mg 2+ And Ti is 4+ Two or more of (3) are provided.
2. The O3-type quaternary single crystal positive electrode material according to claim 1, wherein: the O3 type quaternary monocrystal anode material is a nickel-iron-manganese 111 system.
3. The O3-type quaternary single crystal positive electrode material according to claim 1 or 2, characterized in that: the mass of the auxiliary material accounts for 0.8% -1% of the mass of the O3-type quaternary single crystal anode material.
4. A method for preparing the O3 type quaternary single crystal positive electrode material according to any one of claims 1 to 3, comprising the steps of:
s1, mixing a sodium source, a nickel source, an iron source, a manganese source, an M source and auxiliary materials, and performing 3D ball milling to obtain a mixed material;
s2, sintering and crushing the mixed material for the first time to obtain an initial product of the anode material;
and S3, mixing the primary product of the anode material with a carbon source, ball milling, performing secondary sintering under an inert atmosphere, and sieving to obtain the O3 type quaternary monocrystal anode material.
5. The method for preparing the O3 type quaternary single crystal positive electrode material according to claim 4, which is characterized in that: in the step S1, the sodium source is anhydrous sodium carbonate or sodium nitrate;
the nickel source is nickel oxide and/or nickel sesquioxide;
the iron source is one or more of ferric oxide, ferric oxide and ferric oxide;
the manganese source is one or more of manganous oxide, manganese dioxide and manganese oxide;
the M source is an oxide of the M;
the auxiliary materials are Ca except M 2+ 、Zr 4+ 、Zn 2+ 、Mg 2+ And Ti is 4+ An oxide of two or more of (a) and (b);
the total concentration of metal ions in the total material of the 3D ball mill is 0.8-1.2mol/L;
the 3D ball milling time is as follows: 2.5-3.5h.
6. The method for preparing an O3 type quaternary single crystal positive electrode material according to claim 4 or 5, characterized in that: in step S2, the conditions of the primary sintering are as follows: the temperature is 1000-1050 ℃ and the time is 10-15h.
7. The method for preparing the O3 type quaternary single crystal positive electrode material according to any one of claims 4 to 6, characterized in that: in step S2, the primary sintering process is as follows: heating to 450-500 ℃, preserving heat for 5-6h, heating to 1000-1050 ℃, preserving heat for 10-15h, cooling to 600-650 ℃, preserving heat for 2-3h, and finally cooling to normal temperature;
wherein the heating rate is 2-5 ℃/min, and the cooling rate is 2-5 ℃/min.
8. The method for preparing an O3 type quaternary single crystal positive electrode material according to any one of claims 4 to 7, characterized in that: in the step S3, the carbon source is one or more of sucrose, citric acid, glucose, oxalic acid, formic acid and ascorbic acid;
the dosage of the carbon source is 10-15% of the quality of the initial product of the anode material.
9. The method for preparing an O3 type quaternary single crystal positive electrode material according to any one of claims 4 to 8, characterized in that: in step S3, the conditions of the secondary sintering are as follows: the temperature is 600-650 ℃, and the heat preservation time is 2-3h.
10. A sodium ion battery comprising a positive electrode and a negative electrode; the material of the positive electrode is the O3 type quaternary monocrystal positive electrode material.
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