CN114361437A - NASICON type structure sodium ion positive electrode material and preparation method and application thereof - Google Patents
NASICON type structure sodium ion positive electrode material and preparation method and application thereof Download PDFInfo
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- CN114361437A CN114361437A CN202210017383.8A CN202210017383A CN114361437A CN 114361437 A CN114361437 A CN 114361437A CN 202210017383 A CN202210017383 A CN 202210017383A CN 114361437 A CN114361437 A CN 114361437A
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 89
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 52
- 239000002228 NASICON Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052909 inorganic silicate Inorganic materials 0.000 claims abstract description 128
- 239000011734 sodium Substances 0.000 claims abstract description 124
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 claims abstract description 34
- 239000011159 matrix material Substances 0.000 claims abstract description 32
- 239000000126 substance Substances 0.000 claims abstract description 25
- 229910020564 Na3+xV2 Inorganic materials 0.000 claims abstract description 23
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 239000010406 cathode material Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 125
- 239000000843 powder Substances 0.000 claims description 57
- 239000002243 precursor Substances 0.000 claims description 46
- 238000001354 calcination Methods 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 239000011651 chromium Substances 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 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 22
- 229910052708 sodium Inorganic materials 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 21
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 16
- 239000012300 argon atmosphere Substances 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- WVSBQYMJNMJHIM-UHFFFAOYSA-N (benzene)chromium tricarbonyl Chemical group [Cr].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1 WVSBQYMJNMJHIM-UHFFFAOYSA-N 0.000 claims description 3
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- 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 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 3
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 claims description 3
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 claims description 3
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229940009827 aluminum acetate Drugs 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 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 3
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229940046374 chromium picolinate Drugs 0.000 claims description 3
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 3
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 3
- GJYSUGXFENSLOO-UHFFFAOYSA-N chromium;pyridine-2-carboxylic acid Chemical compound [Cr].OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1.OC(=O)C1=CC=CC=N1 GJYSUGXFENSLOO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- NVDIDFZVSGUPSX-UHFFFAOYSA-N naphthalene phosphoric acid Chemical compound OP(O)(O)=O.OP(O)(O)=O.c1ccc2ccccc2c1 NVDIDFZVSGUPSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 235000011083 sodium citrates Nutrition 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 32
- 239000010405 anode material Substances 0.000 abstract description 11
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 229910017677 NH4H2 Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 238000006479 redox reaction Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920000447 polyanionic polymer Chemical class 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Inorganic materials [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- 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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- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The application provides a sodium ion anode material with an NASICON type structure, and a preparation method and application thereof, belonging to the technical field of nano materials and electrochemistry. The NASICON type structure sodium ion positive electrode material of the present application is represented by Na3V2(PO4)3Is a matrix material, part of PO in the matrix material4 3‑Is coated with SiO4 4‑Instead, the resulting doped SiO4 4‑The chemical formula of the sodium ion cathode material is Na3+xV2(PO4)3‑x(SiO4)x(ii) a Portion V in the base material3+Is replaced by M metal ions to obtain the SiO doped with the M metal ions4 4‑The chemical formula of the sodium ion cathode material is Na3+xV1.5M0.5(PO4)3‑x(SiO4)xWherein the M metal ion is Al3+Or Cr3+One or two of them; x is more than or equal to 0 and less than or equal to 0.5. The NASICON type structure sodium ion positive electrode material provided by the application has the advantages of high theoretical specific capacity, excellent cycle stability and rate capability, and higher energy density and power density.
Description
Technical Field
The application relates to the technical field of nano materials and electrochemistry, in particular to a sodium ion positive electrode material with an NASICON type structure, a preparation method and application thereof.
Background
The energy storage technology has been developed rapidly in the last two decades, and the electrochemical cell has the advantages of high energy density, long cycle life and the like. Lithium ion batteries, as the most representative electrochemical energy storage batteries, have been widely used in industries such as mobile electronic devices, new energy vehicles, and power grid energy storage. However, the lithium storage in the earth crust is low, and cost of the earth crust is increased year by year due to the unregulated exploitation and the absence of a reasonably planned recovery strategy, so that the application of the lithium ion battery in a future energy storage system is greatly limited, and therefore, the search for a new generation of electrochemical energy storage system capable of replacing the lithium ion battery is very important. Sodium and lithium are elements of the same main group, and the sodium and the lithium have similar chemical properties and structures, but compared with the lithium element, the sodium element has abundant reserves, lower cost and higher safety of the sodium-ion battery, so the sodium-ion battery is considered to have important application in the fields of low-speed new energy automobiles, static energy storage and the like.
In recent years, materials researchers have made extensive studies on positive electrode materials for sodium ion batteries, and developed positive electrode materials such as layered oxides, prussian blue compounds, and polyanion compounds. Among them, polyanion compounds such as phosphate are attracting much attention due to their characteristics of high working voltage, stable chemical structure, environmental friendliness, etc., and NASICON-type polyanion materials are considered to be one of the most promising positive electrode materials because their stable three-dimensional structures provide stable and rapid channels for the deintercalation of sodium ions. Wherein Na is3V2(PO4)3As a representative NASICON-type positive electrode material, attention has been paid to its excellent electrochemical properties.
But Na3V2(PO4)3The NASICON type anode material still has the defects of low sodium storage capacity, poor cycle stability, low energy density and the like, and the application of the NASICON type anode material in the field of sodium ion batteries is influenced, so that the improvement and the improvement of the sodium storage capacity, the cycle stability and the energy density of the NASICON type anode material are particularly important.
Disclosure of Invention
The application provides a sodium ion cathode material with a NASICON type structure, and a preparation method and application thereof, aiming at solving the defects of low sodium storage capacity, poor cycle stability, low energy density and the like of the cathode material of the current secondary sodium ion battery.
In a first aspect, the present application provides a sodium ion positive electrode material of NASICON type structure expressed as Na3V2(PO4)3Is a matrix material, part of PO in the matrix material4 3-Is coated with SiO4 4-Instead, the resulting doped SiO4 4-The chemical formula of the sodium ion cathode material is Na3+xV2(PO4)3-x(SiO4)x；0≤x≤0.5。
Preferably, the portion V in the matrix material3+Is replaced by M metal ions to obtain the SiO doped with the M metal ions4 4-The chemical formula of the sodium ion cathode material is Na3+xV1.5M0.5(PO4)3-x(SiO4)xWherein the M metal ion is Al3+Or Cr3+One or two of them; x is more than or equal to 0 and less than or equal to 0.5.
In a second aspect, the present application provides a method for preparing a NASICON-type structured sodium ion positive electrode material, for preparing the NASICON-type structured sodium ion positive electrode material of the first aspect, the method comprising:
according to Na3+xV2(PO4)3-x(SiO4)xRespectively weighing a sodium source, a vanadium source, a phosphorus source and a silicon source according to the stoichiometric ratio corresponding to the chemical formula, adding the raw materials into a beaker, and simultaneously adding 20-40 mL of deionized water and a reducing agent carbon source into the beaker, wherein the Na is3+xV2(PO4)3-x(SiO4)xThe molar ratio of the carbon source to the reducing agent carbon source is 1: 0-10;
placing the beaker on a temperature-controlled magnetic stirrer, and magnetically stirring at a stirring speed of 200-500 r/min at 20-50 ℃ to obtain the Na3+xV2(PO4)3-x(SiO4)xThe precursor solution of (1);
wherein, Na is obtained3+xV2(PO4)3-x(SiO4)xThe precursor solution of (A) is mixed with Na3V2(PO4)3Is a matrix material, and part of PO in the matrix material4 3-Is coated with SiO4 4-And (4) replacing.
Preferably in accordance with Na3+xV2(PO4)3-x(SiO4)xThe method comprises the following steps of respectively weighing a sodium source, a vanadium source, a phosphorus source and a silicon source according to stoichiometric ratios corresponding to the chemical formulas, adding the raw materials into a beaker, and simultaneously adding 20-40 mL of deionized water and a reducing agent carbon source into the beaker, wherein the method comprises the following steps:
according to Na3+xV1.5M0.5(PO4)3-x(SiO4)xRespectively weighing a sodium source, a vanadium source, a phosphorus source, an M metal source and a silicon source according to the stoichiometric ratio corresponding to the chemical formula, adding the raw materials into a beaker, and simultaneously adding 20-40 mL of deionized water and a reducing agent carbon source into the beaker, wherein the Na is3+xV1.5M0.5(PO4)3-x(SiO4)xThe molar ratio of the carbon source to the reducing agent carbon source is 1: 0-10;
placing the beaker on a temperature-controlled magnetic stirrer, and magnetically stirring at a stirring speed of 200-500 r/min at 20-50 ℃ to obtain the Na3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution of (1).
Wherein, Na is obtained3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution of (A) is mixed with Na3V2(PO4)3Is a matrix material, and part of PO in the matrix material4 3-Is coated with SiO4 4-Instead, a portion V in the matrix material3+Is replaced by M metal ions.
Preferably, the preparation method further comprises:
mixing the Na3+xV2(PO4)3-x(SiO4)xThe precursor solution of (3) or the Na3+xV1.5M0.5(PO4)3-x(SiO4)xCarrying out post-treatment on the precursor solution to obtain dry gel, and uniformly grinding the gel to obtain first powder;
pre-calcining the first powder in a tube furnace, and grinding the pre-calcined powder to obtain second powder;
subjecting the second powder to secondary calcination to obtain Na3+xV2(PO4)3-x(SiO4)xPositive electrode material of sodium ion or Na3+xV1.5M0.5(PO4)3-x(SiO4)xAnd (3) a sodium ion positive electrode material.
Preferably, the sodium source comprises one or more of sodium carbonate, sodium bicarbonate, sodium acetate, sodium citrate, and the like; the vanadium source comprises one or more of vanadium dioxide, vanadium pentoxide, ammonium metavanadate, vanadium acetylacetonate, vanadium trioxide and the like; the phosphorus source comprises one or more of phosphoric acid, guanidine phosphate, urea phosphate, naphthalene phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the like; the silicon source comprises one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, tetraisobutyl orthosilicate and the like; the carbon source comprises one or more of citric acid, glucose and the like; the M metal source comprises one or more of an aluminum source and a chromium source;
wherein the aluminum source comprises one or more of aluminum nitrate, aluminum acetate, trimethylaluminum, aluminum isopropoxide, and the like; the chromium source comprises one or more of chromium nitrate, chromium acetate, chromium picolinate, chromium acetylacetonate and chromium benzenetricarbonyl.
Preferably, the Na is3+xV2(PO4)3-x(SiO4)xThe precursor solution of (3) or the Na3+xV1.5M0.5(PO4)3-x(SiO4)xPrecursor solution of (2)Subjecting the liquid to a post-treatment comprising:
mixing the Na3+xV2(PO4)3-x(SiO4)xThe precursor solution of (3) or the Na3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution is dried in a vacuum drying oven at the temperature of 80-150 ℃, and the drying time is 8-12 h.
Preferably, the first powder is pre-calcined in a tube furnace, the pre-calcination comprising:
and placing the first powder in a tube furnace, and pre-calcining for 4-6 hours at 300-500 ℃ in an inert gas atmosphere.
Preferably, the second powder is subjected to a secondary calcination comprising:
and placing the second powder in a tube furnace, and calcining for 8-12 h at 700-900 ℃ in an argon atmosphere.
In a third aspect, the present application provides a use of the NASICON-type structural sodium ion positive electrode material of the first aspect, the use comprising:
the NASICON type structure sodium ion positive electrode material is applied to a positive electrode material of a liquid sodium ion battery.
Compared with the prior art, the method has the following advantages:
in the prior art, Na3V2(PO4)3Has three-dimensional open sodium ion transport channels and higher sodium ion diffusion rate and ion conductivity. Relative to sodium metal electrode, Na3V2(PO4)3A charging and discharging platform is respectively arranged at 1.6V and 3.4V and respectively corresponds to V2+/V3+And V3+/V4+Oxidation-reduction reaction of (1). The application provides a sodium ion anode material with a NASICON type structure, which adopts SiO4 4-Substitute for Na3V2(PO4)3Part of PO in (1)4 3-On the premise of ensuring the original crystal structure to be unchanged and electric neutrality, Na is added3V2(PO4)3In matrix Na+The content of carriers; on the other hand, the application also adopts metal ion Al3+Or Cr3+Substitute for Na3V2(PO4)3Section V of3+To enhance Na3V2(PO4)3Intrinsic conductivity of the matrix and excitation of V4+/V5+(4.0V vs Na+Na), thereby obviously improving the energy density of the matrix. In addition, the material provided by the application is simple in preparation process, the adopted aluminum source and chromium source are low in price, and the liquid sodium ion battery assembled by utilizing the NASICON type structure sodium ion positive electrode material provided by the application has the advantages of high energy density, excellent cycle stability, high rate performance and the like, and has great potential practical application value and commercial value.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of example 1 of the present invention;
FIG. 2 is an X-ray powder diffraction pattern of example 2 of the present invention;
FIG. 3 is an SEM image of example 2 of the present invention;
FIG. 4 is an X-ray powder diffraction pattern of example 3 of the present invention;
FIG. 5 is an X-ray powder diffraction pattern of example 4 of the present invention;
FIG. 6 is an X-ray powder diffraction pattern of example 5 of the present invention;
FIG. 7 is a graph of the charge and discharge test of the first 3 cycles of the liquid sodium-ion battery of example 5 according to the present invention;
FIG. 8 is a plot of cyclic voltammetry as the positive electrode material for a liquid sodium ion battery in example 5 of the present invention;
FIG. 9 is a graph of the cycling performance of the liquid sodium ion battery of example 5 of the present invention as a positive electrode material, with test current strength 1C;
FIG. 10 is an X-ray powder diffraction pattern of example 6 of the present invention;
FIG. 11 is an SEM image of example 6 of the present invention;
FIG. 12 is a graph of the charge and discharge test of the first 3 cycles of the liquid sodium-ion battery of example 6 according to the present invention;
fig. 13 is a graph of cycle performance of example 6 of the present invention as a positive electrode material for a liquid sodium ion battery, and the current intensity was measured at 1C.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with examples are described in detail below. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In a first aspect, the present application provides a sodium ion positive electrode material of NASICON type structure expressed as Na3V2(PO4)3Is a matrix material, part of PO in the matrix material4 3-Is coated with SiO4 4-Instead, the resulting doped SiO4 4-The chemical formula of the sodium ion cathode material is Na3+xV2(PO4)3-x(SiO4)x；0≤x≤0.5。
Due to the adoption of SiO4 4-Substitute for Na3V2(PO4)3Part of PO in (1)4 3-I.e. using SiO of lower negative valence4 4-Therefore, in order to maintain the balance of electricity price, it is necessary to add a larger amount of Na+I.e. increase Na3V2(PO4)3In matrix Na+The content of carriers. Furthermore, SiO is used4 4-Substitute for Na3V2(PO4)3Part of PO in (1)4 3-The original crystal structure and the electric neutrality are not changed.
Preferably, the portion V in the matrix material3+Is replaced by M metal ions to obtain a dopedIs doped with the M metal ion and the SiO4 4-The chemical formula of the sodium ion cathode material is Na3+xV1.5M0.5(PO4)3-x(SiO4)xWherein the M metal ion is Al3+Or Cr3+One or two of them; x is more than or equal to 0 and less than or equal to 0.5.
Base material Na3V2(PO4)3Has three-dimensional open sodium ion transport channels and higher sodium ion diffusion rate and ion conductivity. Relative to sodium metal electrode, Na3V2(PO4)3A charging and discharging platform is respectively arranged at 1.6V and 3.4V and respectively corresponds to V2+/V3+And V3+/V4+Oxidation-reduction reaction of (1). Due to the adoption of metal ions Al3+Or Cr3+Substitute for Na3V2(PO4)3Section V of3+Can enhance Na3V2(PO4)3Intrinsic conductivity of the matrix and excitation of V4+/V5+(4.0V vs Na+Na), and further the energy density of the matrix is obviously improved. Second, Al used in the present application3+And Cr3+The source is wide and the price is low, so the cost of the prepared sodium ion anode material is relatively low.
In a second aspect, the present application provides a method for preparing a NASICON-type structured sodium ion positive electrode material, for preparing the NASICON-type structured sodium ion positive electrode material of the first aspect, the method comprising:
according to Na3+xV2(PO4)3-x(SiO4)xRespectively weighing a sodium source, a vanadium source, a phosphorus source and a silicon source according to the stoichiometric ratio corresponding to the chemical formula, adding the raw materials into a beaker, and simultaneously adding 20-40 mL of deionized water and a reducing agent carbon source into the beaker, wherein the Na is3+xV2(PO4)3-x(SiO4)xThe molar ratio of the carbon source to the reducing agent carbon source is 1: 0-10;
beaker for placingPlacing the mixture on a temperature-controlled magnetic stirrer, and carrying out magnetic stirring at the stirring speed of 200-500 r/min at the temperature of 20-50 ℃ to obtain the Na3+xV2(PO4)3-x(SiO4)xThe precursor solution of (1);
wherein, Na is obtained3+xV2(PO4)3-x(SiO4)xThe precursor solution of (A) is mixed with Na3V2(PO4)3Is a matrix material, and part of PO in the matrix material4 3-Is coated with SiO4 4-And (4) replacing.
Preferably in accordance with Na3+xV2(PO4)3-x(SiO4)xThe method comprises the following steps of respectively weighing a sodium source, a vanadium source, a phosphorus source and a silicon source according to stoichiometric ratios corresponding to the chemical formulas, adding the raw materials into a beaker, and simultaneously adding 20-40 mL of deionized water and a reducing agent carbon source into the beaker, wherein the method comprises the following steps:
according to Na3+xV1.5M0.5(PO4)3-x(SiO4)xRespectively weighing a sodium source, a vanadium source, a phosphorus source, an M metal source and a silicon source according to the stoichiometric ratio corresponding to the chemical formula, adding the raw materials into a beaker, and simultaneously adding 20-40 mL of deionized water and a reducing agent carbon source into the beaker, wherein the Na is3+xV1.5M0.5(PO4)3-x(SiO4)xThe molar ratio of the carbon source to the reducing agent carbon source is 1: 0-10;
placing the beaker on a temperature-controlled magnetic stirrer, and magnetically stirring at a stirring speed of 200-500 r/min at 20-50 ℃ to obtain the Na3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution of (1).
Wherein, Na is obtained3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution of (A) is mixed with Na3V2(PO4)3Is a matrix material, and part of PO in the matrix material4 3-Is coated with SiO4 4-Instead, a portion V in the matrix material3+Is replaced by M metal ions.
Preferably, the preparation method further comprises:
mixing the Na3+xV2(PO4)3-x(SiO4)xThe precursor solution of (3) or the Na3+xV1.5M0.5(PO4)3-x(SiO4)xCarrying out post-treatment on the precursor solution to obtain dry gel, and uniformly grinding the gel to obtain first powder;
pre-calcining the first powder in a tube furnace, and grinding the pre-calcined powder to obtain second powder;
subjecting the second powder to secondary calcination to obtain Na3+xV2(PO4)3-x(SiO4)xPositive electrode material of sodium ion or Na3+xV1.5M0.5(PO4)3-x(SiO4)xAnd (3) a sodium ion positive electrode material.
Mixing Na3+xV2(PO4)3-x(SiO4)xPrecursor solution of (3) or Na3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution is post-treated to obtain dry gel, so that the raw materials are uniformly mixed on the molecular layer.
Preferably, the sodium source comprises one or more of sodium carbonate, sodium bicarbonate, sodium acetate, sodium citrate, and the like; the vanadium source comprises one or more of vanadium dioxide, vanadium pentoxide, ammonium metavanadate, vanadium acetylacetonate, vanadium trioxide and the like; the phosphorus source comprises one or more of phosphoric acid, guanidine phosphate, urea phosphate, naphthalene phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the like; the silicon source comprises one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, tetraisobutyl orthosilicate and the like; the carbon source comprises one or more of citric acid, glucose and the like; the M metal source comprises one or more of an aluminum source and a chromium source;
wherein the aluminum source comprises one or more of aluminum nitrate, aluminum acetate, trimethylaluminum, aluminum isopropoxide, and the like; the chromium source comprises one or more of chromium nitrate, chromium acetate, chromium picolinate, chromium acetylacetonate and chromium benzenetricarbonyl.
Preferably, the Na is3+xV2(PO4)3-x(SiO4)xThe precursor solution of (3) or the Na3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution of (a) is post-treated, the post-treatment comprising:
mixing the Na3+xV2(PO4)3-x(SiO4)xThe precursor solution of (3) or the Na3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution is dried in a vacuum drying oven at the temperature of 80-150 ℃, and the drying time is 8-12 h.
Preferably, the first powder is pre-calcined in a tube furnace, the pre-calcination comprising:
and placing the first powder in a tube furnace, and pre-calcining for 4-6 hours at 300-500 ℃ in an inert gas atmosphere.
Preferably, the second powder is subjected to a secondary calcination comprising:
and placing the second powder in a tube furnace, and calcining for 8-12 h at 700-900 ℃ in an argon atmosphere.
In a third aspect, the present application provides a use of the NASICON-type structural sodium ion positive electrode material of the first aspect, the use comprising:
the NASICON type structure sodium ion positive electrode material is applied to a positive electrode material of a liquid sodium ion battery.
Because the theoretical sodium storage capacity of the sodium ion battery anode material provided by the application is high, the structural stability is good, the circulation and rate performance of the assembled liquid sodium ion battery are excellent, and the assembled liquid sodium ion battery anode material has higher energy density and power density.
In specific implementation, the following components can be assembled:
weighing 0.07g of the NASICON type structure sodium ion anode material of the first aspect, adding 0.02g of acetylene black (SP) as a conductive agent and 0.01g of PVDF as a binder, mixing and fully grinding the raw materials, adding 2mL of N-methyl pyrrolidone (NMP), grinding and dispersing, after uniform size mixing, performing slurry pulling on an aluminum foil with the thickness of 16 microns to prepare an anode plate, taking a metal sodium plate as a cathode and a counter electrode in an anaerobic glove box, taking Whatman GF/D glass fiber as a diaphragm and 1M NaClO4PC is electrolyte, and the CR2032 button cell is assembled.
The above-described preferred conditions may be combined with each other to obtain a specific embodiment, in accordance with common knowledge in the art.
Example 1
This example uses Na3V2(PO4)3As an example of the base material.
According to Na3V2(PO4)3The stoichiometric ratio corresponding to the chemical formula (II) is 6mmol of CH respectively3COONa、4mmol NH4VO3And 6mmol NH4H2PO4And the above raw materials were added to a beaker, and 40mL of deionized water and 4mmol of C were added to the beaker6H8O7. Placing the beaker on a temperature-controlled magnetic stirrer, and magnetically stirring at a stirring speed of 400r/min at 50 ℃ to obtain Na3V2(PO4)3A precursor solution of the precursor of (1). Mixing Na3V2(PO4)3The precursor solution of the precursor is dried in a vacuum drying oven at the temperature of 80 ℃ for 12 hours to obtain dried gel, and then the dried gel is uniformly ground to obtain first powder. And placing a proper amount of first powder in a tube furnace, pre-calcining for 4 hours at 500 ℃ in an argon atmosphere, and grinding to obtain second powder after the pre-calcination is finished. Placing the second powder in a tube furnace, and calcining for 12h at 800 ℃ under argon atmosphere to obtain Na3V2(PO4)3And (3) a sodium ion positive electrode material.
Example 2
This embodiment uses a portion P in the base materialO4 3-Is coated with SiO4 4-Alternative example, Na was prepared3.1V2(PO4)2.9(SiO4)0.1The process of (2) is as follows:
according to Na3.1V2(PO4)2.9(SiO4)0.1The stoichiometric ratio corresponding to the chemical formula (II) is 6.2mmol of CH respectively3COONa、4mmol NH4VO3、5.8mmol NH4H2PO4And 0.2mmol C8H20O4Si, and adding the raw materials into a beaker, and simultaneously adding 40mL of deionized water and 4mmol of C into the beaker6H8O7. Placing the beaker on a temperature-controlled magnetic stirrer, and magnetically stirring at a stirring speed of 400r/min at 50 ℃ to obtain Na3.1V2(PO4)2.9(SiO4)0.1The precursor solution of (1). Mixing Na3.1V2(PO4)2.9(SiO4)0.1The precursor solution is dried in a vacuum drying oven at 150 ℃ for 10 hours to obtain dried gel, and then the dried gel is uniformly ground to obtain first powder. And placing a proper amount of first powder in a tube furnace, pre-calcining for 6 hours at 500 ℃ in an argon atmosphere, and grinding after the pre-calcination is finished to obtain second powder. Placing the second powder in a tube furnace, and calcining for 10 hours at 700 ℃ under argon atmosphere to obtain Na3.1V2(PO4)2.9(SiO4)0.1And (3) a sodium ion positive electrode material.
Example 3
This example uses a portion V in the base material3+Is covered with Al3+Alternative example, Na was prepared3V1.5Al0.5(PO4)3The process of (2) is as follows:
according to Na3V1.5Al0.5(PO4)3The stoichiometric ratio corresponding to the chemical formula (II) is 6mmol of CH respectively3COONa、3mmol C15H21O6V、1mmol Al(NO3)3And 6mmol NH4H2PO4And the above raw materials were added to a beaker, and 40mL of deionized water and 4mmol of C were added to the beaker6H8O7. Placing the beaker on a temperature-controlled magnetic stirrer, and magnetically stirring at a stirring speed of 400r/min at 20 ℃ to obtain Na3V1.5Al0.5(PO4)3The precursor solution of (1). Mixing Na3V1.5Al0.5(PO4)3The precursor solution is dried in a vacuum drying oven at the temperature of 80 ℃ for 8 hours to obtain dried gel, and then the dried gel is uniformly ground to obtain first powder. And placing a proper amount of the first powder in a tube furnace, pre-calcining for 5 hours at 400 ℃ in an argon atmosphere, and grinding after the pre-calcination is finished to obtain second powder. Placing the second powder in a tube furnace, and calcining for 12h at 800 ℃ under argon atmosphere to obtain Na3V1.5Al0.5(PO4)3And (3) a sodium ion positive electrode material.
Example 4
This example uses a portion V in the base material3+Is covered with Cr3+Alternative example, Na was prepared3V1.5Cr0.5(PO4)3The process of (2) is as follows:
according to Na3V1.5Cr0.5(PO4)3The stoichiometric ratio corresponding to the chemical formula (II) is 6mmol of CH respectively3COONa、3mmol C15H21O6V、1mmol Cr(NO3)3And 6mmol NH4H2PO4And the above raw materials were added to a beaker, and 40mL of deionized water and 4mmol of C were added to the beaker6H8O7. Placing the beaker on a temperature-controlled magnetic stirrer, and magnetically stirring at a stirring speed of 400r/min at 50 ℃ to obtain Na3V1.5Cr0.5(PO4)3The precursor solution of (1). Mixing Na3V1.5Cr0.5(PO4)3The precursor solution is dried in a vacuum drying oven at 150 ℃ for 12 hours to obtain dried gel, and then the dried gel is uniformly ground to obtain first powder. Taking an appropriate amount of the first powder and placing inAnd (3) precalcining for 4 hours in a tubular furnace at 300 ℃ under an argon atmosphere, and grinding to obtain second powder after the precalcination is finished. Placing the second powder in a tube furnace, and calcining for 1h at 700 ℃ under argon atmosphere to obtain Na3V1.5Cr0.5(PO4)3And (3) a sodium ion positive electrode material.
Example 5
This example uses part PO in the base material4 3-Is coated with SiO4 4-Instead, and part V3+Is covered with Al3+Instead, the resulting doped SiO4 4-And Al3+Na of (2)3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The preparation process comprises the following steps:
according to Na3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The stoichiometric ratio corresponding to the chemical formula (II) is 6.4mmol of CH3COONa、3mmol NH4VO3、1mmol C9H21AlO3、5.6mmol NH4H2PO4And 0.4mmol H4SiO4And the above raw materials were added to a beaker, and 40ml of deionized water and 4mmol of C were added to the beaker at the same time6H8O7. Placing the beaker on a temperature-controlled magnetic stirrer, and magnetically stirring at a stirring speed of 400r/min at 50 ℃ to obtain Na3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The precursor solution of (1). Mixing Na3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The precursor solution is dried in a vacuum drying oven at the temperature of 80 ℃ for 12 hours to obtain dried gel, and then the dried gel is uniformly ground to obtain first powder. And placing a proper amount of first powder in a tube furnace, pre-calcining for 6 hours at 500 ℃ in an argon atmosphere, and grinding after the pre-calcination is finished to obtain second powder. Placing the second powder in a tube furnace, and calcining for 10 hours at 700 ℃ under argon atmosphere to obtain Na3.2V1.5Al0.5(PO4)2.8(SiO4)0.2And (3) a sodium ion positive electrode material.
In this case, Na is added3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The procedure applied to the battery assembly was as follows: 0.07g of Na of this example was weighed out separately3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The material is used as a positive electrode material, 0.02g of acetylene black (SP) is added as a conductive agent and 0.01g of PVDF is added as a binder, the raw materials are mixed and fully ground, 2mL of N-methyl pyrrolidone (NMP) is added, grinding and dispersion are carried out, after uniform size mixing, the raw materials are subjected to size pulling on an aluminum foil with the thickness of 16 mu m to prepare a positive electrode plate, a metal sodium plate is used as a negative electrode and a counter electrode in an anaerobic glove box, Whatman GF/D glass fiber is used as a diaphragm, and 1MNaClO is used as a 1M sodium chloride (sodium chloride) solution4PC is electrolyte, and the CR2032 button cell is assembled.
Example 6
This example uses part PO in the base material4 3-Is coated with SiO4 4-Instead, and part V3+Is covered with Cr3+Instead, the resulting doped SiO4 4-And Cr3+Na of (2)3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1The preparation process comprises the following steps:
according to Na3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1The stoichiometric ratio corresponding to the chemical formula (II) is 6.2mmol of CH respectively3COONa、3mmol NH4VO3、1mmol Cr(NO3)3、5.8mmol NH4H2PO4And 0.2mmol C8H20O4Si, and adding the raw materials into a beaker, and simultaneously adding 40mL of deionized water and 4mmol of C into the beaker6H8O7. Placing the beaker on a temperature-controlled magnetic stirrer, and magnetically stirring at a stirring speed of 400r/min at 50 ℃ to obtain Na3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1The precursor solution of (1). Mixing Na3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1The precursor solution is dried in a vacuum drying oven at 150 ℃ for 10 hours to obtain dried gel, and then the dried gel is uniformly ground to obtain first powder. And placing a proper amount of first powder in a tube furnace, pre-calcining for 6 hours at 500 ℃ in an argon atmosphere, and grinding after the pre-calcination is finished to obtain second powder. Placing the second powder in a tube furnace, and calcining for 10 hours at 700 ℃ under argon atmosphere to obtain Na3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1And (3) a sodium ion positive electrode material.
In this case, Na is added3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1The procedure applied to the battery assembly was as follows: 0.07g of Na of this example was weighed out separately3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1The material is used as a positive electrode material, 0.02g of acetylene black (SP) is added as a conductive agent and 0.01g of PVDF is added as a binder, the raw materials are mixed and fully ground, 2mL of N-methyl pyrrolidone (NMP) is added, grinding and dispersion are carried out, after uniform size mixing, the raw materials are subjected to size pulling on an aluminum foil with the thickness of 16 mu m to prepare a positive electrode plate, a metal sodium plate is used as a negative electrode and a counter electrode in an anaerobic glove box, Whatman GF/D glass fiber is used as a diaphragm, and 1MNaClO is used as a 1M sodium chloride (sodium chloride) solution4PC is electrolyte, and the CR2032 button cell is assembled.
In order to further illustrate that the NASICON type structure sodium ion cathode material prepared by the method has high theoretical specific capacity, excellent cycle stability and rate capability, the analysis is carried out by combining a specific figure.
FIG. 1 shows Na prepared in example 13V2(PO4)3The X-ray powder diffractogram of (1) shows that Na produced in example 13V2(PO4)3Belongs to a rhombohedral phase NASICON structure, and no impurity phase exists.
FIG. 2 shows Na prepared in example 23.1V2(PO4)2.9(SiO4)0.1The X-ray powder diffractogram of (1) shows that Na produced in example 23.1V2(PO4)2.9(SiO4)0.1Belongs to rhombohedral phase NASICON structure, no impurity phase exists, namely SiO is adopted4 4-Substitute for Na3V2(PO4)3Part of PO in (1)4 3-The original crystal structure is not changed, and the product still belongs to a rhombohedral phase NASICON structure.
FIG. 3 shows Na prepared in example 2 of the present invention3.1V2(PO4)2.9(SiO4)0.1SEM image of (5), it can be seen from the figure that Na prepared in this example3.1V2(PO4)2.9(SiO4)0.1The material particle size is about 10 μm or so.
FIG. 4 shows Na prepared in example 33V1.5Al0.5(PO4)3The X-ray powder diffractogram of (1) shows that Na produced in example 33V1.5Al0.5(PO4)3Belongs to rhombohedral phase NASICON structure, no impurity phase exists, namely Al is adopted3+Substitute for Na3V2(PO4)3Section V of3+The original crystal structure is not changed, and the obtained material still belongs to a rhombus phase NASICON structure.
FIG. 5 shows Na prepared in example 43V1.5Cr0.5(PO4)3The X-ray powder diffractogram of (1) shows that Na produced in example 43V1.5Cr0.5(PO4)3Belongs to rhombohedral phase NASICON structure, has no impurity phase, namely adopts Cr3+Substitute for Na3V2(PO4)3Section V of3+The original crystal structure is not changed, and the obtained material still belongs to a rhombus phase NASICON structure.
FIG. 6 shows Na prepared in example 53.2V1.5Al0.5(PO4)2.8(SiO4)0.2The X-ray powder diffractogram of (1) shows that Na produced in example 53.2V1.5Al0.5(PO4)2.8(SiO4)0.2Belongs to rhombohedral phase NASICON structure, no impurity phase exists, namely Al is adopted3+Substitute for Na3V2(PO4)3Section V of3+And use of SiO4 4-Substitute for Na3V2(PO4)3Part of PO in (1)4 3-The original crystal structure is not changed, and the obtained material still belongs to a rhombus phase NASICON structure.
FIG. 7 shows Na prepared in example 5 of the present invention3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The material is used as the positive electrode material of the liquid sodium-ion battery, and the test magnification is 1C (1C is 191.9mA g)-1) The test voltage range is 1.4V-4.4V vs Na+and/Na. As can be seen from the figure, Na produced by this example3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The material can release 194mAhg when being used as a positive electrode material of a liquid sodium-ion battery-1The first capacity of the material, and the material has better charge and discharge stability. Furthermore, it can be seen that voltage plateaus occur at voltages of 1.6V, 3.4V and 4.1V, i.e. corresponding to V, respectively3+/V2+、V4+/V3+And V5+/V4+Oxidation-reduction reaction of (1).
FIG. 8 shows Na prepared in example 5 of the present invention3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The cyclic voltammetry curve chart of the material as the anode material of the liquid sodium-ion battery has the test voltage range of 1.4V-4.4 Vvs Na+Na, sweep rate 0.2mV s-1. As can be seen from the figure, Na produced in this example3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The material has good electrochemical stability in a test voltage range, and the appearance of 4.1V corresponds to V5+/V4+Oxidation reduction of (2) indicating Al3+Alternative V3+Can stimulateHair V5+/V4+The redox reaction is carried out, and SiO4 is doped in a proper amount3-Nor inhibit V5+/V4+The redox reaction proceeds reversibly.
FIG. 9 shows Na prepared in example 5 of the present invention3.2V1.5Al0.5(PO4)2.8(SiO4)0.2Cycle performance diagram of the material, ambient temperature is room temperature, and test current intensity is 1C (1C-191.9 mA g)-1) The test voltage range is 1.4V-4.4V vs Na+and/Na. As can be seen from the figure, Na produced in this example3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The material has excellent cycling stability when being used as the anode material of the liquid sodium-ion battery, and the specific capacity is 183mAh g after 100 cycles of cycling-1The capacity retention rate was 94.3%.
FIG. 10 shows Na prepared in example 63.1V1.5Cr0.5(PO4)2.9(SiO4)0.1The X-ray powder diffractogram of (1) shows that Na produced in example 63.1V1.5Cr0.5(PO4)2.9(SiO4)0.1Belongs to rhombohedral phase NASICON structure, has no impurity phase, namely adopts Cr3+Substitute for Na3V2(PO4)3Section V of3+And use of SiO4 4-Substitute for Na3V2(PO4)3Part of PO in (1)4 3-The original crystal structure is not changed, and the product still belongs to a rhombohedral phase NASICON structure.
FIG. 11 shows Na prepared in example 6 of the present invention3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1SEM image of (5), it can be seen from the figure that Na prepared in this example3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1The material particles had a uniform size distribution with an average size of about 30 μm.
FIG. 12 is a schematic representation of the practice of the present inventionNa prepared in example 63.1V1.5Cr0.5(PO4)2.9(SiO4)0.1The material is used as the positive electrode material of the liquid sodium-ion battery, and the test magnification is 1C (1C is 181.3mA g)-1) The test voltage range is 1.4V-4.4V vs Na+and/Na. As can be seen from the figure, Na produced by this example3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1163mAhg of material can be released when the material is used as a positive electrode material of a sodium-ion battery-1First capacity of (A), and FIG. 7 (Na)3.2V1.5Al0.5(PO4)2.8(SiO4)0.2The material can release 194mAhg when being used as a positive electrode material of a liquid sodium-ion battery-1First capacity of (d) SiO4 4-Is added with increased Na+The content of carriers. Furthermore, it can be seen that voltage plateaus occur at voltages of 1.6V, 3.4V and 4.1V, i.e. corresponding to V, respectively3+/V2+、V4+/V3+And V5+/V4+Oxidation-reduction reaction of (1).
FIG. 13 shows Na prepared in example 6 of the present invention3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1The cycle performance of the material is shown in the figure, the ambient temperature is room temperature, and the test current intensity is 1C (1C is 181.3mA g-1). As can be seen from the figure, Na produced in this example3.1V1.5Cr0.5(PO4)2.9(SiO4)0.1The material has excellent cycling stability when being used as a positive electrode material of a sodium-ion battery, and the specific capacity is 154mAh g after 100 cycles of cycling-1The capacity retention rate was 94.5%.
The NASICON-type structured sodium ion cathode material, the preparation method and the application thereof provided by the present application are described in detail above, and the principle and the implementation mode of the present application are explained by applying specific examples, and the description of the above examples is only used to help understanding the method and the core idea of the present application; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (10)
1. The NASICON type structure sodium ion positive electrode material is characterized in that Na is used as the sodium ion positive electrode material3V2(PO4)3Is a matrix material, part of PO in the matrix material4 3-Is coated with SiO4 4-Instead, the resulting doped SiO4 4-The chemical formula of the sodium ion cathode material is Na3+xV2(PO4)3-x(SiO4)x；0≤x≤0.5。
2. The NASICON-type structural sodium ion positive electrode material of claim 1, wherein the portion V in the matrix material3+Is replaced by M metal ions to obtain the SiO doped with the M metal ions4 4-The chemical formula of the sodium ion cathode material is Na3+xV1.5M0.5(PO4)3-x(SiO4)xWherein the M metal ion is Al3+Or Cr3+One or two of them; x is more than or equal to 0 and less than or equal to 0.5.
3. A method for preparing the NASICON-type structured sodium ion positive electrode material of claim 1, characterized in that the preparation method comprises:
according to Na3+xV2(PO4)3-x(SiO4)xRespectively weighing a sodium source, a vanadium source, a phosphorus source and a silicon source according to the stoichiometric ratio corresponding to the chemical formula, adding the raw materials into a beaker, and simultaneously adding 20-40 mL of deionized water and a reducing agent carbon source into the beaker, wherein the Na is3+xV2(PO4)3-x(SiO4)xThe molar ratio of the carbon source to the reducing agent carbon source is 1: 0-10;
placing the beaker on a temperature-controlled magnetic stirrer, and magnetically stirring at a stirring speed of 200-500 r/min at 20-50 ℃ to obtain the Na3+xV2(PO4)3-x(SiO4)xThe precursor solution of (1);
wherein, Na is obtained3+xV2(PO4)3-x(SiO4)xThe precursor solution of (A) is mixed with Na3V2(PO4)3Is a matrix material, and part of PO in the matrix material4 3-Is coated with SiO4 4-And (4) replacing.
4. A process according to claim 3, characterized in that it is carried out in the presence of Na3+xV2(PO4)3-x(SiO4)xThe method comprises the following steps of respectively weighing a sodium source, a vanadium source, a phosphorus source and a silicon source according to stoichiometric ratios corresponding to the chemical formulas, adding the raw materials into a beaker, and simultaneously adding 20-40 mL of deionized water and a reducing agent carbon source into the beaker, wherein the method comprises the following steps:
according to Na3+xV1.5M0.5(PO4)3-x(SiO4)xRespectively weighing a sodium source, a vanadium source, a phosphorus source, an M metal source and a silicon source according to the stoichiometric ratio corresponding to the chemical formula, adding the raw materials into a beaker, and simultaneously adding 20-40 mL of deionized water and a reducing agent carbon source into the beaker, wherein the Na is3+xV1.5M0.5(PO4)3-x(SiO4)xThe molar ratio of the carbon source to the reducing agent carbon source is 1: 0-10;
placing the beaker on a temperature-controlled magnetic stirrer, and magnetically stirring at a stirring speed of 200-500 r/min at 20-50 ℃ to obtain the Na3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution of (1);
wherein, Na is obtained3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution of (A) is mixed with Na3V2(PO4)3Is a matrix material, and part of PO in the matrix material4 3-Is coated with SiO4 4-Instead, a portion V in the matrix material3+Is replaced by M metal ions.
5. The method of manufacturing according to claim 4, further comprising:
mixing the Na3+xV2(PO4)3-x(SiO4)xThe precursor solution of (3) or the Na3+xV1.5M0.5(PO4)3-x(SiO4)xCarrying out post-treatment on the precursor solution to obtain dry gel, and uniformly grinding the gel to obtain first powder;
pre-calcining the first powder in a tube furnace, and grinding the pre-calcined powder to obtain second powder;
subjecting the second powder to secondary calcination to obtain Na3+xV2(PO4)3-x(SiO4)xPositive electrode material of sodium ion or Na3+ xV1.5M0.5(PO4)3-x(SiO4)xAnd (3) a sodium ion positive electrode material.
6. The method of claim 4, wherein the sodium source comprises one or more of sodium carbonate, sodium bicarbonate, sodium acetate, sodium citrate, and the like; the vanadium source comprises one or more of vanadium dioxide, vanadium pentoxide, ammonium metavanadate, vanadium acetylacetonate, vanadium trioxide and the like; the phosphorus source comprises one or more of phosphoric acid, guanidine phosphate, urea phosphate, naphthalene phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and the like; the silicon source comprises one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, tetraisobutyl orthosilicate and the like; the carbon source comprises one or more of citric acid, glucose and the like; the M metal source comprises one or more of an aluminum source and a chromium source;
wherein the aluminum source comprises one or more of aluminum nitrate, aluminum acetate, trimethylaluminum, aluminum isopropoxide, and the like; the chromium source comprises one or more of chromium nitrate, chromium acetate, chromium picolinate, chromium acetylacetonate and chromium benzenetricarbonyl.
7. The method according to claim 5, wherein the Na is added3+xV2(PO4)3-x(SiO4)xThe precursor solution of (3) or the Na3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution of (a) is post-treated, the post-treatment comprising:
mixing the Na3+xV2(PO4)3-x(SiO4)xThe precursor solution of (3) or the Na3+xV1.5M0.5(PO4)3-x(SiO4)xThe precursor solution is dried in a vacuum drying oven at the temperature of 80-150 ℃, and the drying time is 8-12 h.
8. The method according to claim 5, wherein the first powder is pre-calcined in a tube furnace, the pre-calcination comprising:
and placing the first powder in a tube furnace, and pre-calcining for 4-6 hours at 300-500 ℃ in an inert gas atmosphere.
9. The method according to claim 5, characterized in that the second powder is subjected to a secondary calcination comprising:
and placing the second powder in a tube furnace, and calcining for 8-12 h at 700-900 ℃ in an argon atmosphere.
10. The application of a NASICON type structure sodium ion positive electrode material is characterized by comprising the following components in percentage by weight: the NASICON type structure sodium ion positive electrode material is applied to a positive electrode material of a liquid sodium ion battery.
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