CN109065855A - Oxide and carbon co-coated cation-doped sodium vanadium phosphate as positive electrode material of sodium-ion battery and preparation method thereof - Google Patents
Oxide and carbon co-coated cation-doped sodium vanadium phosphate as positive electrode material of sodium-ion battery and preparation method thereof Download PDFInfo
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- CN109065855A CN109065855A CN201810765692.7A CN201810765692A CN109065855A CN 109065855 A CN109065855 A CN 109065855A CN 201810765692 A CN201810765692 A CN 201810765692A CN 109065855 A CN109065855 A CN 109065855A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 title claims abstract description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims description 23
- 239000007774 positive electrode material Substances 0.000 title abstract description 4
- 239000011734 sodium Substances 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 26
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 40
- 229910019142 PO4 Inorganic materials 0.000 claims description 37
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 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 16
- 229910052593 corundum Inorganic materials 0.000 claims description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 16
- 150000001768 cations Chemical class 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000010792 warming Methods 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
- 239000002994 raw material Substances 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 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
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 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
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000002345 surface coating layer Substances 0.000 claims description 2
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims 7
- 239000012002 vanadium phosphate Substances 0.000 claims 7
- 239000002552 dosage form Substances 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract 1
- ZCPSPTHSPJKCRR-UHFFFAOYSA-K [Na+].[Na+].P(=O)([O-])([O-])[O-].[V+5] Chemical compound [Na+].[Na+].P(=O)([O-])([O-])[O-].[V+5] ZCPSPTHSPJKCRR-UHFFFAOYSA-K 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229910019463 NaV2 Inorganic materials 0.000 description 1
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 1
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011701 zinc Substances 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本发明公开了一种氧化物与碳共包覆阳离子掺杂的钠离子电池正极材料磷酸钒钠及其制备方法，该正极材料由Na3V2‑xMx(PO4)3/C·mAl2O3表示，包括本体Na3V2‑xMx(PO4)3和表面包覆层Al2O3和碳，其中M为Fe、Co、Mg、Zn、Na中的至少一种，0<x<0.5，0<m≤15％。本发明通过对阳离子掺杂的磷酸钒钠进行包覆，可以增强电极材料的导电性以及其在电解液中的稳定性，进而提高材料的电化学性能。
The invention discloses an oxide and carbon co-coated cation-doped sodium vanadium phosphate sodium ion battery positive electrode material and a preparation method thereof. The positive electrode material is composed of Na 3 V 2‑x M x (PO 4 ) 3 /C· mAl 2 O 3 means, including bulk Na 3 V 2‑x M x (PO 4 ) 3 and surface coating Al 2 O 3 and carbon, wherein M is at least one of Fe, Co, Mg, Zn, Na , 0<x<0.5, 0<m≤15%. The invention can enhance the conductivity of the electrode material and its stability in the electrolyte by coating the cation-doped sodium vanadium phosphate, thereby improving the electrochemical performance of the material.
Description
Technical field
The present invention relates to a kind of preparation methods of sodium-ion battery positive material more particularly to a kind of oxide to wrap altogether with carbon
The sodium-ion battery positive material vanadium phosphate sodium and preparation method thereof for covering cation doping, belongs to battery manufacturing field.
Background technique
With the development of society, the energy is increasingly by the concern of the mankind, wherein lithium ion battery is because of its long-life, high ratio
Can, it is pollution-free, can be used for the new-energy automobiles such as BEV, PHEV, and receive significant attention.But because of its inadequate resource, lead to original
Material end price increase aggravates the cost burden of Liao Ge manufacturing enterprise.Researchers are promoted to develop to research direction by resource
On the sodium-ion battery of sodium element composition abundant.The working principle of sodium-ion battery is similar with lithium ion battery, but and lithium from
Sub- battery is compared, and sodium-ion battery possesses resourceful, cheap advantage, thus by the favor of researcher.
Because sodium ion radius ratio lithium ion radius is big, the process of deintercalation and insertion is easy to cause electrode material between positive and negative anodes
Expect structure collapses, Na3V2(PO4)3With NASICON three-dimensional structure, enough channels can be provided for the migration of sodium ion, had
Have the advantages that stable structure, voltage platform are high, thermal stability is good.However, to result in its electronic conductivity low for vanadium phosphate sodium structure,
Affect its cycle life and high rate performance.Therefore it needs to promote its chemical property by means such as coating-dopings.
Summary of the invention
The present invention is to provide a kind of oxide to avoid above-mentioned existing deficiencies in the technology and carbon coats sun altogether
Sodium-ion battery positive material vanadium phosphate sodium of ion doping and preparation method thereof, it is therefore an objective to improve NaV2(PO4)3Electrochemistry
Energy.
The representation method that oxide of the invention coats the vanadium phosphate sodium positive electrode of cation doping with carbon altogether is
Na3V2-xMx(PO4)3/C·mAl2O3, including ontology Na3V2-xMx(PO4)3With surface coating layer Al2O3And carbon, wherein M be Fe,
At least one of Co, Mg, Zn, Na, 0 < x < 0.5,0 < m≤15%.Preparation method includes the following steps:
(1) according to Na:V:M:PO4: C=3:(2-x): the molar ratio of x:3:2 weighs sodium source, vanadium source, the source M, phosphorus source, carbon
Source；
(2) above-mentioned raw materials and ball milling pearl are added in ball grinder according to the mass ratio of 1:3, injection is a certain amount of volatile to be had
Solvent forms homogeneous slurry, carries out wet ball grinding, grinds, be placed in vacuum tube furnace after drying, risen under atmosphere of inert gases
Temperature keeps the temperature 12~16 hours, grinds after being cooled to room temperature, obtain carbon-coated Na to 750~900 DEG C3V2-xMx(PO4)3/C；
(3) Al is pressed2O3Covering amount, i.e., Na:Al=3:2m in molar ratio weighs Al (OH)3, with carbon coating obtained above
Vanadium phosphate sodium carry out wet ball grinding, grind, be placed in vacuum tube furnace after drying, 300 DEG C are warming up under atmosphere of inert gases,
Heat preservation 3 hours, grinds after being cooled to room temperature, and obtains the Na that aluminium oxide and carbon coat altogether3V2-xMx(PO4)3/C·mAl2O3。
Preferably, the carbon source is at least one of glucose, citric acid, oxalic acid.
Preferably, the sodium source is at least one of sodium dihydrogen phosphate, disodium hydrogen phosphate.
Preferably, the vanadium source is V2O5、NH4VO3At least one of.
Preferably, phosphorus source is at least one of ammonium dihydrogen phosphate, ammonium phosphate.
Preferably, the source M is at least one of sulfate, nitrate, acetate of M.
Preferably, step (2) the ball milling pearl is agate bead, zirconium oxide ball milling pearl or aluminium oxide ball milling pearl.
Preferably, step (2) the volatile organic solvent is acetone or alcohol.
Compared with prior art, the beneficial effects of the present invention are embodied in:
1, the present invention is coated by the vanadium phosphate sodium to cation doping, while enhancing the electric conductivity of electrode material
Its stability in the electrolytic solution can be improved, and then improve the cyclical stability of material.
2, this method has carried out ball milling twice, and in synthesis Na3V2-xMx(PO4)3Al is carried out after/C2O3Cladding, can make sample
Product particle is more uniform, Al2O3It is uniformly coated on Na3V2-xMx(PO4)3/ C Surface is conducive to improve Na3V2(PO4)3Electrification
Learn performance.
Detailed description of the invention
Fig. 1 is comparative example 1, Na prepared by embodiment 13V2(PO4)3/ C and Na3V1.9Mg0.1(PO4)3/ C10wt%
Al2O3The first charge-discharge curve graph of positive electrode；
Fig. 2 is comparative example 1, Na prepared by embodiment 13V2(PO4)3/ C and Na3V1.9Mg0.1(PO4)3/ C10wt%
Al2O3The cycle performance curve graph of positive electrode；
Fig. 3 is comparative example 1, Na prepared by embodiment 13V2(PO4)3/ C and Na3V1.9Mg0.1(PO4)3/ C10wt%
Al2O3The high rate performance figure of positive electrode.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples.
Embodiment 1
The present embodiment prepares Na as follows3V1.9Mg0.1(PO4)3/ C10wt%Al2O3Positive electrode:
(1) sodium carbonate 0.795g, ammonium metavanadate are weighed according to the molar ratio of Na:P:V:C:Mg=3:3:1.9:2:0.1
1.1113g, ammonium dihydrogen phosphate 1.7254g, citric acid 2.1014g, magnesium nitrate hexahydrate 0.128g；
(2) above-mentioned raw materials and agate bead are added in ball grinder according to the mass ratio of 1:3, inject a certain amount of acetone and is formed
Homogenate carries out wet ball grinding, grinds, be placed in vacuum tube furnace after drying, be warming up to 750~900 under atmosphere of inert gases
DEG C, 12~16 hours are kept the temperature, is ground after being cooled to room temperature, obtains carbon-coated Na3V1.9Mg0.1(PO4)3/C；
(3) 10wt%Al is pressed2O3Covering amount weigh 0.3432gAl (OH)3, with carbon-coated phosphorus obtained above
Na3V1.9Mg0.1(PO4)3/ C carries out wet ball grinding, grinds, is placed in vacuum tube furnace after drying, is heated up under atmosphere of inert gases
To 300 DEG C, 3 hours are kept the temperature, is ground after being cooled to room temperature, obtains the Na that aluminium oxide and carbon coat altogether3V1.9Mg0.1(PO4)3/C·
10wt%Al2O3。
For gained sample as sodium-ion battery positive material, electrochemical property test is as follows: 7:2:1 in mass ratio weighs this
The Na of embodiment preparation3V1.9Mg0.1(PO4)3/ C10wt%Al2O3, acetylene black, positive plate is made in Kynoar, with metal
Sodium piece is as the cathode to electrode, using glass fibre as diaphragm, the NaClO of 1mol/L4It (PC) is electrolyte, the group in glove box
Dress up 2032 type button cells.
Assembled battery is carried out to 0.5C charge and discharge cycles test, voltage range 2.5-3.8V at room temperature.For the first time
Charging and discharging curve is as shown in Figure 1, the first discharge specific capacity of the material is 102.68mAhg-1, cycle performance curve such as Fig. 2 institute
Show, capacity retention ratio of the circulation after 100 weeks is 86.29%, and high rate performance is as shown in Figure 3.To sum up, manufactured in the present embodiment
Na3V1.9Mg0.1(PO4)3/ C10wt%Al2O3Compare Na3V2(PO4)3/ C, for the first time discharge capacity, capacity retention ratio and multiplying power
Performance is improved.
Comparative example 1
This comparative example prepares Na as follows3V2(PO4)3/ C positive electrode material:
(1) sodium carbonate 0.795g, ammonium metavanadate 1.1698g, phosphoric acid are weighed according to the molar ratio of Na:P:V:C=3:3:2:2
Ammonium dihydrogen 1.7254g, citric acid 2.1014g；
(2) above-mentioned raw materials and agate bead are added in ball grinder according to the mass ratio of 1:3, inject a certain amount of acetone and is formed
Homogenate carries out wet ball grinding, grinds, be placed in vacuum tube furnace after drying, be warming up to 750~900 under atmosphere of inert gases
DEG C, 12~16 hours are kept the temperature, is ground after being cooled to room temperature, obtains carbon-coated Na3V2(PO4)3/C。
For gained sample as sodium-ion battery positive material, electrochemical property test is as follows: 7:2:1 in mass ratio weighs this
The Na of embodiment preparation3V2(PO4)3Positive plate is made in/C, acetylene black, Kynoar, bears using metallic sodium piece as to electrode
Pole, using glass fibre as diaphragm, the NaClO of 1mol/L4(PC) it is electrolyte, 2032 type button electricity is assembled into glove box
Pond.
Assembled battery is carried out to 0.5C charge and discharge cycles test, voltage range 2.5-3.8V at room temperature.For the first time
Charging and discharging curve is as shown in Figure 1, the first discharge specific capacity of the material is 92.356mAhg-1, cycle performance curve such as Fig. 2 institute
Show, capacity retention ratio of the circulation after 100 weeks is 61.36%, high rate performance as shown in figure 3, high rate performance under 1C, 2C compared with
Difference need to be modified raising high rate performance to it.
Embodiment 2
The present embodiment prepares Na as follows3V1.8Mg0.2(PO4)3/ C5wt%Al2O3Positive electrode:
(1) sodium carbonate 0.795g, ammonium metavanadate are weighed according to the molar ratio of Na:P:V:C:Mg=3:3:1.8:2:0.2
1.053g, ammonium dihydrogen phosphate 1.7254g, citric acid 2.1014g, magnesium nitrate hexahydrate 0.256g；
(2) above-mentioned raw materials and zirconium oxide ball milling pearl are added in ball grinder according to the mass ratio of 1:3, inject a certain amount of ethyl alcohol
Homogeneous slurry is formed, wet ball grinding is carried out, grinds, be placed in vacuum tube furnace after drying, be warming up to 750 under atmosphere of inert gases
~900 DEG C, 12~16 hours are kept the temperature, is ground after being cooled to room temperature, obtains carbon-coated Na3V1.8Mg0.2(PO4)3/C；
(3) 5wt%Al is pressed2O3Covering amount weigh 0.1716gAl (OH)3, with carbon-coated phosphorus obtained above
Na3V1.8Mg0.2(PO4)3/ C carries out wet ball grinding, grinds, is placed in vacuum tube furnace after drying, is heated up under atmosphere of inert gases
To 300 DEG C, 3 hours are kept the temperature, is ground after being cooled to room temperature, obtains the Na that aluminium oxide and carbon coat altogether3V1.8Mg0.2(PO4)3/C·
5wt%Al2O3。
For gained sample as sodium-ion battery positive material, electrochemical property test is as follows: 7:2:1 in mass ratio weighs this
The Na of embodiment preparation3V1.8Mg0.2(PO4)3/ C5wt%Al2O3, acetylene black, positive plate is made in Kynoar, with metallic sodium
Piece is as the cathode to electrode, using glass fibre as diaphragm, the NaClO of 1mol/L4(PC) it is electrolyte, is assembled in glove box
At 2032 type button cells.
Assembled battery is carried out to 0.5C charge and discharge cycles test, voltage range 2.5-3.8V at room temperature.The material
The first discharge specific capacity of material is 97.35mAhg-1, capacity retention ratio of the circulation after 100 weeks is 83.18%.
Embodiment 3
The present embodiment prepares Na as follows3V1.7Mg0.3(PO4)3/ C15wt%Al2O3Positive electrode:
(1) sodium carbonate 0.795g, ammonium metavanadate are weighed according to the molar ratio of Na:P:V:C:Mg=3:3:1.7:2:0.3
0.9943g, ammonium dihydrogen phosphate 1.7254g, citric acid 2.1014g, magnesium nitrate hexahydrate 0.384g；
(2) above-mentioned raw materials and aluminium oxide ball milling pearl are added in ball grinder according to the mass ratio of 1:3, inject a certain amount of acetone
Homogeneous slurry is formed, wet ball grinding is carried out, grinds, be placed in vacuum tube furnace after drying, be warming up to 750 under atmosphere of inert gases
~900 DEG C, 12~16 hours are kept the temperature, is ground after being cooled to room temperature, obtains carbon-coated Na3V1.7Mg0.3(PO4)3/C；
(3) 15wt%Al is pressed2O3Covering amount weigh 0.5184gAl (OH)3, with carbon-coated phosphorus obtained above
Na3V1.7Mg0.3(PO4)3/ C carries out wet ball grinding, grinds, is placed in vacuum tube furnace after drying, is heated up under atmosphere of inert gases
To 300 DEG C, 3 hours are kept the temperature, is ground after being cooled to room temperature, obtains the Na that aluminium oxide and carbon coat altogether3V1.7Mg0.3(PO4)3/C·
15wt%Al2O3。
For gained sample as sodium-ion battery positive material, electrochemical property test is as follows: 7:2:1 in mass ratio weighs this
The Na of embodiment preparation3V1.7Mg0.3(PO4)3/ C15wt%Al2O3, acetylene black, positive plate is made in Kynoar, with metal
Sodium piece is as the cathode to electrode, using glass fibre as diaphragm, the NaClO of 1mol/L4It (PC) is electrolyte, the group in glove box
Dress up 2032 type button cells.
Assembled battery is carried out to 0.5C charge and discharge cycles test, voltage range 2.5-3.8V at room temperature.The material
The first discharge specific capacity of material is 93.77mAhg-1, capacity retention ratio of the circulation after 100 weeks is 80.49%.
Embodiment described above is only that preferred embodiments of the present invention will be described, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, those of ordinary skill in the art are to technical side of the invention
The various changes and improvements that case is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (9)
1. the sodium-ion battery positive material vanadium phosphate sodium that a kind of oxide and carbon coat cation doping altogether, it is characterised in that:
The positive electrode is by Na3V2-xMx(PO4)3/C·mAl2O3It indicates, including ontology Na3V2-xMx(PO4)3With surface coating layer Al2O3
And carbon, wherein M is at least one of Fe, Co, Mg, Zn, Na, 0 < x < 0.5,0 < m≤15%.
2. the sodium-ion battery positive material vanadium phosphate sodium that oxide described in a kind of claim 1 and carbon coat cation doping altogether
Preparation method, which comprises the steps of:
(1) according to Na:V:M:PO4: C=3:(2-x): the molar ratio of x:3:2 weighs sodium source, vanadium source, the source M, phosphorus source, carbon source；
(2) above-mentioned raw materials and ball milling pearl are added in ball grinder according to the mass ratio of 1:3, are injected a certain amount of volatile organic molten
Dosage form carries out wet ball grinding, grinds, be placed in vacuum tube furnace after drying, is warming up under atmosphere of inert gases at homogeneous slurry
750~900 DEG C, 12~16 hours are kept the temperature, is ground after being cooled to room temperature, obtains carbon-coated Na3V2-xMx(PO4)3/C；
(3) Al is pressed2O3Covering amount weigh Al (OH)3, wet ball grinding is carried out with carbon-coated vanadium phosphate sodium obtained above, is dried
It grinds, is placed in vacuum tube furnace after dry, 300 DEG C are warming up under atmosphere of inert gases, keep the temperature 3 hours, ground after being cooled to room temperature
Mill obtains the Na that aluminium oxide and carbon coat altogether3V2-xMx(PO4)3/C·mAl2O3。
3. the sodium-ion battery positive material vanadium phosphate that oxide according to claim 2 and carbon coat cation doping altogether
The preparation method of sodium, it is characterised in that: step (1) carbon source is at least one of glucose, citric acid, oxalic acid.
4. the sodium-ion battery positive material vanadium phosphate that oxide according to claim 2 and carbon coat cation doping altogether
The preparation method of sodium, it is characterised in that: step (1) sodium source is at least one of sodium dihydrogen phosphate, disodium hydrogen phosphate.
5. the sodium-ion battery positive material vanadium phosphate that oxide according to claim 2 and carbon coat cation doping altogether
The preparation method of sodium, it is characterised in that: step (1) the vanadium source is V2O5、NH4VO3At least one of.
6. the sodium-ion battery positive material vanadium phosphate that oxide according to claim 2 and carbon coat cation doping altogether
The preparation method of sodium, it is characterised in that: step (1) phosphorus source is at least one of ammonium dihydrogen phosphate, ammonium phosphate.
7. the sodium-ion battery positive material vanadium phosphate that oxide according to claim 2 and carbon coat cation doping altogether
The preparation method of sodium, it is characterised in that: step (1) source M is at least one of sulfate, nitrate, acetate of M.
8. the sodium-ion battery positive material vanadium phosphate that oxide according to claim 2 and carbon coat cation doping altogether
The preparation method of sodium, it is characterised in that: step (2) the ball milling pearl is agate bead, zirconium oxide ball milling pearl or aluminium oxide ball milling pearl.
9. the sodium-ion battery positive material vanadium phosphate that oxide according to claim 2 and carbon coat cation doping altogether
The preparation method of sodium, it is characterised in that: step (2) the volatile organic solvent is acetone or alcohol.
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